Metal-Organic Framework Composites: Volume 1 ZIF-8 Based Materials for Pharmaceutical Waste 9783110792607, 9783110792539

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Metal-Organic Framework Composites

Also of interest Metal-Organic Framework Composites. Volume : ZIF- Based Materials for Water Decontamination Ahmad, Pervaiz, Younas, Luque, Alsaiari, Harraz (Eds.),  ISBN ----, e-ISBN (PDF) ----

Nanomaterials for Water Remediation Mishra AK, Hussain, Mishra SB (Eds.),  ISBN ----, e-ISBN (PDF) ----

Inorganic and Organometallic Polymers Pal Singh Chauhan, Singh Chundawat,  ISBN ----, e-ISBN (PDF) ----

BioChar. Applications for Bioremediation of Contaminated Systems Thapar Kapoor, Shah (Eds.),  ISBN ----, e-ISBN (PDF) ----

Organometallic Chemistry. Fundamentals and Applications Haiduc, Silaghi-Dumitrescu,  ISBN ----, e-ISBN (PDF) ----

Metal-Organic Framework Composites Volume 1: ZIF-8 Based Materials for Pharmaceutical Waste Edited by Awais Ahmad, Muhammad Pervaiz, Zohaib Saeed, Rafael Luque, Mabkhoot Alsaiari and Farid A. Harraz

Editors Awais Ahmed Departamento de Química Orgánica Universidad de Córdoba Campus de Rabanales Carretera Nacional IV-A, Km. 396 14014 Córdoba Spain

Muhammad Pervaiz Department of Chemistry Government College University Lahore Punjab 54000 Islamic Republic of Pakistan

Zohaib Saeed Department of Chemistry Government College University Lahore Punjab 54000 Islamic Republic of Pakistan

Rafael Luque Departamento de Química Orgánica Universidad de Córdoba Campus de Rabanales Carretera Nacional IV-A, Km. 396 14014 Córdoba Spain

Mabkhoot Alsaiari Najran University (PCSED) Advanced materials and Nano Research Centre Najran 11001 Kingdom of Saudi Arabia

Farid A. Harraz Najran University (PCSED) Advanced materials and Nano Research Centre Najran 11001 Kingdom of Saudi Arabia

ISBN 978-3-11-079253-9 e-ISBN (PDF) 978-3-11-079260-7 e-ISBN (EPUB) 978-3-11-079262-1 Library of Congress Control Number: 2022945032 Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at http://dnb.dnb.de. © 2023 Walter de Gruyter GmbH, Berlin/Boston Cover image: akinbostanci/E+/Getty Images Typesetting: Integra Software Services Pvt. Ltd. Printing and binding: CPI books GmbH, Leck www.degruyter.com

Acknowledgments The authors/editors would like to acknowledge the support of the deputy for research and innovation-Ministry of Education, Kingdom of Saudi Arabia for this research through grant (NU/IFC/INT/01/003) under the institutional funding committee at Najran University, Kingdom of Saudi Arabia.

https://doi.org/10.1515/9783110792607-202

Contents Acknowledgments List of contributors

V IX

Muhammad Pervaiz, Talha Mumtaz, Arooj Ather, Zohaib Saeed, Umer Younas, Rana Rashad Mahmood Khan, Ikram Ahmad, Syed Majid Bukhari, Ayoub Rashid, Ahmad Adnan 1 Metal-organic framework introduction 1 Muhammad Pervaiz, Talha Mumtaz, Zohaib Saeed, Umer Younas, Ikram Ahmad, Shahzad Shareef, Ayoub Rashid, Syed Mohsin Ali Naqvi, Ahmad Adnan 2 Metal-organic framework properties 13 Naqeeb Ullah, Talha Mumtaz, Muhammad Pervaiz, Zohaib Saeed, Umer Younas, Ikram Ahmad, Asma Zaidi, Ayoub Rashid, Ahmad Adnan 3 Metal-organic framework for heterogeneous catalysis 21 Talha Mumtaz, Rizwan Sikanadar, Arooj Ather, Muhammad Shahzeb, Hazqail Umar Khan, Muhammad Pervaiz 4 Homogeneous catalysis using MOFs 29 Zoya Mazhar, Fareeha Andleeb, Rana Rashad Mahmood Khan, Muhammad Pervaiz, Ayoub Rashid Ch., Hafiz Muhammad Faizan Haider, Ahmad Adnan 5 MOF: an emerging material for biomedical applications 35 Ramsha Saleem, Rana Rashad Mahmood Khan, Bisma Khanam, Ayoub Rashid Ch., Muhammad Pervaiz, Zohaib Saeed, Ahmad Adnan 6 Pharmaceutical wastes: an overview 51 Hoorish Qamar, Rana Rashad Mahmood Khan, Ramsha Saleem, Muhammad Pervaiz, Nazir Ahmad, Hafiz Muhammad Faizan Haider, Ahmad Adnan 7 Recent advancement and development in MOF-based materials for the removal of pharmaceutical waste 73

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Contents

Aqmar-ur-rehman, Rana Rashad Mahmood Khan, Hoorish Qamar, Ramsha Saleem, Yussra Naeem, Ayoub Rashid Ch., Aqib Adnan, Muhammad Pervaiz 8 Future prospective of metal-organic frameworks for pharmaceutical wastes 95 Muhammad Yahya Tahir, Awais Ahmad, Rafael Luque 9 MOF – a promising material for energy applications Sadia Muzammil, Awais Ahmad, Rafael Luque 10 Polymer-coated MOF for pharmaceutical waste removal

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137

Maryam Adil, Awais Ahmad, Rafael Luque 11 MOF-derived nanocomposites for the removal of ciprofloxacin Index

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List of contributors Metal Organic Frameworks VOL 1 Chapter 1 Muhammad Pervaiz Department of Chemistry Government College University Lahore Lahore Pakistan [email protected] Talha Mumtaz Department of Chemistry Government College University Lahore Lahore Pakistan Arooj Ather Department of Chemistry Government College University Lahore Lahore Pakistan

Syed Majid Bukhari Department of Chemistry University of Sahiwal Sahiwal Pakistan Ayoub Rashid Department of Chemistry Government College University Lahore Lahore Pakistan Ahmad Adnan Department of Chemistry Government College University Lahore Lahore Pakistan

Zohaib Saeed Department of Chemistry Government College University Lahore Lahore Pakistan

Chapter 2 Muhammad Pervaiz Department of Chemistry Government College University Lahore Lahore Pakistan [email protected]

Umer Younas Department of Chemistry The University of Lahore Lahore Pakistan

Talha Mumtaz Department of Chemistry Government College University Lahore Lahore Pakistan

Rana Rashad Mahmood Khan Department of Chemistry Government College University Lahore Lahore Pakistan

Zohaib Saeed Department of Chemistry Government College University Lahore Lahore Pakistan

Ikram Ahmad Department of Chemistry University of Sahiwal Sahiwal Pakistan

Umer Younas Department of Chemistry The University of Lahore Lahore Pakistan

https://doi.org/10.1515/9783110792607-204

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List of contributors

Ikram Ahmad Department of Chemistry University of Sahiwal Sahiwal Pakistan

Zohaib Saeed Department of Chemistry Government College University Lahore Lahore Pakistan

Shahzad Shareef Department of Chemistry Government College University Lahore Lahore Pakistan

Umer Younas Department of Chemistry The University of Lahore Lahore Pakistan

Ayoub Rashid Department of Chemistry Government College University Lahore Lahore Pakistan

Ikram Ahmad Department of Chemistry COMSATS University Islamabad, Abbottabad Campus Khyber Pakhtunkhwa Pakistan

Syed Mohsin Ali Naqvi Department of Chemistry Government College University Lahore Lahore Pakistan Ahmad Adnan Department of Chemistry Government College University Lahore Lahore Pakistan Chapter 3 Naqeeb Ullah Department of Chemistry Government College University Lahore Lahore Pakistan Talha Mumtaz Department of Chemistry Government College University Lahore Lahore Pakistan Muhammad Pervaiz Department of Chemistry Government College University Lahore Lahore Pakistan [email protected]

Asma Zaidi Department of Chemistry COMSATS University Islamabad, Abbottabad Campus Khyber Pakhtunkhwa Pakistan Ayoub Rashid Department of Chemistry University of Sahiwal Sahiwal Pakistan Ahmad Adnan Department of Chemistry Government College University Lahore Lahore Pakistan Chapter 4 Talha Mumtaz Department of Chemistry Government College University Lahore Lahore Pakistan

List of contributors

Rizwan Sikanadar Department of Chemistry Government College University Lahore Lahore Pakistan

Muhammad Pervaiz Department of Chemistry Government College University Lahore Lahore Pakistan

Arooj Ather Department of Chemistry Government College University Lahore Lahore Pakistan

Ayoub Rashid Ch. Department of Chemistry Government College University Lahore Lahore Pakistan

Muhammad Shahzeb Department of Chemistry Government College University Lahore Lahore Pakistan

Hafiz Muhammad Faizan Haider Department of Chemistry Government College University Lahore Lahore Pakistan

Hazqail Umar Khan Department of Chemistry Government College University Lahore Lahore Pakistan

Ahmad Adnan Department of Chemistry Government College University Lahore Lahore Pakistan

Muhammad Pervaiz Department of Chemistry Government College University Lahore Lahore Pakistan [email protected]

Chapter 6 Ramsha Saleem Department of Chemistry Government College University Lahore Lahore Pakistan

Chapter 5 Zoya Mazhar Department of Chemistry Government College University Lahore Lahore Pakistan

Rana Rashad Mahmood Khan Department of Chemistry Government College University Lahore Lahore Pakistan [email protected]

Fareeha Andleeb University of Agriculture Faisalabad Punjab Pakistan

Bisma Khanam Department of Chemistry Government College University Lahore Lahore Pakistan

Rana Rashad Mahmood Khan Department of Chemistry Government College University Lahore Lahore Pakistan [email protected]

Ayoub Rashid Ch. Department of Chemistry Government College University Lahore Lahore Pakistan

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List of contributors

Muhammad Pervaiz Department of Chemistry Government College University Lahore Lahore Pakistan

Hafiz Muhammad Faizan Haider Department of Chemistry Government College University Lahore Lahore Pakistan

Zohaib Saeed Department of Chemistry Government College University Lahore Lahore Pakistan

Ahmad Adnan Department of Chemistry Government College University Lahore Lahore Pakistan

Ahmad Adnan Department of Chemistry Government College University Lahore Lahore Pakistan

Chapter 8 Aqmar-ur-Rehman Department of Chemistry Government College University Lahore Lahore Pakistan

Chapter 7 Hoorish Qamar Department of Chemistry Government College University Lahore Lahore Pakistan

Rana Rashad Mahmood khan Department of Chemistry Government College University Lahore Lahore Pakistan

Rana Rashad Mahmood Khan Department of Chemistry Government College University Lahore Lahore Pakistan

Hoorish Qamar Department of Chemistry Government College University Lahore Lahore Pakistan

Ramsha Saleem Department of Chemistry Government College University Lahore Lahore Pakistan

Ramsha Saleem Department of Chemistry Government College University Lahore Lahore Pakistan

Muhammad Pervaiz Department of Chemistry Government College University Lahore Lahore Pakistan

Yussra Naeem Department of Chemistry Government College University Lahore Lahore Pakistan

Nazir Ahmad Department of Chemistry Government College University Lahore Lahore Pakistan

Ayoub Rashid Ch. Department of Chemistry Government College University Lahore Lahore Pakistan

List of contributors

Aqib Adnan Department of Chemistry Government College University Lahore Lahore Pakistan Muhammad Pervaiz Department of Chemistry Government College University Lahore Lahore Pakistan Chapter 9 Muhammad Yahya Tahir Department of Environmental Science Government College University Faisalabad Punjab 38000 Pakistan Awais Ahmad Departamento de Química Orgánica Universidad de Córdoba Campus de Rabanales, Edificio Marie Curie (C-3), Ctra Nnal IV, Km 396 Córdoba Spain Rafael Luque Departamento de Química Orgánica Universidad de Córdoba Campus de Rabanales, Edificio Marie Curie (C-3), Ctra Nnal IV, Km 396 Córdoba Spain Chapter 10 Sadia Muzammil Department of Environmental Science Government College University Faisalabad Punjab 38000 Pakistan

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Awais Ahmad Departamento de Química Orgánica Universidad de Córdoba Campus de Rabanales, Edificio Marie Curie (C-3), Ctra Nnal IV, Km 396 Córdoba Spain Rafael Luque Departamento de Química Orgánica Universidad de Córdoba Campus de Rabanales, Edificio Marie Curie (C-3), Ctra Nnal IV, Km 396 Córdoba Spain Chapter 11 Maryam Adil Department of Environmental Science Government College University Faisalabad Punjab 38000 Pakistan Awais Ahmad Departamento de Química Orgánica Universidad de Córdoba Campus de Rabanales, Edificio Marie Curie (C-3), Ctra Nnal IV, Km 396 Córdoba Spain Rafael Luque Departamento de Química Orgánica Universidad de Córdoba Campus de Rabanales, Edificio Marie Curie (C-3), Ctra Nnal IV, Km 396 Córdoba Spain

Muhammad Pervaiz✶, Talha Mumtaz, Arooj Ather, Zohaib Saeed, Umer Younas, Rana Rashad Mahmood Khan, Ikram Ahmad, Syed Majid Bukhari, Ayoub Rashid, Ahmad Adnan

1 Metal-organic framework introduction Abstract: Metal-organic frameworks are the class which consists of metal ions (node) or clusters coordinated with the organic linker to form one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) structures. They are the subcategory of coordination polymers. The organic ligands are referred as “struts” or “linkers.” They are also known as porous coordination polymers because they are porous in nature. They are made up of organic linkers (mostly polydentate) and metal-containing node (also known as secondary building units).

1.1 Introduction Metal-organic frameworks (MOFs) are a spacious class of crystalline materials which consist of a special feature to absorb fluid (up to 90% free volume) and extensive internal surface areas, expanding beyond the limit of 6,000 m2/g [1, 2]. The properties, such as porosity and large surface area for the geometry and component of both organic molecules and inorganic molecules, which have high degree of variability, make MOFs apt for the applications in energy cleaning and storage of gases, for example, H2 and CH4, which consist of huge volume for adsorbents to satisfy the several needs of separation. MOFs also have applications in membranes, catalysis, thin-film materials, and in diagnostic instrumentations that are continuously gaining importance. On a basic level, MOFs symbolize the vision of chemical structures and the strength of combining organic chemistry and inorganic chemistry [3]. In present century, probability to diverge the porous shape, configuration and synthesis of element (Al:Si and isomorphic replacement of transition-metal in the tetrahedral site) has deliver Zeolite, the derivatives of Zeolite are the most suitable material used in different fields such as in separation, catalysis, and gas adsorption,

✶

Corresponding author: Muhammad Pervaiz, Department of Chemistry, Government College University, Lahore, Pakistan, e-mail: [email protected] Talha Mumtaz, Arooj Ather, Zohaib Saeed, Rana Rashad Mahmood Khan, Ayoub Rashid, Ahmad Adnan, Department of Chemistry, Government College University, Lahore, Pakistan Umer Younas, Department of Chemistry, The University of Lahore, Lahore, Pakistan Department of Chemistry, COMSATS University Islamabad, Abbottabad Campus, Pakistan Ikram Ahmad, Syed Majid Bukhari, Department of Chemistry, University of Sahiwal, Sahiwal, Pakistan

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Figure 1.1: Illustration showing metal-organic framework.

photo-catalysis and in shape of material for the quantum characteristics of condensed phases. These applications have been connected in both experimental and theoretical studies [4]. Although MOFs are admirable than zeolite in numerous respects, a particular property of MOFs is the considerable surface area. MOFs consist of secondary building elements which are connected by organic linkers. These secondary building elements are metal clusters or ions which are coordinated by oxygen atom or nitrogen atom and infrequently by fluorine and other nonmetals [5]. MOFs are different from zeolite in multiple aspects. The major difference of the MOFs has extensive dissimilarity and variableness of their shape in fusion with minor topological limitations on the establishment of porous 3D frameworks [6]. A remarkable number of the latest MOF structure manufactured every year to verify their flexibility and increase the interest in their possible applications. Zeolite are synthesized by tetrahedral molecule and divergence in their topology which are based on fixed number of structure of secondary elements; however, inorganic secondary building elements of MOFs can be either a distinct metal atom or at least complex cluster and 1D, 2D, or 3D expanded inorganic substructures. MOFs are identified by high stability and significant pore volume (greater than 50% of total volume). In different circumstances, the possibility of the initial building elements makes it feasible to diverge some criterion, for example, the size of pore (greater than 98` A pore diameter), density (greater than 0.126 g/cm3), and also the particular surface area (greater than 1,000–10,000 m2/g), which gives latest technique to manufacture materials with customized physico-chemical properties [7].

1.2 Structural features The components of MOFs can be differentiated on the basis of the metal ion (secondary building unit (SBU)) and organic molecules which are linked with the former to give porous shape. The elements of these structures give a huge number of

1 Metal-organic framework introduction

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MOF. Particularly, more than 100 forms of geometries of SBU can be retained by Cambridge Crystallographic Data Center. In every structure, central metal has been substituted. MOF-5 is the first synthesized MOF, which consists of ZnO4 (tetrahedral). When carbon chain elongates, it becomes possible to make the material of same structures which have symmetry but different pore size [8]. Different MOFs

Secondary building unit

BDC linker Octahedron (CN = 6) (Zn)

MOF-5 BDC linker MIL-101

Trigonal Prism (CN = 6) (Cr) BDC linker Cuboctahedron (CN = 12) (Zr)

UiO-66

Figure 1.2: Different types of MOFs depending on different secondary building units.

1.3 Terephthalic structure of MOFs Tranche-montagne proposed that coordination number of SBU merges through the various Linkers to form a frame work structure. There are two possible conditions in substitution and selection of metal ion, either retained symmetrical structure when the carbon chain elongate or symmetry can be changed due to change in the arrangement of functional groups. MOFs can be distinguished by pore size, symmetry, characteristics, and structure. The length of carbon-chain linker helps to determine the size of pores and also determines the number of the benzene rings present in it; addition of functional group and various substituents are the basic reasons for the special property of pores in the MOFs [9].

1.4 Symmetry with elongation in chain length The variation in the properties of MOF can be carried out by the proper selection of the metal node and bridging ligand. This property of the material increases the absorbing ability [10].

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Figure 1.3: 3D framework of UiO-66 MOF.

1.5 History of MOFs Before 1990s, zeolites were the well-known crystalline absorptive materials [11]. But in terms of flexibility and porosity, they did not demonstrate them ideal for the absolute eradication of organic pollutants from aqueous solutions. After these limitations, in 1995, Omar M. Yaghi invented and introduced a novel category of composite materials which presents good structural characteristics and benefit of regeneration capacities [12]. In 2006, Liu introduced several expressions [13]. In 2013, Ghasemzadeh presented absorbent-coordinated system [14]. In 2008, Bureekaew described the nanoporous coordinated polymers [15], and in 2012, Liu introduced a series of MOFs which consists similar network topology (isoreticular MOFs); all these were designated to these materials because during the period of their discovery, there was no verified nomenclature [13]. At present, more than 70,000 MOFs have been formulated by the extensive studies on these hybrid materials. Analyzers have mostly focused on few of them including MOF-5, MOF-74, porous coordination network (PCN)-222, MIL-53 (Matérial Institut Lavoisier) [16], UiO-66 (UiO stands for University of Oslo) [17], MILs PCN [18], and ZIFs (zeolitic imidazolate frameworks) because of their validness for several drain water remediation processes. They also have diverse metal nodes which contain various metal compounds, for example, Zn(II), Cu(II), Al(III), Fe (III), or Zr(IV). During 2015–2017, Z. Wang, Yang, D. Wang, and Liu concluded that a collection of metal-based microscale materials can be prepared with MOFs as basic materials including MIL-100(Fe), NH2-MIL-101-AL, Cu-BTC-MOF, MOF-74(Zn), and MOF-235(Fe). From 2013 to 2021, different scientists, Zhang, Lin, Kumar, Cao, and Daradmare,

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investigated these entracing properties to expand the applications of MOFs in a variety of processes, such as gas storage, separation, sensing, catalysis, and medicine, therefore moderately fusing the research space between engineering and environmental management network. Finally, from last two decades, MOFs have been the center of attention, and in 2020 they were widely observed for the elimination of organic contaminants from the aqueous solution [19].

1.6 Chemistry of MOFs MOFs are made up of organic and inorganic units. The organic units or linkers contain carboxylates, or anions, for example, sulfonate, phosphonate, and mixture of heterocyclic molecules. The inorganic units consist of the metal ions are known as SBUs. Their configuration is resolute with the coordination number, coordination figure, and the nature of functional groups. Various SBU configurations by individual number of points of expansion, for example, octahedron, trigonal prism, square paddle wheel, and triangle have been observed in the structure of MOFs. In precept, the di-topic, tri-topic, tetra-topic, or multi-topic bridging linkers react with metal node with a great extent to empty or labile site [20]. Metal ligand

Metal node

Figure 1.4: Illustration showing the components of MOFs, that is, metal cluster and organic linker molecules.

1.7 Structure of metal-organic framework The compulsive and important development in the area is to merge MOFs with the working order of nanoparticles, yielding the new nanocomposite substance with unique characteristics, and their performance. The nano‐MOFs are superior to traditional nanomedicines owing to their fundamentals, chemical diversity, biodegradability, and high space. The important characteristics depend on the

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particle configuration, magnitude, and the surface structure. These can be attained as crystalline or as amorphous substance. The flexibility of framework depends upon the softness of porous crystals, for example, pressure, temperature, and interconnection of light may be appear by the MOFs, also in the nonexistence of nonparticipating desorption and adsorption [21]. The final geometry of MOF is carried out by both Secondary Building Unit (SBU) linker and organic ligand connector. The variety of MOFs can be prepared by the organic linkers and metal-containing units that can be custom-fit for different applications as ligands have been mentioned in table 1.1 and 1.2. Large spaces in the MOFs may result in the development of formation of the mutually penetrate structures. Consequently, it is very essential to inhibit them by selecting the organic linkers carefully. By sensible selecting the metal nodes and the organic ligands, also by modifying the synthesizing circumstances, the size of pore is recognized to be tuned, and formal arrangement can be ordered. The characteristic to absorb fluids allows the applications in the separation of gas molecules, catalysis, the microelectronics, optics, and also have applications in the drug delivery, sensing, bioreactors, and. MOFs are capable of accommodating small molecules because their pores have openings’ size up to 2 nm. That is why the opening pores hardly allow large molecules like proteins and the enzymes. Different attempts are occupied to decrease the size of crystal to nanometer scale and to increase the size of pores 2–50 nm (mesopore regime). The large opening pores have benefits of the surface alteration with a large number of working abilities, without removing the porous ability, also recognized the encapsulation of the macromolecule. The formulation of the MOFs includes the conditions of reaction and different methods, for example, diffusion, solvothermal, ionothermal, microwave techniques, ultrasound conduction, directed synthesis of template, and others [22]. Table 1.1: Organic ligands used to prepare the metal-organic framework. 

Hbdc: terephthalic acid



Hbtc: ,,-benzenetricarboxylic acid



HAbck: -aminoterephathalic acid



Pyridine--carboxylic acid



Hatc:adamantanetetracarboxylic acid



Hbpdc: biphenyl--ʹ-dicarboxylic acid



Hdhbck: ,-dihydroxy-,-benzenedicarboxylic acid



2 ndc: 2,6-naphthalenedicarboxylic acid



Hatb: ,,,-adamantanettrabenoic acid



Htapb: ,′,″-(triazzine-,,-triyttris(benzene-,-diyl)) tribenzoic acid

1 Metal-organic framework introduction

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Table 1.2: Ligands consist of nitrogen, sulfur, phosphorous, and the heterocycles used for the preparation of MOFs [23]. 

,ʹbipyridine



,,-Tris(-pyridyl)-,,-triazine



Hexamethylene tetra amine



,,-Benzenetriphosphoric acid



,-Naphthalenedisulfonic acid



,-Bis(imidazole--ylmethyl)benzene (bix)



Tetrakis (-cyanaphenyl)methane

Metal ions (vacant sits)

1-D polymer

Bridging poly-dentate ligand

2-D polymer

3-D polymer

Figure 1.5: MOFs with the bridging linker and different metal nodes [24].

1.8 Synthesis The summary of the preparation of MOFs though different approaches is shown in the figure given below. Most of the MOFs take place through liquid-phase synthesis. In liquid-phase synthesis, separate ligand solutions and metal salt are mixed together in a reaction vial. The solvent used for the liquid-phase synthesis reactions can be selected on various aspects, that is, redox potential, reactivity, stability constant, solubility, and so on. As to determine the thermodynamic and energy of activation for specific reaction, selection of solvent plays an important role. On the other hand, researchers also used solid-phase technique for the synthesis of MOFs. It is because solid-phase synthesis is more rapid and easier technique. Beside this, solid-phase technique has some drawbacks, such as in obtaining single crystals

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and in determining their structural features solid-phase synthesis technique always faces difficulties, which is quite easy in liquid phase, that is solution form [25]. Electrochemical – 1% used method Energy: Electrical energy Temperature: 270 – 300 K Time: 10 – 40 mins Mechanochemical Method – 4% used method Energy: Mechanical energy Temperature: 300 K Time: 30 mins – 2 hours Slow evaporation – 3% used method Energy: No external energy Temperature: 298 K Time: 7 days – 7 month

Solvothermal – 70% used method Energy: Thermal energy Temperature: 350 – 450 K Time: 50 – 96 hours

Metal Salt

+ Ligand

+ Solvent

Microwave – 10% used method Energy: Microwave radiations Temperature: 300 – 373 K Time: 4 mins – 4 hours Sonochemical – 5% used method Energy: Ultrasonic radiations Temperature: 273 – 313 K Time: 30 – 180 mins

Figure 1.6: Illustration showing synthetic conditions for different MOF’s preparation and percentage MOF’s preparation through various synthesizing route.

The regular method of crystallization used for the preparation of MOFs from the last few decades is the slow evaporation process. However, generally, the synthesis of MOFs takes place through various methods such as solvothermal methods, electrochemical synthesis, microwave synthesis, sonochemical synthesis, and mechanochemical synthesis. The slow evaporation process is conventional process to synthesize MOFs that mostly do not require any energy supply from external [26].

1.9 Metal biomolecule frameworks Biomolecules naturally exist in the large amount. They are usually hard, cost‐effective, and ductile with many coordination areas, showing geometrically different, biologically capable of existing together MOFs. MOFs can also be synthesized by the nontoxic endogenous cations (e.g., calcium, magnesium, iron, and zinc) and the ligands consisting of naturally existing biomolecules and their derivatives. These bio-MOFs are usually biocompatible and convenient for the medical applications. The mixture of nontoxic cations with naturally occurring ligands are also related with various healing effects such as anticarcinogenic task, anti‐inflammatory, antimicrobial, and antiallergic. Bio-MOFs are constructed and designed on the basis of criteria of specific composition which is controlled by discreetly selecting the metal nodes and organic ligands as a basic element, which are nontoxic, biologically and environmentally well suited. Biomolecules, for example, amino acids, peptides linkage, carbohydrates, proteins,

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1 Metal-organic framework introduction

Figure 1.7: Bio-metal-organic framework (bio-MOF) [28].

Applications

Bio-MOFs

Ligand

Metal

Sorption of the Ar and CH

[Cu(trans- fumaric Acid)]

Fumaric-Acid

Copper

Desorption of HO

[Ni(succinic acid)(OH)(HO)]

Succinic Acid

Ni

Sorption of different kinds of guests

[Mn(HCOO)]·(CHOH)·HO

Formic-Acid

Mn

Sorption of CO

[Ni(L- Asp)(bipy)]HO

L- Asp and bipy, ,- bis (-pyridyl)ethane

Ni

Sorption of H

Co(L- Asp)(bipy)]·HO

L- Asp and ,’ - bipy

Co

Selective sorption of CO

Co(Ade)(COCH)·DMF·HO

Ade

Cobalt

Figure 1.8: Some important bio-MOFs and their applications [28].

nucleobases, and many other naturally occurring products, for example, cyclodextrins, porphines, and carboxylic acids, working as the growing building blocks for establishment and composition of MOFs with impressive properties and applications which cannot be attain by using conventional organic linkers [27].

1.10 Conclusion MOFs are made up of metal clusters and organic linker molecules that connect to form crystalline structures in 1D, 2D, or 3D. MOFs have a somewhat recent history. Zeolites were only identified as absorbent materials in 1990. The secondary building components determine the final shape of MOFs. MOFs are prepared using a variety of processes, including sonochemical, solvochemical, mechanochemical, electrochemical, microwave, and slow evaporation, among others. MOFs also serve a significant function in biology, such as sorption, desorption, and catalysis.

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[6] [7] [8]

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Zhou, H.C., J.R. Long, and O.M. Yaghi, Introduction to metal–organic frameworks. Chemical Reviews, 2012. 112(2): p. 673–674. Sharmin, E. and F. Zafar, Introductory chapter: Metal organic frameworks (MOFs). In Metalorganic frameworks. 2016: IntechOpen. Cohen, S.M., Modifying MOFs: New chemistry, new materials. Chemical Science, 2010. 1(1): p. 32–36. Tedds, S., A. Walton, D.P. Broom, and D. Book, Characterisation of porous hydrogen storage materials: Carbons, zeolites, MOFs and PIMs. Faraday Discussions, 2011. 151: p. 75–94. Bae, Y.S., A.O. Yazaydın, and R.Q. Snurr, Evaluation of the BET method for determining surface areas of MOFs and zeolites that contain ultra-micropores. Langmuir, 2010. 26(8): p. 5475–5483. Rangnekar, N., N. Mittal, B. Elyassi, J. Caro, and M. Tsapatsis, Zeolite membranes – A review and comparison with MOFs. Chemical Society Reviews, 2015. 44(20): p. 7128–7154. Zornoza, B., B. Seoane, J.M. Zamaro, C. Téllez, and J. Coronas, Combination of MOFs and zeolites for mixed‐matrix membranes. ChemPhysChem, 2011. 12(15): p. 2781–2785. Allen, F.H., S.D.B.M. Bellard, M.D. Brice, B.A. Cartwright, A. Doubleday, H. Higgs, . . . and D.G. Watson, The Cambridge Crystallographic Data Centre: Computer-based search, retrieval, analysis and display of information. Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry, 1979. 35(10): p. 2331–2339. Clausen, H.F., R.D. Poulsen, A.D. Bond, M.A.S. Chevallier, and B.B. Iversen, Solvothermal synthesis of new metal organic framework structures in the zinc–terephthalic acid–dimethyl formamide system. Journal of Solid State Chemistry, 2005. 178(11): p. 3342–3351. Hu, J.M., V.A. Blatov, B. Yu, K. Van Hecke, and G.H. Cui, An unprecedented “strongly” selfcatenated MOF containing inclined catenated honeycomb-like units. Dalton Transactions, 2016. 45(6): p. 2426–2429. Ma, Y., W. Tong, H. Zhou, and S.L. Suib, A review of zeolite-like porous materials. Microporous and Mesoporous Materials, 2000. 37(1–2): p. 243–252. Li, H., M. Eddaoudi, M. O’Keeffe, and O.M. Yaghi, Design and synthesis of an exceptionally stable and highly porous metal-organic framework. Nature, 1999. 402(6759): p. 276–279. Shekhah, O., J. Liu, R.A. Fischer, and C. Wöll, MOF thin films: Existing and future applications. Chemical Society Reviews, 2011. 40(2): p. 1081–1106. Ghasemzadeh, M.A., B. Mirhosseini‐Eshkevari, and M.H. Abdollahi‐Basir, MIL‐53 (Fe) Metal–Organic Frameworks (MOFs) as an efficient and reusable catalyst for the one‐pot four‐ component synthesis of pyrano [2, 3‐c]‐pyrazoles. Applied Organometallic Chemistry, 2019. 33(1): p. e4679. Bureekaew, S., S. Amirjalayer, M. Tafipolsky, C. Spickermann, T.K. Roy, and R. Schmid, MOF‐ FF – A flexible first‐principles derived force field for metal‐organic frameworks. Physica Status Solidi (B), 2013. 250(6): p. 1128–1141. Chen, J., X. Zhang, F. Bi, X. Zhang, Y. Yang, and Y. Wang, A facile synthesis for uniform tabletlike TiO2/C derived from Materials of Institut Lavoisier-125 (Ti)(MIL-125 (Ti)) and their enhanced visible light-driven photodegradation of tetracycline. Journal of Colloid and Interface Science, 2020. 571: p. 275–284. Molavi, H., M. Zamani, M. Aghajanzadeh, H. Kheiri Manjili, H. Danafar, and A. Shojaei, Evaluation of UiO‐66 metal organic framework as an effective sorbent for Curcumin’s overdose. Applied Organometallic Chemistry, 2018. 32(4): p. e4221.

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[18] Li, H., X. Cao, C. Zhang, Q. Yu, Z. Zhao, X. Niu, and Z. Li, Enhanced adsorptive removal of anionic and cationic dyes from single or mixed dye solutions using MOF PCN-222. RSC Advances, 2017. 7(27): p. 16273–16281. [19] Daradmare, S., M. Xia, J. Kim, and B.J. Park, Metal–organic frameworks/alginate composite beads as effective adsorbents for the removal of hexavalent chromium from aqueous solution. Chemosphere, 2021. 270: p. 129487. [20] Furukawa, H., K.E. Cordova, M. O’Keeffe, and O.M. Yaghi, The chemistry and applications of metal-organic frameworks. Science, 2013. 341(6149): p. 1230444. [21] Dey, C., T. Kundu, B.P. Biswal, A. Mallick, and R. Banerjee, Crystalline metal-organic frameworks (MOFs): Synthesis, structure and function. Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials, 2014. 70(1): p. 3–10. [22] Zhang, S., Q. Yang, X. Liu, X. Qu, Q. Wei, G. Xie, and S. Gao, High-energy metal–organic frameworks (HE-MOFs): Synthesis, structure and energetic performance. Coordination Chemistry Reviews, 2016. 307: p. 292–312. [23] Blanco, G., J.M. Quintela, and C. Peinador, Synthesis of new heteroaromatic nitrogen ligands: Pyrimido‐[4 ″, 5 ″: 4′, 5′]‐thieno [3′, 2′: 4, 5] thieno [3, 2‐d] pyrimidines and 1, 2, 3‐triazine [4 ″, 5 ″: 4′, 5′] thieno [3′, 2′: 4, 5] thieno [3, 2‐d]‐1, 2, 3‐triazines. Journal of Heterocyclic Chemistry, 2006. 43(4): p. 1051–1056. [24] Cha, G.Y., H. Chun, D.Y. Hong, J. Kim, K.H. Cho, U.H. Lee, and Y.K. Hwang, Unique design of superior metal-organic framework for removal of toxic chemicals in humid environment via direct functionalization of the metal nodes. Journal of Hazardous Materials, 2020. 398: p. 122857. [25] Stock, N. and S. Biswas, Synthesis of metal-organic frameworks (MOFs): Routes to various MOF topologies, morphologies, and composites. Chemical Reviews, 2012. 112(2): p. 933–969. [26] Han, Y., H. Yang, and X. Guo, Synthesis methods and crystallization of MOFs. Synthesis Methods and Crystallization, 2020: p. 524–218. [27] Li, T., D.L. Chen, J.E. Sullivan, M.T. Kozlowski, J.K. Johnson, and N.L. Rosi, Systematic modulation and enhancement of CO 2: N 2 selectivity and water stability in an isoreticular series of bio-MOF-11 analogues. Chemical Science, 2013. 4(4): p. 1746–1755. [28] Cai, H., Y.L. Huang, and D. Li, Biological metal–organic frameworks: Structures, host–guest chemistry and bio-applications. Coordination Chemistry Reviews, 2019. 378: p. 207–221.

Muhammad Pervaiz✶, Talha Mumtaz, Zohaib Saeed, Umer Younas, Ikram Ahmad, Shahzad Shareef, Ayoub Rashid, Syed Mohsin Ali Naqvi, Ahmad Adnan

2 Metal-organic framework properties Abstract: Metal-organic frameworks (MOFs) are crystalline materials with metal ions which are connected to organic ligands. MOF’s belongs to a large family of nanoporous materials. These are the organic crystalline compounds which are formed by a group of atoms of metal which are connected together by an organic linker in 3D structure. MOFs can generate luminescence in variety of ways which may include MLCT, LMCT, LLCT, MMCT, and so in. Here, M means metal, L means ligand, and CT means charge transfer. There comes new class of materials by connecting the crystalline structures of MOFs and produce an order in which they conduct electricity and produce any materials such as electrical sensors and many more. To produce MOFs which are good conductors of electricity, many strategies are formed. MOFs are well known materials because of their porosity and surface area. Essential and appropriate materials which link the MOFs with each other and the nodes of metal are used to tune the arrangements and pore size of the MOFs. Moreover, scalability and process ability are rosy properties of MOFs.

2.1 Luminescent properties of MOFs MOFs belong to a large family of nanoporous materials. These are the organic crystalline compounds which are formed by a group of atoms of metal which are connected together by an organic linker in 3D structure [1]. They have diverse properties and their structure is uniform and due to this they have attracted a lot of interest of the researchers. Investigation of many applications related to MOFs have been done. The first about MOFs was reported in 2002. There is a new type of property related to the MOFs which is its luminescent property; here luminescence is produced by both organic and inorganic materials used in the construction of MOFs [2]. So, MOFs can generate luminescence in variety of ways which may include MLCT, LMCT, LLCT, MMCT, and so on. Here, M means metal, L means ligand and CT means charge transfer.

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Corresponding author: Muhammad Pervaiz, Department of Chemistry, Government College University, Lahore, Pakistan, e-mail: [email protected] Talha Mumtaz, Zohaib Saeed, Shahzad Shareef, Ayoub Rashid, Syed Mohsin Ali Naqvi, Ahmad Adnan, Department of Chemistry, Government College University, Lahore, Pakistan Umer Younas, Department of Chemistry, The University of Lahore, Lahore, Pakistan Ikram Ahmad, Department of Chemistry, University of Sahiwal, Sahiwal, Pakistan

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Also some of the atoms which are present in MOFs structure are used in producing luminescence in MOFs. They have importance in industry. They can generate many different types of sensor and luminescent materials from MOFs. Researchers have great interest in reading about the properties of MOF-5. They have a high storage for hydrogen and they can produce luminescent and these are the two most important properties of MOF-5. MOF-5 is most important structure among all the structures of MOFs because it has quantum dots (QD), has a central atom in the form of Zn4O tetrahedral nodes which help in getting luminescence property among MOFs [3]. Many researchers have investigated about the electronic transitions by emission spectra produced by ZnO QDs. The researchers investigated that due to the transfer of charge in ZnO, the luminescent is produced [4]. The charge transfer is in the form of: −

O2 Zn + ! O − Zn + This charge transfer occurs in every Zn4O13 tetrahedral atom which can produce luminescent property in MOF-5. At 525 nm, the photoluminescence property of MOF-5 was observed and this was due to the LMCT property of the MOFs which was carried when 1,4-benzenedicarboxylate (BDC2−) was connected to the group of Zn4O13. Many researchers also investigated about the nanoparticle of MOF luminescent property [5]. There is a similarity between the MOF-5 and ZnO in the green emission by transition. So, the emission that was studied in MOF-5 actually originated first from ZnO QDs. Feng et al. investigated about the luminescent properties of impure ZnO and MOF-5 and pure MOF-5 [6]. At 365 nm, the particles of impure ZnO and MOF-5 excite and emit a luminescence at 535 nm but at 345 nm, the particles of pure MOF-5 excite and emit a luminescence at 397 nm and also there was emission of H2BDC ligand at 382 nm.

2.2 Different conductivity properties of MOFs There is a similarity between the MOF-5 and ZnO in the green emission by transition. So, the emission that was studied in MOF-5 actually originated first from ZnO QDs. Feng et al, investigated about the luminescent properties of impure ZnO and MOF-5 and pure MOF-5 as also illustrated in fig 2.1 [6]. At 365 nm, the particles of impure ZnO and MOF-5 excite and emit a luminescence at 535 nm but at 345 nm, the particles of pure MOF-5 excite and emit a luminescence at 397 nm and also there was emission of H2BDC ligand at 382 nm. There comes new class of materials by connecting the crystalline structures of MOFs and produce an order in which they conduct electricity and produce any materials such as electrical sensors and many more [7]. To produce MOFs which are good conductors of electricity, many strategies are formed as depicted in fig 2.2. Now-a-days, a new approach of electrical conductor MOF have been produced which is ptype semiconducting MOF in which redox mechanism is used in producing electricity.

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15

19000

Intensity

18000

17000

16000

15000

12000 400

500

600

700

800

900

1000

1100

Wavelength (nm) Figure 2.1: Luminescent properties of Zr(IV) MOF.

Gandara et al, now-a-days proposed a new strategy in which he produced Ohmic conductivity by using metal triazolate MOFs. In this strategy, the mechanism that how conductivity is produced in this strategy is not defined but it may be due to the presence of Fe(II) in the structure [8]. In an alternating approach, to produce an electrical transport property in MOFs, the pores of MOFs are used. Here, it can be described that there are some molecules which can conduct electricity in impure MOFs and can form a mechanism of carrier mobility. For testing this strategy, there are some molecules which are used to generate conductivity of electricity in MOFs such as Cu3 (BTC)2. Here, the redox-active molecule such as TCNQ is used to exchange the coordination positions of Cu(II) with them, when they are soluble in water [9]. Moreover, the EPR spectra are used to describe that how many additional spins of copper is exchanged when it connects with carboxylate units. This strategy is further defined by using a thin-film device which is composed of Cu3(BTC)2 which was produced on electrodes which was used to control the flow of Ohmic current. This was described in six patterns. Silicon wafers were used which were covered by SiO2 and it was then again platted on Pt pads which were 100 nm thick and have a gap of 100 µm, 150 µm, and 200 µm. After this, Cu3 (BTC)2 were grown on the wafers. The results were shown by XDR reading and images were formed by SEM technique [10]. So, these results give the reading about the Ohmic current and electrical conductivity produced by the MOFs.

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5

Cu3(BTC)2 Cu3(BTC)2×H2O 10

15

20

25

30

2θ (degrees) Figure 2.2: Readings of MOF about Ohmic current and electrical conductivity.

2.3 Porosity and surface area MOFs are well-known materials because of their porosity and surface area. Essential and appropriate materials which link the MOFs with each other and the nodes of metal are used to tune the arrangements and pore size of the MOFs. We can define the isoreticular MOFs as the materials which have same arrangement and use different organic linkers for performing different functions [11]. We can observe the structure and the chemical energy which can have impact in electrochemical processes of MOFs by controlling the porosity and chemical energy in the isoreticular MOFs. There are also some effects that develop on the molecular diffusion due to the distribution of the pores of MOFs which are in the form of micropores and mesopores which can develop strategic channels and pore space. Their higher surface area is used to control the catalytic processes in lithium–oxygen batteries; there is reduction of oxygen. These properties of porosity and surface area are not known before in inorganic solids and therefore very important for the applications in electrochemical processes [12].

2.4 Scalability and processability The emotional ubiquity of MOFs over the most recent 20 years makes it challenging to recollect that MOF is still an early field. To use these materials commercially by moving it from laboratory, processability and stability of MOFs are important areas of examination. On a large scale, there is a demonstration of MOFs synthesis in many companies [13]. These companies get advantage from different field of chemistry for the study of MOFs. These are in the form of:

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– – –

17

Flow chemistry Electrochemical chemistry Mechanochemical chemistry

2.4.1 Mechanochemical chemistry In the synthesis of MOFs by using mechanochemical methods, without using solvents or any heating process for a long period of time, we generally use physical mixing of different electrical nodes of MOFs with different linkers, which do not produce any waste and not very cost effective. By altering the component’s reagents, mechanochemical synthesis [14] is used to make different mixed-metal bulks of MOFs. We can use different low-cost metal products such as salts of metals, hydroxides, or carbonates which can produce MOFs at lower cost production.

2.4.2 Flow chemistry We can also produce MOFs by using microwave irradiation (MI) from which by using precursor solutions, we can produce MOFs. From other solvothermal methods, there is less energy required for microwave heating as it actually depends upon localized heating rather than heating the whole solution [15].

2.4.3 Electrochemical chemistry We can use electrochemical devices to produce MOFs from simple chemical components. Here, we get a special class of materials which is called as SURMOFs which is formed by the solution-phase layer-by-layer deposition, which control the thickness of film as well as molecular and structural properties of this class [16]. From electrochemical synthesis, we can grow the MOFs uniformly and also allow the deposition with accurate thickness of deposing layers. We can control the film thickness from vapor deposition which may include two classes of deposition such as atomic layer deposition and chemical vapor deposition, in which we can grow the MOFs on flat surfaces and also on fibers. Due these techniques or branches, there is vast electrochemical applications of MOFs [17].

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Important Physical and chemical properties

Porosity and high surface area

Charge conduction

Metal organic framework

Scalability and processability

Figure 2.3: Illustration showing metal-organic framework and some of their properties.

2.5 Conclusion The main significant factors of MOFs are described in this article: brightness, pore size, scalability, and processability. They are used in flow chemistry, electrochemical chemistry, and mechanochemical chemistry because of their features. MOFs with a high surface area are useful for managing the catalytic process in Li-based batteries, which are the energy and power source of the future.

References [1] [2] [3]

Cui, Y., et al., Luminescent functional metal–organic frameworks. 2012. 112(2): p. 1126–1162. Kitagawa, S.J.C.S.R., Metal–organic frameworks (MOFs). 2014. 43(16): p. 5415–5418. Liu, Y., et al., Strategies to fabricate metal–organic framework (MOF)-based luminescent sensing platforms. 2019. 7(35): p. 10743–10763. [4] Zhao, S.-N., et al., Luminescent lanthanide MOFs: A unique platform for chemical sensing. 2018. 11(4): p. 572. [5] Müller-Buschbaum, K., et al., MOF based luminescence tuning and chemical/physical sensing. 2015. 216: p. 171–199. [6] Allendorf, M.D., et al., Luminescent metal–organic frameworks. 2009. 38(5): p. 1330–1352. [7] Sun, L., et al., Is iron unique in promoting electrical conductivity in MOFs? 2017. 8(6): p. 4450–4457. [8] Li, P. and B.J.I.J.o.C. Wang, Recent development and application of conductive MOFs. 2018. 58(9–10): p. 1010–1018. [9] Bhardwaj, S.K., et al., An overview of different strategies to introduce conductivity in metal–organic frameworks and miscellaneous applications thereof. 2018. 6(31): p. 14992–15009. [10] Sun, L., et al., Measuring and reporting electrical conductivity in metal–organic frameworks: Cd2 (TTFTB) as a case study. 2016. 138(44): p. 14772–14782. [11] Chen, J., et al., Tunable surface area, porosity, and function in conjugated microporous polymers. 2019. 58(34): p. 11715–11719.

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[12] Furukawa, H., et al., Ultrahigh porosity in metal-organic frameworks. 2010. 329(5990): p. 424–428. [13] Julien, P.A., C. Mottillo, and T.J.G.C. Friščić, Metal–organic frameworks meet scalable and sustainable synthesis. 2017. 19(12): p. 2729–2747. [14] Tanaka, S., Mechanochemical synthesis of MOFs. In: Metal-organic frameworks for biomedical applications. 2020: Elsevier, p. 197–222. [15] Batten, M.P., et al., Continuous flow production of metal-organic frameworks. 2015. 8: p. 55–59. [16] Liu, L., et al., The applications of metal− organic frameworks in electrochemical sensors. 2018. 5(1): p. 6–19. [17] Zhu, B., et al., Conductive metal-organic frameworks for electrochemical energy conversion and storage. 2021. 446: p. 214119.

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3 Metal-organic framework for heterogeneous catalysis Abstract: The properties, synthesis, and future of metal-organic frameworks (MOFs) are discussed in this article. The network established by the MOF is extremely adaptable, making it extremely useful. MOFs are synthesized using a variety of techniques, including sonochemical, electrochemical, mechanochemical, electrochemical, and microwave-aided processes. Many food products and other commodities are now made employing MOFs as a heterocatalyst in processes. Furthermore, their eco-friendly qualities and green synthesis make them significant in the past, present, and future.

3.1 Introduction Catalytic processes are used to make more than 95% (by volume) of today’s chemical products. Metal-organic framework (MOF) is an excellent choice for solid catalysts in this regard [1]. In 1965, Tomic describes supramolecular structure, often known as MOF [2]. Working on MOF advances has grown quite popular and eyecatching in the recent two decades. When it comes to some organic molecules, MOFs are not the best catalysts to utilize (e.g., some aliphatic amines). MOFs, according to the International Union of Pure and Applied Chemistry [4], are coordination networks with an open framework that contains potential voids [5]. They are solid materials with the ability to form extended crystal structures. They are crystalline hybrid materials with a crystalline structure. Cross-linking of cluster nodes or metal ions (secondary building) and functional organic ligands (organic building blocks) forms a net-like structure in these coordination porous polymers [6].

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Corresponding author: Muhammad Pervaiz, Department of Chemistry Government College University Lahore, Pakistan, e-mail: [email protected] Naqeeb Ullah, Talha Mumtaz, Zohaib Saeed, Ahmad Adnan, Department of Chemistry, Government College University, Lahore, Pakistan Muhammad Pervaiz, Department of Chemistry, Government College University, Lahore, Pakistan; Umer Younas, Department of Chemistry, The University of Lahore, Lahore, Pakistan Ikram Ahmad, Asma Zaidi, Department of Chemistry, COMSATS University Islamabad, Abbottabad Campus, Pakistan Ayoub Rashid, Department of Chemistry, University of Sahiwal, Sahiwal, Pakistan

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coordinatively unsaturated metal sites basic linkers metal nanoparticles MOFs as solid catalysts large pore size lattice stability

Figure 3.1: MOF’s features as solid catalyst for production of fine chemicals [3].

Metal organic framework is an excellent choice for solid catalysts in this regard as shown in fig 3.1. On nodes, one or more metal ions, such as Al+3, Cr+3, Cu+2, Zn+2, or Zn+4, form a coordinative bond with an organic bridging ligand via a specific functional group, such as carboxylate or pyridyl as in fig 3.2. These structure are bonded through a coordination bond exists in 1D, 2D and in 3D networks as in fig 3.3. Biomedicine has seen the most modern applications, such as drug delivery [14] and biological imaging as in fig 3.4. There are numerous procedures that can be employed to introduce an active site. We switched to another method if one didn’t work. The sites can be made by (a) including salts of the catalytically active metal of interest into the MOF synthesis. (b) Incorporating the active catalyst (e.g., organo-catalysts or transition metal catalysts) into the organic linkers, e.g., by covalent modification of the linkers, and (c) loading MOFs with active species after synthesis, e.g., by post-synthetic modification (PSM), including solvent assisted ligand exchange (SALE) as explained in fig 3.5 and 3.6. MOFs have structural characteristics that make them desirable catalytic supports. They can have enormous pore diameters (0.3–3.8 nm) and large surface areas, similar to zeolites (500–6500 m2g−1). By carefully selecting organic ligands, these surface qualities can be altered in the desired direction. MOFs’ properties have led to their usage as heterogeneous catalysts in a number of processes as in fig 3.7. Hydrogenation reactions of CO2, crotonaldehyde, propene, ethane, benzene and propyne etc as in fig 3.8. These structure are bonded through a coordination bond exists in 1D, 2D, and 3D networks [8, 9]. A bi-dentate organic ligand is commonly coupled to a metal ion to create a skeleton in MOFs. Acid/basic groups and/or transition metals are two of the four methods for introducing catalytic active sites into frameworks [10].

Figure 3.2: Metals nodes (blue) and organic ligands (green) combine to synthesize MOFs [11].

3 Metal-organic framework for heterogeneous catalysis

3D

2D

23

1D

Figure 3.3: Schematic diagram of MOF’s framework showing different dimensions [6].

They have high structural possibilities or variations, different dimensionalities [12], high surface area, enhanced activity, selectivity in particular organic reactions, differences in activities, shape/size selectivity, high porosity [13], pore size tunability, high permeability to new molecules, high metal content, high tailorability, high mechanical stability, and high thermal stability due to their structural network combination mechanism (sometimes above 400 °C) [2]. The combination of these characteristics, as well as the varied chemical inorganic-organic composition, has drawn the attention of many researchers, resulting in numerous articles, patents, and reviews. MOFs can be constructed with structural and dynamic properties to bridge the gap between zeolites and surface metal–organic catalysts. MOFs have become increasingly popular as heterogeneous catalysts in the last two decades, and they have been hailed as a new green protocol that offers an environmentally beneficial alternative to catalysis. In MOF’s catalytic operation, complex catalytic problems such as chemoselectivity, region selectivity, and stereo-selectivity still exist. The characteristics of the MOF are still being investigated. MOFs’ catalysis adaptability is reflected in their design versatility [2]. That is why, during the last century, there have been incentives to replace homogeneous processes with efficient and environmentally friendly heterogeneous processes. Biomedicine has seen the most modern applications, such as drug delivery [14] and biological imaging [15]. Gas storage, catalysis, purification, sensing devices, and separation are all examples of applications.

Separation

Gas storage

Sensor

Drug storage

MOF

Purification

Catalyst

Figure 3.4: Potential applications of MOFs [11].

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3.2 Why MOFs are used in hetrocatalysis? The parameters are discussed as [7]: (i) Due to the structure’s adaptability and excellent tailoring capacity, enormous numbers of MOFs can be synthesized. (ii) There are numerous procedures that can be employed to introduce an active site. We switched to another method if one did not work. The sites can be made by (a) including salts of the catalytically active metal of interest into the MOF synthesis. (b) Incorporating the active catalyst (e.g., organo-catalysts or transition metal catalysts) into the organic linkers, for example, by covalent modification of the linkers, and (c) loading MOFs with active species after synthesis, for example, by post-synthetic modification, including solvent assisted ligand exchange. L

M

Cavity

MNPs Figure 3.5: Methods of inducing catalytic active sites into MOFs [16].

Metal ion or Cluster

Encapsulated catalyst

Functionalized linker Figure 3.6: Illustration showing the available active sites in the MOFs for catalysis processes [3].

(iii) MOFs have structural characteristics that make them desirable catalytic supports. They can have enormous pore diameters (0.3–3.8 nm) and large surface areas, similar to zeolites (500–6,500 m2/g). By carefully selecting organic ligands, these surface qualities can be altered in the desired direction. MOFs’ properties have led to their usage as heterogeneous catalysts in a number of processes [7], such as (i) electrolytic CO2 reduction.

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(ii) CO2 reduction by photocatalysis (iii) CO, ethanol, ethanol, cyclohexene, and ethyl benzene catalytic oxidation Gasification/Reforming

MOFs derived catalyst

Partial oxidation

MOFs

CO

Oxidation

Fuel Chemicals

Energy aspects

Environmental protection concern

Figure 3.7: Schematic diagram of showing two aspects of heterogeneous catalytic for conversion of CO [17].

(iv) Hydrogenation reactions of CO2, crotonaldehyde, propene, ethane, benzene, propyne, and so on. (v) Catalytic dehydrogenation of cyclohexane to benzene (vi) Catalytic dehydration (vii) Cycloaddition MOFs

CO2

Epoxides

Figure 3.8: Illustration for cycloaddition of CO2 forming epoxides, capturing done by MOFs [6].

3.3 Synthesis Different synthetic processes, such as solvothermal [18], slow diffusion [19], electrochemical [20], mechanochemical [21], and microwave-aided heating [22], are used to create MOFs [8].

3.3.1 Solvothermal synthesis (i) Traditional techniques: This synthesis is based on the use of traditional heating methods. The reaction temperature is the most important variable in this case. Solvothermal and

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nonsolvothermal processes are classed this way. This gives us an idea of the type of reaction we will be looking at. (ii) High-throughput methods: These solvothermal synthesis methods are widely utilized to speed up the discovery of new Nobel compounds and the improvement of reaction mechanisms [9], for example, imidazolate-based MOFs (ZIFs). Microwave-assisted method (latest): The interaction of electromagnetic waves with mobile electric charges is used in this synthesis. As a synthesis medium, polar solvents molecules or ions in a solution of electrons or ions in solids are utilized. MW-assisted MOF synthesis has mostly focused on (1) crystallization acceleration and (2) the production of nanoscale products, but it has also been utilized (3) to increase product purity and (4) for selective polymorph synthesis [9]. The electrical resistance heats the material, creating an electric current. Electromagnetic fields organize molecules in solution, while fluctuating fields cause molecule orientations to shift. When the suitable frequency is used, a collision occurs, resulting in an increase in kinetic energy [23]. Direct heating is said to be the most efficient way. The choice of solvent and the amount of energy input are both taken into consideration [9]. V-di-carboxylates isoreticular frameworks with MIL-47 topology, for example, metal (III) carboxylate-based MOFs.

3.3.2 Electrochemical synthesis Researchers at Badische Anilin-und Soda-Fabrik (BASF) were the first to report on the electrochemical synthesis of MOFs in 2005 as the scope is depicted in fig 3.9. Electrochemical production of microcrystalline powders and films has been reported previously [23]. The pioneering work was done by BASF researchers, who created synthesis processes for several Cu- and Zn-based MOFs. For example, patents on Zn and Cu carboxylates; first electrochemical synthesis; and systematic exploration of Zn, Cu, Mg, and Co [9].

3.3.3 Mechanochemical synthesis Mechanical force can cause a variety of physical (mechano-physics) and chemical reactions. Mechanical breakage of intramolecular bonds is followed by a chemical transformation in mechanochemical synthesis. For example, [Cu(INA)2] initial report; solvent-free synthesis; phase identification [9].

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3.4 Applications and scope

CO

Oxidation (CO2 production), FTS (Hydrocarbon production)

CO2

CH4

Hydrogenation (CH3OH,CH4, CO, HCOOH formation), Cycloaddition (COCs), Carboxylation (Carboxylic acids)

Oxidation (CH3OH, CH3COOH formation)

Figure 3.9: Illustration of different applications and scope of MOFs [17].

3.5 Conclusion MOFs are a multifaceted subject of study. Production becomes very significant due to high selectivity in solvents, dimensions, structure, and networks created. Furthermore, because of its environmentally friendly character, it will become increasingly important in the future [23]. Scientists will be drawn to it because of its green synthesis features.

References [1] [2] [3] [4] [5] [6] [7] [8] [9]

Bavykina, A., et al., Metal–organic frameworks in heterogeneous catalysis: Recent progress, new trends, and future perspectives. 2020. 120(16): p. 8468–8535. Calvino-Casilda, V. and R.J.R.P.o.C.E.M. Martin-Aranda, Advances in metal-organic frameworks for heterogeneous catalysis. 2011. 4(1): p. 1–16. Dhakshinamoorthy, A., et al., Metal organic frameworks as heterogeneous catalysts for the production of fine chemicals. 2013. 3(10): p. 2509–2540. Batten, S.R., et al., Terminology of metal–organic frameworks and coordination polymers (IUPAC Recommendations 2013). 2013. 85(8): p. 1715–1724. Furukawa, H., et al., The chemistry and applications of metal-organic frameworks. 2013. 341 (6149): p. 1230444. Tombesi, A. and C.J.I. Pettinari, Metal organic frameworks as heterogeneous catalysts in olefin epoxidation and carbon dioxide cycloaddition. 2021. 9(11): p. 81. Alqarni, D.S.A., Heterogeneous catalysis with Metal Organic Framework (MOF)-derived materials. 2018: Monash University. Li, H., et al., Design and synthesis of an exceptionally stable and highly porous metal-organic framework. 1999. 402(6759): p. 276–279. Stock, N. and S.J.C.R. Biswas, Synthesis of metal-organic frameworks (MOFs): Routes to various MOF topologies, morphologies, and composites. 2012. 112(2): p. 933–969.

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[10] Pettinari, C., et al., Application of metal−organic frameworks. 2017. 66(6): p. 731–744. [11] Chaemchuen, S., et al., Metal–organic frameworks for upgrading biogas via CO 2 adsorption to biogas green energy. 2013. 42(24): p. 9304–9332. [12] Wang, Z., G. Chen, and K.J.C.R. Ding, Self-supported catalysts. 2009. 109(2): p. 322–359. [13] Lee, J., et al., Metal–organic framework materials as catalysts. 2009. 38(5): p. 1450–1459. [14] Sun, Y., et al., Metal–organic framework nanocarriers for drug delivery in biomedical applications. 2020. 12(1): p. 1–29. [15] Wang, H.-S.J.C.C.R., Metal–organic frameworks for biosensing and bioimaging applications. 2017. 349: p. 139–155. [16] Liu, J., et al., Applications of metal–organic frameworks in heterogeneous supramolecular catalysis. 2014. 43(16): p. 6011–6061. [17] Cui, W.-G., et al., Metal-organic framework-based heterogeneous catalysts for the conversion of C1 chemistry: CO, CO2 and CH4. 2019. 387: p. 79–120. [18] Zhang, Y., et al., Electrocatalytically active cobalt-based metal–organic framework with incorporated macroporous carbon composite for electrochemical applications. 2015. 3(2): p. 732–738. [19] Wu, J.-Y., et al., Influence of counteranions on the structural modulation of silver–di (3-pyridylmethyl) amine coordination polymers. 2013. 13(7): p. 2953–2964. [20] Campagnol, N., et al., Luminescent terbium-containing metal–organic framework films: New approaches for the electrochemical synthesis and application as detectors for explosives. 2014. 50(83): p. 12545–12547. [21] Masoomi, M.Y., A. Morsali, and P.C.J.C. Junk, Rapid mechanochemical synthesis of two new Cd (II)-based metal–organic frameworks with high removal efficiency of Congo red. 2015. 17(3): p. 686–692. [22] Khan, N.A. and S.H.J.C.C.R. Jhung, Synthesis of metal-organic frameworks (MOFs) with microwave or ultrasound: Rapid reaction, phase-selectivity, and size reduction. 2015. 285: p. 11–23. [23] Shekhah, O., et al., MOF thin films: Existing and future applications. 2011. 40(2): p. 1081–1106.

Talha Mumtaz, Rizwan Sikanadar, Arooj Ather, Muhammad Shahzeb, Hazqail Umar Khan, Muhammad Pervaiz✶

4 Homogeneous catalysis using MOFs Abstract: The metal-organic frameworks (MOFs), as we know, have diversity in the pore size and this depend upon different fields of chemistry, such as cluster chemistry, organic chemistry, and X-ray crystallography. The pore size and the space between pores of MOFs can provide us with different physical and chemical structures. Due to high crystals in the materials, we can distribute one or more active site homogeneously. There are issues related to MOFs which is cost and stability related. A right combination of all these properties such as stability, cost, and labor should be chosen correctly.

4.1 Introduction Metal organic frameworks (MOFs) are special class of compounds which are porous in nature and are made up of different organic linkers and nodes of metals. Due to diversity in its structure and functions and also in their arrangements, they are becoming more attractive class of compounds in the history of the chemistry [1]. This can be described as many researches and many articles are being written nowadays on MOFs. There are five main developments in the field of MOFs. There are many advances in the study of cluster chemistry [2]. 1. Post-synthetic modifications and the organic synthesis of ligand preparation 2. There are improvements in the X-ray crystallographic uses in the determination of the structure and to evaluate the sorption properties; many improvements are done in the development of different hardware and software. 3. Study of the interconnection of MOFs with different fields 4. Huge number of applications of MOFs in industries and in other areas The MOFs, as we know, have diversity in the pore size and this depends upon different fields of chemistry, such as cluster chemistry, organic chemistry, and X-ray crystallography. The pore size and the space between pores of MOFs can provide us with different physical and chemical structures. The time is near when there is expansion in the research of MOFs and many different compounds and useful materials will be formed by using MOFs [3]. We can easily alter the pathway of a chemical reaction

✶

Corresponding author: Muhammad Pervaiz, Department of Chemistry, Government College University, Lahore, Pakistan, e-mail: [email protected] Talha Mumtaz, Rizwan Sikanadar, Arooj Ather, Muhammad Shahzeb, Hazqail Umar Khan, Department of Chemistry, Government College University, Lahore, Pakistan

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and we can change the whole chemical reactions by using MOFs. We can use MOFs as a crystal for the determinations of the structure of different macromolecules such as proteins. So, in this way, MOFs have diversity of applications.

4.2 Catalysis of MOFs By comparing the different structures of MOFs with each other, one can investigate about the catalytic properties of MOFs. In different industries, zeolites and mesoporous aluminosilicates are used in different catalytic processes. Acidic zeolites are stable at high temperatures and there is a limit in its pore size and due to these properties they are, under critical conditions, used in gas phase reactions and also used by industries in controlling or processing different processes such as cracking, making isomers, and making alkyls but if a metal oxide such as sulfide or any complex metal is present then they are used in oxidation and reduction processes [4]. Due to high crystal property and limitations in pore size, they can provide diversity of applications as shown in fig 4.1. Due high crystals in the materials we can distribute one or more active site homogeneously. This high crystal property also used to reduce the diffusion and the limits of the pore size. In this way, nature of the active site is controlled PSM of MOFs are done to form heterogeneous compounds from known homogeneous catalysts. PSM can be done for both organic and inorganic materials. There is two step synthesis of heterogeneous vanadyl- iminophenol complex by using IRMOF-3, which as an amino functional MOF-5. From this cyclohexene catalysis takes place [10]. Corma and co-workers use this approach to form a functional material which was composed of gold iminophenol and through this material catalysis of butadiene hydrogenation takes place as shown in fig 4.2 [5]. There are issues related to MOFs which is cost and stability related. A right combination of all these properties, such as stability, cost, and labor, should be chosen Fine chemicals

Intermediate

Bulk chemicals

Cost decreases Thermal stability increases Zeolites Challenges

Successful applications

MOF’s Successful applications

Challenges

Figure 4.1: Comparison of advantages and disadvantages between zeolite and MOFs from fine to bulk chemicals on the basis of cost and thermal stability.

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correctly [6]. To provide specific sites for catalysis in the crystal form of PCPs, following three classes can be used: – Framework activity – Encapsulation of active species – Post-synthetic modifications

4.3 Framework activities The framework activities are divided into two forms: – Activity at inorganic nodes – Activity at organic or pseudo-organic linkers

4.3.1 Activity at organic nodes In this type of activity, the special parts are active sites in the framework of MOFs in the catalytic activities. The framework activity of the catalysis of the cyanosilylation of aldehydes by using the 2D BPY (cadmium bipyridine) framework [Cd(BPY)]n (NO3)2n in which the center part of the cadmium is the active Lewis-acid site. Similar Lewis-acid site is shown in different other MOFs. In inorganic type, copper paddle wheel dimers are used which are inorganic units such as [Cu3 (BTC)2(H2O)3]n, and in these dimers the coordination spheres of the Cu (II) is completed by using water molecules. Water molecules are removed by using a vacuum pump and this helps in the activation of the materials which are catalyzed by Lewis acid catalyzed cyanosilylation of carbonyl groups [7].

4.3.2 Activity at organic or pseudo-organic linkers The catalytic activity of organic or pseudo-organic linkers which have functionally active ligands in them are used commercially. These may include metal complexes, transition metals, and other metal oxide such as sulfides. Recently, some studies are reported about the work in which there is catalysis of epoxidation of olefins by using Mn(III) and catalysis of acyl transfer to pyridylcarbinols by using Zn(II) [8]. There is an example of amino-functionalized MOF [(Zn4O) (atpa)3] which is a catalyst for condensation of benzaldehyde with ethyl cyanoacetat.

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4.4 Encapsulation of active species Encapsulation means that there is a noncovalent interaction of active sites within the pores of MOFs and catalytic actions take place in this. Framework is only a support system for the catalyst and surface area and pore-size stability are very important in this regard. Metal complexes are included in this category. There is no diversity of application in this field but researches are done due to the large pore size of the MOFs [9]. MOF-5 are industrially developed by using researchers at Badische Anilin-und Soda-Fabrik (BASF) technique and this technique is also used for the development of different nanoparticles such as gold, copper, platinum, and zinc and also used for their storage and purification. The materials formed from this technique have a vast amount of applications.

4.5 Post-synthetic modifications Post-synthetic modification (PSM) of MOFs are done to form heterogeneous compounds from known homogeneous catalysts. PSM can be done for both organic and inorganic materials. There is two-step synthesis of heterogeneous vanadyl iminophenol complex by using IRMOF-3, which as an amino-functional MOF-5. From this cyclohexene, catalysis takes place [10]. Corma and co-workers use this approach to form a functional material which was composed of gold iminophenol and through this material catalysis of butadiene hydrogenation takes place.

N NH2 2-hydroxy benzaldehyde HO

] c) 2 ca (a ) (O [V

Complex

Figure 4.2: Illustration showing post synthetic modification in metal organic framework step by step.

To exploits the maximum capacity of MOFs, it is essential to get the association between the active site and its catalytic behavior [11]. This can only be done when the catalysis is performed between crystalline PCPs which can give us:

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a. To decide the specific place of the molecules in the catalytic site and fine design of the system by single crystal by using X-ray diffraction technique b. By determining the sample crystallinity and its homogeneous structure by using XRD c. To interconnect the data which is obtained from the XRD with the data which is already present in the XRD So, the homogeneity of the catalysts should be maintained in order to control the crystal size and the structure and also the pore size.

4.6 Conclusion MOFs offer a wide range of applications in cluster chemistry, organic chemistry, and x-ray crystallography due to their various pore diameters. Although MOFs are ineffective at achieving thermal stability, they are inexpensive and have numerous uses in catalysis. Due to the massive crystal nature, one or more active sites are easily introduced. When it comes to managing the pore size of MOFs, homogeneity is crucial. Heterogeneity is also effective for increasing chemical and physical attributes after synthetic alteration.

References [1] [2] [3] [4] [5] [6] [7] [8]

Luz, I., F.L.i. Xamena, and A.J.J.o.C. Corma, Bridging homogeneous and heterogeneous catalysis with MOFs:“Click” reactions with Cu-MOF catalysts. 2010. 276(1): p. 134–140. Xiong, G., et al., Cluster-based MOFs with accelerated chemical conversion of CO 2 through C–C bond formation. 2017. 53(44): p. 6013–6016. Kitagawa, S.J.C.S.R., Metal–organic frameworks (MOFs). 2014. 43(16): p. 5415–5418. García-García, P., M. Müller, and A.J.C.S. Corma, MOF catalysis in relation to their homogeneous counterparts and conventional solid catalysts. 2014. 5(8): p. 2979–3007. Ranocchiari, M. and J.A.J.P.C.C.P. van Bokhoven, Catalysis by metal–organic frameworks: Fundamentals and opportunities. 2011. 13(14): p. 6388–6396. Genna, D.T., et al., Heterogenization of homogeneous catalysts in metal–organic frameworks via cation exchange. 2013. 135(29): p. 10586–10589. Syed, Z.H., et al., Metal–organic framework nodes as a supporting platform for tailoring the activity of metal catalysts. 2020. 10(19): p. 11556–11566. Zhang, Z., et al., Modulating the basicity of Zn-MOF-74 via cation exchange with calcium ions. 2019. 48(40): p. 14971–14974.

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Liu, H., et al., Controllable encapsulation of “clean” metal clusters within MOFs through kinetic modulation: Towards advanced heterogeneous nanocatalysts. 2016. 128(16): p. 5103–5107. [10] Wang, Z. and S.M.J.C.S.R. Cohen, Postsynthetic modification of metal–organic frameworks. 2009. 38(5): p. 1315–1329. [11] Mandal, S., et al., Post‐synthetic modification of metal–organic frameworks toward applications. 2021. 31(4): p. 2006291. [9]

Zoya Mazhar, Fareeha Andleeb, Rana Rashad Mahmood Khan✶, Muhammad Pervaiz, Ayoub Rashid Ch., Hafiz Muhammad Faizan Haider, Ahmad Adnan

5 MOF: an emerging material for biomedical applications Abstract: Metal-organic frameworks (MOFs) have evolved into a large family of crystalline structures with extraordinarily high permeability and internal areas. Different forms of MOFs that connect with organic can be utilized as a medium for the covalent adhesion of particular substances that operate as receptors or increase chemicals in bioimaging applications. In water vapor, the MOF degradation process may be seen as a series of substitution processes in which hydroxide is replaced by metals-coordinated linkers. The temperature of the reaction is one of the most important aspects in the synthesis of MOFs, and there are typically two temperature varieties recognized: solvothermal and nonsolvothermal. Temperature changes in the reaction have a significant impact on the formation of products as well as the shape of crystals, resulting in denser structures being created at higher temperatures. We applied sophisticated methods for fabricating MOFs with medicines for biological purposes. MOF nanocarriers have been shown to achieve drug delivery and controlled drug release in recent studies, making them a promising class for drug delivery, including anticancer drugs, metabolic labeling molecules. MOFs have been exploited for imaging distinction and molecular therapies in preliminary biological applications.

5.1 Introduction Metal-organic frameworks (MOFs), also known as porous conjugated polymers (PCPs), are mesoporous substances produced up of conductive organic ligands. MOFs have applications in sustainable energy. Catalysis and biological imaging are just a few of the other emerging uses. MOFs, also known as porous conjugated polymers, are mesoporous substances produced with conductive organic ligands. These are the

✶

Corresponding author: Rana Rashad Mahmood Khan, Department of Chemistry, Government College University, Lahore, Pakistan, e-mail: [email protected] Zoya Mazhar, Muhammad Pervaiz, Ayoub Rashid Ch., Hafiz Muhammad Faizan Haider, Ahmad Adnan, Government College University, Lahore, Pakistan Fareeha Andleeb, University of Agriculture, Faisalabad

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materials that have many applications due to their ability to develop as well as finetuneable and consistent pore architectures. The regulated inclusion of MOFs and functional materials leads to the formation of unique multifunctional composites/ hybrids that exhibit new features that are superior to those of the individual components, thanks to the collective behavior of the functional units. This is an intensive literature review topic that is continuously growing as shown in fig 5.1. In the field of bioimaging, MOFs are valued for their low deadliness, high water strength as in fig 5.2. Meanwhile, the kinetics of crystallization must be adequate for bearing the preferred growth phase and nucleation as depicted in fig 5.3. The structure of large crystals is commonly determined as shown in fig 5.4. In this part, we applied sophisticated methods for fabricating MOFs with medicines for biological purposes as depicted in fig 5.5. According to their complexity and manufacturing processes for sensor development, MOF-containing biosensors are split into three groups. These groups primarily concern those polymers are prepared by using conventional syntheses called raw MOFs & those polymers are prepared by using ‘grafting to’ approaches as in fig 5.6. As a result, it’s critical to use a dependable host matrix in biosensors. MOFs may trap molecules in an artificial environment while maintaining their activity. In a nutshell, these particles are stable under a variety of chemical & temperature conditions as in fig 5.7.

Physical & chemical properties

Charge conduction

Properties of Metal Organic Framework

Porosity and high surface area

Scalability and processability

Figure 5.1: Multifunctional properties of MOF.

Many types of MOFs, such as crystalline MOFs, are made up by putting together inorganic materials (metals, clusters, chains, etc.) [2], and polycomplex organic materials with an alignment of structures and varied designs that result in remarkable

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chemical and physical characteristics with a broad array of applications [3]. These absorbent coordination polymers have been significantly considered in gas storage [4], selective adsorption and separation [5], catalysis, and biomedical applications in numerous areas. Molecular imaging [6] and biological sensing are some of the main applications [7]. Furthermore, because of the porous shell and homogenous and customizable cavity, they are prime candidates for medication and gene delivery [8]. Customized MOFs may also detect certain molecules more precisely, such as cells or tissues. In the field of bioimaging, MOFs are valued for their low deadliness and high water strength [9]. Self - assembly strategies

Aggregation of particles

Self-assembly in solution 1. Molecular structure & interaction. 2. Solution conditions

Self-assembly by template 1. Polymer templates 2. Inorganic templates

Self Self assembly at assembly on air-water substrate interface

Thermodynam -ically stable

Fabrication of various 2DOBMs Well-defined structures

DNA/RNA based 1. Grids 2. Arrays 3. Lattices

Protein based 1. Films 2. Membranes 3. Nano sheets

Peptide based 1. Peptide sheets 2. Peptoid sheets

Polymer Based

Surface modification

Structural tailoring

Functional controlling

From molecules to Nano scale 2DOBMs (Nano sheets, Nano grids etc.)

Functionalization with NPs, Carbon materials etc.

Biomedical Application Structural hierarchy

Sensors & Biosensors

Cell growth

Drug Delivery

Bio imaging & Biotherapy

Aid to assists in healing

Figure 5.2: Schematic diagram of MOF as biomedical applications.

5.2 Synthesis of MOFs The biosynthesis of MOFs has drawn plenty of attention in the past 20 years since it permits the creation of a broad collection of unique frameworks. Lately, there have been many erroneous debates and fascinating individual opinions about this phrase [10]. The phrase “design” has been used to describe the composition of MOFs in a

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few instances. The alternative definition of “design” is “to carry out, customize, develop, or manufacture by a plan,” which does not apply to MOF synthesis. However, its ramifications and definitions have prompted changes in this sector. Scaffold knowledge, organic linker functioning, and typical manufacturing circumstances of inorganic structure blocks or metal coordination environments all aid the researchers in designing the synthesis. The main goal of MOF synthesis is to establish a suitable environment for the formation of inorganic structures without the need for organic linker breakdown. Meanwhile, the kinetics of crystallization must be adequate for bearing the preferred growth phase and nucleation.

MOF precursors

Solvents

Carbon based materials

– Conventional heating – Solvothermal – Microwave irradiation – Ultrasonication

Separation and drying

Figure 5.3: Synthesis of MOF–carbon composites.

The chemical stability of MOF means the capability to maintain their planned formation for a long period in a specific chemical environment [11]. The two primary aspects prompting the chemical instability of MOFs are the outer element (environment) and the internal element. Because MOFs have been widely used as bioimaging platforms in bodily fluids, concentrating on their stability in aqueous solutions can provide valuable insight into system design. In water vapor, the MOF degradation process may be seen as a series of substitution processes in which hydroxide is replaced by metals-coordinated linkers [12]. As a result, increasing the strength of coordination bonds across inorganic bundles is an immediate strategy to prevent this process [13]. Specifically, varied approaches can result in unique materials with a variety of sound structures, fragment

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volumes, and equivalent mass allocations, all of which can alter the characteristics of MOFs. Nanocrystalline MOFs, for example, have been proposed for biological platforms because of their benign features and high loading efficiency [14]. MOFs’ unique physicochemical properties can be determined by their structures and pore size. The structure of MOFs can be affected by a variety of variables throughout the synthesis process, including hydrolysis as a diverse component and internal factors [15]. MOF-based molecules are made via chemical reactions involving organic and inorganic portions. Various studies have lately focused on assessing the influence of the artificial method on the formation of MOFs. Various synthesis methods, including standard and unconventional pathways, have been employed to produce a range of MOF derivatives. The specifics of both will be explained further down.

5.2.1 Conventional method “Conventional synthesis” refers to reactions that occur by using ordinary electricity and no parallelization of processes. The temperature of the reaction is one of the most important aspects in the synthesis of MOFs, and there are typically two temperature varieties recognized: solvothermal and nonsolvothermal. A solvothermal process is a reaction that occurs in blocked containers above the boiling point of the solvent under autogenous pressure. Synthetic needs reactions that are nonsolvothermal are simplified when they occur at or below the boiling point. At room temperature, the subsequent reactions may be detected, and at higher temperatures, they can be carried out.

Organic solutions Polymer + Drug + Polar solvent + Surfactants + Oil

Solvent and residual Water evaporation

Aqueous solution Stabilizer in water (Surfactant) Figure 5.4: Synthesis of MOF by solvent evaporation technique.

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In classic MOF synthesis, a solvent removal approach is utilized to vaporize a coating of fluid reactants, and content variations are employed to disperse reactants gently into one other, or by gradually chilling the reaction mixture or managing a temperature gradient. The structure of large crystals is commonly determined. This approach, also known as a straight precipitation process, shows the crystallization of various MOFs in a short period. Surprisingly, several of these, such as ZIF-8, have unusual chemical and thermal stabilities. The response times, on the other hand, may lengthen the duration of time required for MOF breakdown.

5.2.2 Alternative synthesis method As previously stated, the formulation of MOFs is usually done in a solvent system, at 250 ° C. Traditional electric heating methods, such as heat transfer rate from a microwave or a hot source, are frequently used to generate this energy. Pneumatic waves (ultrasound), electron beam, electrostatic force, and mechanical power can all be utilized to generate energy. The energy source is determined by the pressure, time, and energy each molecule introduced to a system. These variables have a significant influence on product development and morphology. Sonochemical, electrochemical, and mechanochemical synthesis, ionic liquids as a synthetic medium, microfluidic system, reverse-phase microemulsions, and microwave-assisted synthesis are some of the alternative synthesis approaches as in table 1. Table 5.1: Methods of synthesis of MOFs and its properties. Methods of synthesis

Properties

1. Conventional solvothermal

Time consuming, other solvents [] required more changes in precursors

2. Sonochemical

Ultrasonic waves are required, high temperature and pressure

[]

3. Electrochemical

Low temperature is required, rapid synthesis

[]

4. Mechanochemical

Quantitative yield, water is the only by-product

[]

5. Ionothermal

Easy recyclability, no vapor pressure

[]

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5.3 Metal-organic framework for biomedical applications MOFs for biological applications have received a lot of interest due to their high surface. MOFs are a potential class of nanocarriers for drug supply [17].

5.3.1 MOF in drug delivery The use of MOF in biomedical applications for drug delivery is gaining popularity. When MOFs are scaled down to nano-sized particles, they become effective nanocarriers for delivering drugs for imaging, chemotherapy, photothermal treatment, photodynamic therapy.

5.3.2 Strategies to functionalize MOF for drug delivery MOFs have unique qualities, such as a highly organized structure, a large surface area, and a substantial volume of pores. It enables them to adsorb catalytic compounds on their multiple channels and keep them contained inside the framework. Furthermore, active chemicals can be added to MOFs by covalent bonding as a result of a post-synthesis alteration. In this part, we applied sophisticated methods for fabricating MOFs with medicines for biological purposes.

Figure 5.5: Strategies to finalize MOF for drug delivery.

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5.3.2.1 Surface adsorption Functional molecules can be adsorbed on the surface of MOFs due to their large surface area. MOFs are presynthesized then stirred in a functional molecule’s solution to produce surface adsorption. The primary forces in this approach are Van der Waals forces and hydrogen bonding. In this simple method, there are no specific requirements on the pores’ size or functional molecules of MOFs. However, due to the weak forces between molecules and the MOF framework, the leaching problem is difficult to overcome. For enzyme immobilization, surface adsorption has been frequently used [20]. Adsorption of the MP-11 catalyst on nanocrystalline Cu-based MOF [21], hydrogen bonding, interactions [22]. In supplement to enzymes, through surface adsorption, nucleic acids may be restrained on MOFs [23].

5.3.2.2 Pores encapsulation MOFs are used as a host material for the substrates that are loaded, preventing them from leaching and providing a secure shield against external influences. Pore encapsulation by de novo synthesis is a flexible and effective technique to introduce functional compounds into MOFs. At the same time, MOFs synthesis and encapsulation of substrate takes place. This technique has mostly been employed to incorporate anticancer medicines inside MOF substrates [24]. Camptothecin was encased into the framework of narrow size distribution ZIF-8 nanoscale particles of homogeneous crystallite size (70 nm). Decreased toxicity was discovered in studies on the MCF-7 [25]. HeLa cells are treated with anticancer nanoparticles; autophagy suppression was shown to be more effective ecause of its strong monodispersity, perfect size for cellular absorption, synthesis in a moderate environment and ease for surface modification. MOF synthesis required conditions such as organic solvents and the environment. These are often abrasive for molecules like enzymes to preserve their structural and functional properties. Encapsulation of pores by using a post-synthetic modification technique offers a potent way to integrate molecules under moderate circumstances. The Ma groups claimed in 2011 that they have immobilized (MP-11) in a mesoporous MOF called Tb-Meso MOF [26].

5.3.2.3 Covalent binding Though contacts desorption and cavity entrapment techniques have been utilized to include a wide range of functional molecules into MOFs, the relatively weak interactions between the molecules and the MOFs have limited their use. MOFs result in leaching difficulties. In light of this, immobilization by covalent

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binding appears to be a viable option. The MOF interface, in particular, includes a broad spectrum of activity, including hydroxyl and carboxyl, that may be exploited to make covalent connections with chemical groups [27]. Through postsynthetic alterations, increased fluorescent dye protein was conjugated to the MOF surface [28]. According to research, miscibility and responsiveness in the transisomerization of 1-phenyl ethanol are well preserved in CAL-B-MOF bioconjugates. The degradation of bovine serum albumin protein by trypsin-MIL-88BNH2 (Cr) was as successful as the digestion of trypsin. Inorganic complexes provide another type of catalytic site in MOFs for chemically attaching molecules. Using a coordination science technique, the outermost metallic terminals of MOF nanomaterials were tightly linked with end phosphatemodified oligonucleotides. Regardless of MOF structure, this method allows for particle surface functionalization. DNA may also be chemically altered to change the interparticle forces.

5.3.3 Functionalized MOFs Designing functional molecules as the building block is another way to functionalize MOFs. Inorganic metals can coordinate with various reactive chemical groups found in biomolecules. Nucleobases and saccharides have been used as organic ligands in the creation of bio-MOFs thus far. Bio-MOFs have a higher level of biological functioning. However, because most biomolecules are very flexible and have little symmetry, it is difficult to make high-quality crystals of MOFs. O and N atoms can be used to coordinate with metal ions because of loner pair electron donors. Because of the several binding ways given by four N atoms, adenine has been extensively researched in the development of bio-MOFs [29].

5.3.4 Applications in drug delivery One of the major problems for conventional chemotherapy is the need to use high drug dose as a consequence of poor biodistribution resulting in frequent doserelated side effects [30]. This necessitates the development of unique and effective medication delivery technologies (DDSs). MOF nanocarriers have been shown to achieve drug delivery and controlled drug release in recent studies, making them a promising class for drug delivery, including anticancer drugs, metabolic labeling molecules, and antiglaucoma medication. Pinocytosis contains caveolin endocytosis and clathrin endocytosis [31]. During the clathrin-mediated endocytosis, receptors are responsible for cargo recognition, followed by the formation of clathrin-coated vesicles, which are usually up to 200 nm in size [32]. These vesicles combine with early endosomes, then into late

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endosomes. The late endosomes merge with lysosomes, which leads to the breakdown of the DDS, decreasing its therapeutic effects [33].

5.3.5 Application of MOF materials as drug delivery systems for cancer therapy and dermal treatment MOF nanocarriers have been proven in recent research to accomplish drug delivery and regulated drug release. Due to this, it becomes a potential class for anticancer medications, antibacterial agents, antiglaucoma medication, metabolic labeling compounds, and hormone administration. Passive delivery (such as folic acid and hyaluronic acid), have all been employed to achieve targeted delivery thus far (pH, temperature, and pressure).

5.3.5.1 A nano-sized MOF for oral drug delivery MOFs can trap biomolecules in their cavities or integrate them during synthesis in biomedical applications. MOFs can be used as carriers to target the particular regions of the body for controlled drug release because of their vast surface area, high porosity, and tailorable features. The creation of NMOFs has recently shown promise in cancer treatment. The functionalization of MOFs’ interior and exterior surfaces has resulted in viable systems for therapy. Furthermore, NMOFs have got a lot of attention in bioimaging applications. By integrating paramagnetic metal ions MOFs might be used in MRI and optical imaging, respectively. Although MOFs offer several advantages in biological applications, clinical applications pose significant difficulties. For example, the presence of heavy metals that is used in the accumulation of MOFs in the body causes problems in controlling drug delivery.

5.4 MOF as biosensors According to their complexity and manufacturing processes for sensor development, MOF-containing biosensors are split into three groups. These groups’ primary concern are polymers that are prepared by using conventional syntheses called raw MOFs, and those polymers are prepared by using “grafting to” approaches [34].

5 MOF: an emerging material for biomedical applications

45

5.4.1 MOFs applications in biosensors Various forms of MOFs can be used for the attachment of specific materials that operate as receptors to increase chemical and electrical signals in bio sensing applications. Furthermore, modified MOFs have better precision in recognizing particular molecules like tissues, and so on.

Organophosphorus Pesticides High sensitivity

Organic Linkers

nt esce luor

sor Sen

High selectivity

F

Rapid response

Metal Ions

MOF

Colo rime tric Sen sor

Current

Electrochemical Sensor

Simplicity Potential

Real time detection

Metal-Organic Frameworks based Biosensor Figure 5.6: Metal-organic framework based biosensors.

5.4.2 MOF in biosensors This chemistry, which began in aqueous solutions, is one of the most important aspects of supramolecular chemistry. Because of their insolubility, studies of MOFs are often restricted to the crystalline form. The solid and liquid phase, in certain situations, the solid and gas phase, might provide a real picture of the host–guest assembly process. Many methodologies for biorecognition of molecules based on superpotential MOFs have been presented in the design, production, and development of these particles. As a result, it is critical to use a dependable host matrix in biosensors. MOFs may trap molecules in an artificial environment while maintaining their activity. In a nutshell, these particles are stable under a variety of chemical and temperature conditions.

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Electrochemical sensors

Carrier of sensing elements

Functional MOFs

Gas sensors

Optical sensors

Figure 5.7: Applications of metal-organic framework.

5.4.3 The function of MOFs in biosensors Alterations of materials give appropriate for biomedical sensing and biosensing [35]. MOFs’ functions are improved as a result of the range of materials and cargos, which expands their potential applications. Modifications create ideal conditions for imaging or other treatments to work. Modification of MOFs can solve issues including cytotoxicity and metabolism of drugs. To synthesize strong particles in biosensors, it is necessary to functionalize MOFs with different groups. Moreover, the presence of linkers in MOF structures leads to a variety of chemical interactions with biomolecules, including hydrogen bonding, stacking, and electrostatic attraction. MOFs have been modified in a variety of ways to serve as biosensor platforms. Hydrogen bonding is an example of chemical interactions.

5.5 MOF in biomedical imaging MOFs have several benefits over traditional nanomedicines, including chemical changes. MOFs may be produced as crystalline or amorphous materials under comparatively modest conditions. To improve the final particle qualities, the particle size and morphology may all be readily weakened. To distribute active agents using NMOFs,

5 MOF: an emerging material for biomedical applications

47

researchers have used two broad strategies: integrating active agents into the frameworks. NMOF surfaces that have been modified with silica increase their stability. MOFs have been widely investigated as magnetic resonance imaging (MRI) contrast agents due to their ability to transport high quantities of paramagnetic metal ions. MOFs containing Gd3+ and Mn2+ have demonstrated good effectiveness as T1-weighted contrast agents, with high per metal, and per particle MR relaxivities. T2-weighted contrast enhancement has been shown in Fe3+-containing MOFs. Researchers detected negative signal elevation in the liver and spleen after intravenous injection of iron carboxylate NMOFs in Wistar rats, which faded with time, indicating the NMOF’s breakdown and removal. Anticancer medicines and other chemotherapeutics have been delivered using MOFs. Cisplatin prodrugs were integrated into NMOFs at extremely high quantities, either by using the prodrug as a building block or by attaching the prodrug to the framework after it had been synthesized. These MOFs were encased in silica and used to target cancerous cells. Some distinct medicinal compounds were overloaded at unprecedented amounts within carboxylate MOFs. In-vitro studies found that the nanoencapsulated drug had equivalent effectiveness to the free drug, and the NMOF displayed sustained drug release with no burst effects [22]. MOFs are composed of organic ligands and metal ions (or clusters). With properties of large surface area, high porosity, tunable chemical composition, and potential for post-synthetic modification, different types of MOFs have been developed and applied in many important fields, such as gas storage/separation, catalysis, molecular sensing, and biomedicine. For biosensing or bioimaging, the luminescence properties of MOFs can be bestowed by the introduction of either organic ligands or metal centers (ions or clusters) [22] with intrinsic luminescence properties, or luminescent guest molecules or ions. Since organic ligands directly influence the biomedical applications of MOFs, strict screening of organic ligands is necessary. For MOFs to be better applied in the field of biomedicine, organic ligands of MOFs with good biocompatibility and low toxicity have been employed. Because of its inherent biodegradability and the ability to employ biocompatible building elements, MOFs might be useful in biological applications. I hope to offer the most current advances in MOF research for biosensing and bioimaging in this review. MOF imaging systems’ compositional tenability should substantially ease their further development for clinical translation.

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5.6 Conclusions MOFs have evolved into a large family of crystalline structures with extraordinarily high permeability and internal areas. Different forms of MOFs that connect with organic can be utilized as a medium for the covalent adhesion of particular substances that operate as receptors or increase chemicals in bioimaging applications. Temperature changes in the reaction have a significant impact on the formation of products as well as the shape of crystals, resulting in denser structures being created at higher temperatures. We applied sophisticated methods for fabricating MOFs with medicines for biological purposes. This chemistry, which began in aqueous solutions, is one of the most important aspects of supramolecular chemistry. Because of their insolubility, studies of MOFs are often restricted to the crystalline form. The solid and liquid phase, in certain situations, the solid and gas phase, might provide a real picture of the host–guest assembly process. MOF nanocarriers have been shown to achieve drug delivery and controlled drug release in recent studies, making them a promising class for drug delivery, including anticancer drugs, metabolic labeling molecules, and antiglaucoma medication. MOFs have been widely investigated as MRI contrast agents due to their ability to transport high quantities of paramagnetic metal ions. Invitro studies found that the nano-encapsulated drug had equivalent effectiveness to the free drug, and the NMOF displayed sustained drug release with no burst effects.

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[31] Mellman, I., Endocytosis and molecular sorting. Annual Review of Cell and Developmental Biology, 1996. 12(1): p. 575–625. [32] Sevimli, S., et al., The endocytic pathway and therapeutic efficiency of doxorubicin conjugated cholesterol-derived polymers. Biomaterials Science, 2015. 3(2): p. 323–335. [33] McMahon, H.T. and E. Boucrot, Molecular mechanism and physiological functions of clathrinmediated endocytosis. Nature Reviews. Molecular Cell Biology, 2011. 12(8): p. 517–533. [34] Carrasco, S., Metal-organic frameworks for the development of biosensors: A current overview. Biosensors, 2018. 8(4): p. 92. [35] Hasanzadeh, M., et al., Immunosensing of breast cancer prognostic marker in adenocarcinoma cell lysates and unprocessed human plasma samples using gold nanostructure coated on organic substrate. International Journal of Biological Macromolecules, 2018. 118: p. 1082–1089.

Ramsha Saleem, Rana Rashad Mahmood Khan✶, Bisma Khanam, Ayoub Rashid Ch., Muhammad Pervaiz, Zohaib Saeed, Ahmad Adnan

6 Pharmaceutical wastes: an overview Abstract: During the last decades, the growth of pharmaceuticals as lifesavers has aroused the issue of water contamination with pharmaceutical waste (PhW). The PhW comprises drugs including antibiotics, anticonvulsants, antihypertensives, antidepressants, hormones, NSAIDs, vaccines, serums, and the patient’s medications. The human and veterinary excretory products, hospital effluents, aquaculture, and disposal of unused or expired medication contribute to the origin of pharmaceutical pollution in the aquatic environment. These compounds in their original forms or the forms of metabolites or conjugates of glucuronic acid and sulfuric acid get entry into the sewage water via excretion. The traditional wastewater plants cannot remove the pharmaceutical contaminants efficiently and they enter the aquatic environment. These compounds have severe effects on humans, plants, animals, fish, and protozoa. Hence, various technologies have been developed to eliminate the contaminants of pharmaceuticals from water bodies. Several strategies have been limited by high expenses, less effective removal, and toxic sludge production. Adsorption is found to be advantageous over all other methods as it is simple, cost-effective, highly effective, and feasible.

6.1 Introduction Pharmaceutical waste (PhW) refers to any medication waste which is not fully consumed or remains unused throughout the pharmaceutical supply and uses chain. As pharmaceutical products are necessary for human health, to fulfill the growing need for pharmaceutical products, healthcare industries produce a huge number of drugs annually [1]. These pharmaceutical products contain biologically active ingredients referred to as active pharmaceutical ingredients (API). Any chemical constituent having pharmaceutical function with useful effects to diagnose, prevent, treat, or cure disease and affect the body’s structure and function is considered an API. The API performs specific functions in animals and humans and is not completely degraded

✶

Corresponding author: Rana Rashad Mahmood Khan, Department of Chemistry, Government College University, Lahore, Pakistan, e-mail: [email protected] Ramsha Saleem, Bisma Khanam, Ayoub Rashid Ch., Muhammad Pervaiz, Zohaib Saeed, Ahmad Adnan, Department of Chemistry, Government College University, Lahore, Pakistan

https://doi.org/10.1515/9783110792607-006

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after metabolic reactions in the body. These chemicals are released into the environment from various sources and are referred to as PhW products [2]. PhW includes a variety of materials such as expired, split, contaminated drugs (used or unused), personally discarded patient’s medication, discarded drugs, abandoned material (connecting tubes, masks, syringes, vials, bottles with residues), and containers that are used to keep hazardous waste drugs, spill cleanup materials, absorbents, and home use personal care products [3]. A major part of PhW is various drugs, serums, and vaccines such as antibiotics, hormones, chemotherapy products, and antidepressants. In response to acute or chronic illness, only a part of the active ingredient in the metabolized drug. The nonmetabolized part along with metabolized part enters the aquatic system by waste discharge [4, 5]. All these substances either from industrial or domestic sources discharged directly or indirectly into the water where they remain persistent for a longer time. In the 1970s, environmental contaminations due to pharmaceutical products were raised. The first analysis to estimate the concentration of pharmaceuticals in surface and potable water was performed in 1980. A very small amount of these pharmaceutical active compounds largely affects human health and the ecosystem. So, the removal of these waste materials from the environment is of utmost. Since the 1990s, the technology became adequately advanced to quantify the concentration of PhAC in water samples at low levels, that is, μg/L and ng/L [6]. Now, different methods have been established for the removal of API from the environment. But still, now different challenges arise for their removal due to their small concentration. The conventional methods for WWT involve coagulation, filtration, biological processes, sedimentation, membrane filtration, chlorination, adsorption (using carbon nanotubes, activated carbon, ozonation, and graphene oxide), photocatalysis, UV irradiation, and many others [7–11]. The effects of API in the environment on nontarget species are unknown. However, one study revealed that in Pakistan, the residual diclofenac was responsible to minimize the vulture population. The long-term exposure to API largely affects the physiology and growth of organisms. Therefore, unwanted medicine should be disposed of properly to overcome environmental and public health risks. Because the improper disposal of leads to accidental toxicity and ultimately results in landfill pilfering, antimicrobial resistance, water pollution, rising healthcare costs, and death. All these effects may be reduced by raising public awareness regarding disposal practices [12].

6 Pharmaceutical wastes: an overview

53

6.2 Classification of PhW PhW includes all the expired or dispensed drugs that are unwanted and also the contaminated medications. These waste materials pollute the environment on a large scale when disposed improperly. The Environmental Protection Agency established Resource Conservation and Recovery Act (RCRA) which classifies PhW into different categories according to their physical nature, degradability, human health, and environment [13]. The major types of PhW are: 1. Over-the-counter drug waste 2. Hazardous waste 3. Nonhazardous waste 4. Controlled drug waste 5. Veterinary-use pharmaceuticals 6. Agricultural-use pharmaceuticals

6.2.1 Over-the-counter drug waste The term over the counter is related to nonprescription medicines. These drugs are used to relieve allergies, headaches, acid, and cold reflux. The most used over-thecounter drugs are acetaminophen (to cure fever, minor aches, pain), diphenhydramine (antihistamines), dextromethorphan (cough suppressants), and so on. These drugs are used on large scale all over the world. When these medicines are dropped down the sink or toilet, they can contaminate water and pollute landfills when flushed. In this way, these drugs disturb the sewage treatment process by affecting surface water microbial ecology. These drugs may cause injury if misused by children or left carelessly. Therefore, these drugs should be disposed of properly [13].

6.2.2 Hazardous waste Hazardous drug waste may be defined as any waste that can cause serious illness or even death if it is poorly transported, stored, treated, or disposed. Such waste has significant hazardous effects on human health and the environment. The hazardous waste material is further listed by RCRA, using various alphabet letters. These lists are K-list, F-list, P-list, and U-list. The P and U-list waste include acute hazardous waste material [14]. The F-list hazardous waste contains all types of waste materials that come from specific industries and manufacturing processes. The F-listed waste mostly comes from diagnostic laboratories in which solvent procedures are performed. The most common examples of nonhalogenated solvents in the F-list are methanol, benzene, xylene, cyclohexane, toluene, isobutanol, and acetone. Apart from solvent wastes,

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certain industry wastes that fall into this category are wastes released during chlorinated aliphatic hydrocarbons production, dioxins containing waste, and waste released during electroplating or metal finishing [13]. The K-listed wastes are specific regarding their source and are from particular industrial and manufacturing sectors. These sectors include veterinary pharmaceuticals and organic chemicals manufacturing units. The K-listed waste includes the following types of waste: distillation tar residues released from arsenic or organoarsenic compounds in veterinary pharmaceutical manufacture and activated carbon used in the production of veterinary pharmaceutical also releases residue when arsenic or organo-arsenic compounds are used [13]. Acute hazardous PhW that are listed as P- and U-list wastes are very toxic. The P-listed waste drugs include acute toxic drugs (nicotine, warfarin, epinephrine, physostigmine, and phentermine), which cause severe effects. The containers that are used to hold these drugs are also listed as P-listed waste material. The U-listed waste material contains toxic drugs (phenol, chloral hydrate, and selective antineoplastic material) as well as the containers that are used to store these drugs. All the chemotherapy waste materials are included in U-list [13].

6.2.3 Nonhazardous waste The waste material that contains noncontrolled prescription medicines (not subjected to some limitations) are used to treat diabetes, blood pressure, bacterial infections, and so on. Although these drugs are not considered as harmful as hazardous drug waste but they should also be disposed properly [15].

6.2.4 Controlled drug waste The waste materials may be defined as drugs that must be controlled because they are highly addictive and can be toxic or easily abused if taken in large amounts. The most common examples of controlled drugs are marijuana, alcohol, cocaine, and opiates.

6.2.5 Veterinary-use drugs These are the drugs that are used for prophylactic and therapeutic purposes in animals to cure infections and for prevention of diseases [16]. The most commonly used veterinary drugs are antibiotics that are given to animals for growth purposes.

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6 Pharmaceutical wastes: an overview

6.3 Classification of pharmaceutical dosage from waste The pharmaceutical products include any type of prescription or nonprescription drugs for human and animal use. These drugs that remain active after metabolism contain APIs in their structure [17, 18]. On the activity of these active ingredients, some of the pharmaceuticals are detected in the environment in a large amount. The most commonly analyzed pharmaceuticals and their conjugates and metabolites in the environment are: antibiotics, antihypertensives, antidepressants, lipid regulators, anticonvulsants, hormones, and nonsteroidal anti-inflammatory drugs [17]. Table 6.1 shows the physicochemical properties of some of the most frequently detected pharmaceutical dosage forms in the environment. Table 6.1: Physicochemical properties of various frequently detected pharmaceutical dosage form waste [19–22]. Pharmaceutical dosage form

Structure

Molecular pKa Weight

log Kow

. Antibiotics Erythromycin

O

.

.–.

.

.

.–. −.

.

.–.

HO O N

OH

HO O

O OH

O

O

O

O OH

Ofloxacin

N

O N

N

HO F O

Ciprofloxacin (CIP)

O

HN N

N OH

F O

O

.

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Table 6.1 (continued) Pharmaceutical dosage form

Structure

Molecular pKa Weight

Sulfamethoxazole (SMX)

H N

O

log Kow

.

.–.

.

.

.–.

.

.

–

–

.

.

.

S O

N

O

H2N

Amoxicillin

O HO O N O OH

S N H

H

H2N

Oxacillin N O H S

H N O

N O HO O

Trimethoprim

O O

NH2

N N

O

NH2

. Antidepressants Fluoxetine

F F

.

.

.

.

.

.

.

–

–

F N H

O

Diazepam

Cl

N N

Meprobamate

O

O H2N

O O

O

NH2

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6 Pharmaceutical wastes: an overview

Table 6.1 (continued) Pharmaceutical dosage form

Structure

Molecular pKa Weight

log Kow

. Anticonvulsants Carbamazepin

.

.

.

.

–

–

.

–

–

.

.

.

.

.–.

.

.

.

.

.

.

.

.–.

.

N NH2

O

Primidone

O NH N H

O

Phenobarbital

H N

O

O

HN O

. Antihypertensives Metoprolol

OH H N

O

.

O

Propanolol N H

O OH

Atenolol

OH

H N

O O NH2

Losartan HO

N N

Cl

Furosemide

N

O

H2N

N

NH N

O

S OH O Cl

N H O

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Table 6.1 (continued) Pharmaceutical dosage form

Structure

Molecular pKa Weight

Diltiazem

log Kow

.

.

.

.

–

–

.

.

.

.

.

.

S O N

N

O

O O

. Lipid Regulators Benzafibrate

O O

O

OH N H

Cl

Clofibric acid

O O OH Cl

Gemfibrozil

O O

OH

. Hormones Estrone

O

.

.

.

.

–

–

.

.

.

H H

H

HO

Mestranol

HO H H

H

O

. NSAIDS Aspirin

O O O

OH

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6 Pharmaceutical wastes: an overview

Table 6.1 (continued) Pharmaceutical dosage form

Structure

Diclofenac

Molecular pKa Weight O

Cl

log Kow

.

.

.

.

.

., .

.

.

.

.

.

.–.

OH

H N Cl

Ibuprofen

O OH

Acetaminophen

OH

O N H

Naproxen

O

O

HO

6.4 Sources of PhW The use and consumption of pharmaceuticals have been increasing continually with the advancement in medical technology. The annual consumption rate of pharmaceuticals differs greatly from country to country [23]. By making an indication about the annual sale of a specific drug, the occurrence of that drug in the environment can be determined. Over the last decade, the global annual use of human as well as veterinary pharmaceuticals has increased. Both developing and developed countries use veterinary medicines for prophylaxis and to enhance the growth of livestock and agriculture and commercial aquaculture [24]. All the metabolites and residues of these pharmaceuticals are released into wastewater [25]. PhW gets entry to the aquatic system by hospital waste, human and veterinary waste, and effluents of pharmaceutical industries (Figure 6.1).

6.4.1 Domestic release The trends in the consumption of pharmaceutical drugs by humans worldwide are of prime significance as they help us identify the type of PhW in water and then modify the removal method. Pharmaceutical drugs are most widely employed by

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Figure 6.1: Ways of entry of PhW into the aquatic system.

humans and animals to treat diseases and infections. The annual consumption rate of antibiotics is 100,000 to 200,000 tons worldwide [20]. The pharmaceutical drugs consumed by humans cannot be completely metabolized in their bodies. They are excreted via urine or feces in the form of unmetabolized drugs, degraded products, or conjugates of glucuronate or sulfate. The content of unmetabolized drugs excreted varies from 10% to 90% [26]. The unused or expired drugs also contribute significantly to the domestic release of PhW. It is estimated that about 75% of the total pharmaceuticals sold in Germany and 25% of that in Austria are disposed in the waste or drained off [27]. In a study survey in the USA, it was found that more than 50% of people keep unused or expired medicines in their homes and the other half drained them in the toilet; only 22% of people return the unused or expired medicines to the pharmaceutical stores to dispose of them in a proper way [28]. Another study survey in Kuwait revealed that almost 45.4% population have unused medication in their homes. The main reason behind the storage of old and unused medicines is the variability in the prescription of doctors or self-discontinuation [27]. Domestic sources are found to be the dominant origin of

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PhW in our environment. For example, in USA and Europe, they make 75% of the total PhW [29]. Figure 6.2 illustrates the domestic sources of PhW in sewerage water.

Unabsorbed metabolites

Unmetabolized

Unused/ Expired

Human Consumption

Metabolized

Absorbed into blood

Excretion

Wastewater

Figure 6.2: Domestic sources of pharmaceutical waste in water.

6.4.2 Veterinary release Pharmaceuticals including antibiotics are used to treat infections and promote growth in animals. Therefore, they get entry into the water and soil via the excretion of animals. The second most common route of entry of antibiotics to our ecosystem is the use of animal waste comprising residues as manure to fertilize the land. The contaminated manure leads to antibiotic pollution in the soil and then exceeds aquatic pollution due to the flow of water from the soil to the surrounding water bodies [30].

6.4.3 Hospital effluents Hospitals are the most concerning source of PhW in water bodies as they are the hub of the consumption of pharmaceuticals [31]. The PhW in hospital effluents has resulted from the use of pharmaceuticals for diagnostic, laboratory, and research purposes and the excretion of humans. The PhW from hospitals includes API,

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metabolites of drugs, disinfectants, sterilants, gadolinium, radioactive tracers, and so on (Figure 6.3) [32]. API Disinfectants

MRI

HN N

O

N OH

F O

64

Gd

O

O

Gadolinium

HO

O

Pt

O

Hg

HO HO

NH I I N

O

I

OH

HN O

HO

ICM

Heavy Metals

Anesthetics Figure 6.3: Components of PhW in HWW.

The most consumed drugs in the hospitals are the therapeutic class that includes antibiotics, anti-inflammatories, analgesics, anesthetics, and laxatives [33]. The concentration of contaminants of 12 human-used drugs has been estimated to be 151 μg/ L in the hospital effluents [19]. The type and amount of drug waste depend on the type of treatment taking place. Kanama et al. studied hospital effluents Ngaka Modiri South Africa and revealed that bezafibrate, ofloxacin, and chloramphenicol are below the limit of quantification, whereas ibuprofen and paracetamol were found to be dominant drug waste. The concentrations of ibuprofen and paracetamol were estimated to be 0.3–63 μg/L and 21–119 μg/L, respectively [21]. The study in Brazil and Mexico identified the presence of estrone, estradiol, ampicillin, amoxicillin, and norfloxacin in hospital effluents and then in water bodies [34]. The hospital wastewater (HWW) is released into the local sewerage water which takes it to the traditional sewerage water treatment plant. The traditional plants are unable to remove the waste efficiently and the treated water containing pharmaceutical contaminants becomes part of surface water, groundwater, and then drinking water [32]. Figure 6.4 shows

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the concentration of different PhW in HWW. However, a mixture of PhW and their degraded products have been detected in hospital effluents in different parts of the world.

13

24

1.65 11 100

5.9

0.16

1008

Analgesics

Antibiotics

Cystostatics

Beta-blockers

ICM

Gadolinium

Platinum

Mercury

Hormones

Figure 6.4: Concentration of different PhW (μg/L) in HWW [32].

6.4.4 Aquaculture Aquaculture is defined as the farming of aquatic organisms including fish, mollusks, and crustaceans [29]. The global consumption of fish is continually increasing, with the major development in aquacultures, that is, from 3,077 million kg in 1999 to 5,255 million kg in 2008 production of fish via aquaculture [35]. The production of fish by aquaculture is estimated to be 54% and 60% of its consumption by humans in 2030 [36, 37]. The high requirements of fish need large production of fish. Fish in aquaculture are more susceptible to diseases. They act as hosts to many parasites and thus suffer from parasitic infections [38]. Hence, almost 500 various pharmaceuticals are used to prevent and treat infections [35]. Praziquantel is one of the pharmaceutical drugs, most commonly employed to treat parasitic infections in fish [39]. Antibiotics are used to promote growth and avoid bacterial infections in fish. It is reported that approximately 1 million kg and 7 million kg of oxytetracycline and chlortetracycline are used in aquaculture per annum [40]. It is directly introduced into the aquaculture, and this acts as a major route of its contamination in water bodies as only 20–30% of the pharmaceuticals get absorbed

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into the body of fish and the remaining 70–80% sustains in the water and then enters the surface and groundwater [41].

6.5 Occurrence of pharmaceuticals in aquatic system Various studies have revealed that several pharmaceuticals and their degraded products are present in surface water, groundwater, and drinking water (Table 6.2). Table 6.2: Occurrence of various pharmaceutical dosage forms in different parts of the world. Drug

Country

Sample type

Max. concentration

Reference

ng/L . Antibiotics .

[]

. ± .

[]

HWW

, ± ,

[]

Switzerland

HWW

, ± 

[]

Difloxacin hydrochloride

China

Chaohu lake water

.

[]

Erythromycin

Portugal

HWW



[]

South Africa

River water

.

[]

China

Chaohu lake water

.

[]

Beibu Gulf water

.

[]

Amoxicillin

Nigeria

Lagos water

Cephalosporins

China

Sediments

Ciprofloxacin

Switzerland

Clarithromycin

Enrofloxacin

.

Enoxacin

. ± .

[]

.

[]

. ± .

[]

Beibu Gulf water

.

[]

Chaohu lake water

.

[]

. ± .

[]

Macrolides

Sediments

Penicillin

Chaohu lake water

Quinolones

Sediments

Sulfamethoxazole Sulfadiazine Sulfonamides

China

Sediments

Sulfamethoxazole

Germany

Groundwater

Trimethoprim

China

Beibu Gulf water



.

.

[] []

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Table 6.2 (continued) Drug

Country

Sample type

Max. concentration

Reference

ng/L . Antidepressants Diazepam

Beijing

Urban sea

.–.

[]

Fluoxetine

Brazil

Cotia river

.

[]

Sorocoba river

.

Guarapiranga reservoir

.

Portugal

Venlafaxine

Leca river water

.

[]

River water

.

[]

Sediments

.

Leca river water Oxazepam

Beijing

Urban sea



[]

.–.

[]

.–.

Temazepam . Anticonvulsants

.

[]

Marine water

.

[]

US

WWT effluents



[]

Ibuprofen

Germany

Drinking water



[]

Paracetamol

USA

Drinking water

.

[]

Paracetamol

USA

Groundwater

.

[]

Spain

Raw water

.

[]

Phenobarbital

Germany

WWTP effluents

Carbamazepine

Tunisia

Primidone . NSAIDS

. Hormones Estrone Estriol



Tamoxifen

.

Ethinyl estradiol

.

μg/L.

1

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6.6 Removal of pharmaceuticals from an aquatic environment To date, several techniques have been developed to remove PhW from an aquatic environment (Figure 6.5). These techniques include ozonation [8, 59], chlorination, biological [60], membrane reactors [61], photocatalysis [62, 63], advanced oxidation process [64], and adsorption [10, 65]. Table 6.3 illustrates the advantages and limitations of various removal methods of PhW from water.

Figure 6.5: Ways to remove the pharmaceutical waste from waterbodies.

Table 6.3: Advantages and limitations of removal techniques of PhW from wastewater with their brief description. Removal technique

Description

Advantages

Limitations

WWTP

Activated sludge

Low cost Easy to use Efficient removal of high sorption drugs

Production of contaminated and toxic sludge Low degradation

Chlorination

Oxidation using chlorine

Efficient removal of highly reactive compounds

Toxic byproducts

References

[–]

[]

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Table 6.3 (continued) Removal technique

Description

Advantages

Limitations

CoagulationFlocculation

Formation of flocs and their aggregation

Wide pH range Removal % removal rate Low degradability

References

No application in large scale water treatment Recovery of catalyst is difficult

[, ]

Difficult to operate High energy requirement Toxic oxidized byproducts

[, , ]

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6.7 Conclusion and future prospects Pharmaceutical drugs are the cause of emerging toxins that cannot be inhibited, but these contaminants, even at low concentration, is a threat to human health and our ecosystem. However, the efficient removal method of PhW is required. The removal of PhW from the aquatic environment is of prime significance for the health of living organisms as well as for balance in the ecosystem. The prospects in this topic are: – It was observed that research has been done on the occurrence, effect, and removal methods of the pharmaceutical drugs while there is a lack of research on the degraded products, metabolites, and conjugates of the drugs produce. These products are much more toxic than the parent compound; hence, more research is required in the study of the effects and elimination of these degraded products. – Strict regulations must be implemented for effluent released from hospitals. – WWTPs should be equipped with advanced PhW removal technologies to avoid their entry into waterbodies. – The occurrence of pharmaceuticals in water bodies of developing countries especially China should be monitored.

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Hoorish Qamar, Rana Rashad Mahmood Khan✶, Ramsha Saleem, Muhammad Pervaiz, Nazir Ahmad, Hafiz Muhammad Faizan Haider, Ahmad Adnan

7 Recent advancement and development in MOF-based materials for the removal of pharmaceutical waste Abstract: Metal-organic frameworks (MOFs) have been used to treat pharmaceutical waste for a long time now. Promising characteristics of MOFs and their flexible nature ensure the successful removal of pharmaceutical waste. Forces of attractions such as electrostatic, hydrophobic, and pi–pi interactions are responsible for the efficient adsorption of adsorbates over MOFs. MOFs can be molded according to the requirement of the type of waste to be treated. Innovations are being made to develop less toxic and environment-friendly MOFs. MIL-101, a prominent MOF, has been functionalized by the addition of acidic and basic groups to efficiently remove naproxen. Similarly, the addition of TiO2 to MIL-100(Fe) increases the photocatalytic activity to remove tetracycline up to 92%. Hundreds of novel MOFs have been synthesized in recent years which yield a great percentage of waste removal. To further improve the adsorption capacity of MOFs, different types of fabrications are being including, that is, the addition of certain functional groups, combining with semiconductor or polymers, and green synthesis of MOFs. Scientists are also moving toward the green synthesis for the MOFs to ensure the eco-friendly sustenance of MOFs and living beings. Several ways have been devised to adopt green synthesis which involves the use of eco-friendly solvents and less toxic metals.

7.1 Introduction With every step forward toward modernization, mankind is dragged 10 steps behind by the risks which come along with modernization. Biomedical and pharmaceutical fields are progressing day by day to make a healthier lifestyle possible for mankind and other living creatures. This too comes with side effects. For the past many years,

✶

Corresponding author: Rana Rashad Mahmood Khan, Department of Chemistry, Government College University, Lahore, Pakistan, e-mail: [email protected] Hoorish Qamar, Ramsha Saleem, Muhammad Pervaiz, Nazir Ahmad, Hafiz Muhammad Faizan Haider, Ahmad Adnan, Department of Chemistry, Government College University, Lahore, Pakistan https://doi.org/10.1515/9783110792607-007

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pharmaceutical waste has been treated just like other waste. There has been no proper management for the disposal. This act of human beings might have been affected for a long time. The knowledge of the composition of pharmaceutical waste and how to discard it comes first than any other activity [1].

7.1.1 Pharmaceutical waste When it comes to defining pharmaceutical waste, any sort of limitation should be avoided. Our cities are now crowded with healthcare centers, medicare, pharmacies, and hospitals. Any sort of waste coming out of these vicinities will be regarded as pharmaceutical waste. Pharmaceutical waste can be found in a considerable amount on our lands, water, and air. With the increasing drug synthesis and usage, we are at potent risk of passive medication by the drug which is actively present around us [2]. That is why there is a need for proper management and disposal of pharmaceutical waste. Geological Society of the United States of America, for the first time, issued a report providing proof for the existence of pharmaceutical and other organic waste in surface waters in March 2002 [3]. Our water treatment plants are not made to treat pharmaceutical waste. They are only meant for the sediments and micro-organisms present in the water. To overcome the forthcoming havoc, many nations have joined hands for sustainable development by the year 2030. This also includes the correct usage and disposal of medication/pharmaceutics [4]. Common pharmaceutical waste comprises of: – Plastic packing materials – Glass wares – Medicines/drugs – Syringes or tubes – Personal safety equipment like gloves, head caps, and masks Figure 7.1 mentions the common sources of pharmaceutical wastes. Pharmaceutical waste is considered a major risk for human health and the environment due to three main reasons. Major three types of pharmaceutical waste are mentioned in Figure 7.2. Based on the action, MOFs provide three pathways to treat the waste as shown in Figure 7.4. pollutant and MOFs in the following Figure 7.5: – Pharmaceutical waste is generally more persistent in terms of life as compared to other regular waste. – Microorganisms generally have less degradation capacity toward them. – Aquatic life is equally susceptible to the dangers of pharmaceutical wastes [5].

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Pharmaceutical waste from hospitals, industries, and households

Pharmaceutical waste from livestock, agriculture and other animals Pharmaceutical production

Waste water Solid waste management

Landfill dumping

Figure 7.1: Common sources of pharmaceutical wastes.

7.1.2 Composition of pharmaceutical waste According to a survey, there are more than 4,000 different types of pharmaceuticals available in the market [6]. We cannot gather or classify the components present in pharmaceutical waste because of their never-ending diversity. Yet, we can distribute them into some general categories.

Pharmaceutical waste

Solid pharmaceutical waste Liquid pharmaceutical waste Hazardous pharmaceutical waste

Scalpels Contaminated gloves, masks, bandages

Sludg. Unused liquid medicines

Empty or expired pill bottles Injectors, nebulizers

Contaminated solvent

Figure 7.2: Types of pharmaceutical waste.

Acetone, Methanol, Benzene

Arsenic trioxide, epinephrine, Nicotine Acidic waste from the residual chemical treatments. Dioxins

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We cannot say that pharmaceutical waste only comes from medical facilities. Our households are also responsible for producing generous pharmaceutical wastes. Pharmaceutical waste from the households generally include syrups (expired or nonexpired), creams, ointments, capsules/tablets, and bandages [7].

7.1.3 Most prominent compounds in pharmaceutical waste The most common drug present in pharmaceutical waste is paracetamol (Figure 7.3(a)). Its concentration in wastewater is quite prominent, that is, 10–23 µg/L [8]. Studies have shown that even after the subjection of treatments, wastewater still contains considerable amounts of paracetamol. Removal of paracetamol from wastewater is the current rising challenge for environmental protection [9]. Another drug that is found most prominently in the wastewater is acetylsalicylic acid (aspirin). Its structure is shown in Figure 7.3(b). This drug has been found in major concentration of 54 µg/L. Another drug reported by Essandoh et al. [10] is ibuprofen, which is also found in considerable quantities in wastewater, 69 µg/L [10]. Among antibiotics, tetracycline (Figure 7.3(c)) is the second most used antibiotic. Its concentration in wastewater is rising each day. Degradation of tetracycline is not accomplished by any regular method. Its removal has gathered the attention of scientists since its rising concentration has been observed [11]. Ciprofloxacin is also a widely used antibacterial drug whose removal from wastewater is another great concern for environmentalists [12]. Hydroquinone, another deadly compound (when in-contacted in large amounts), is also found in the liquid waste from hospitals or other medical centers [13]. Figure 7.3(d) shows the structure of hydroquinone. Another toxic compound from the pharmaceutical industry is Naphthol (Figure 7.3 (e,f)). They are equally dangerous in their ionized and deionized forms. Removal of such compounds from the wastewater must be the top priority as it damages the aquatic life instantly [14].

7.2 Metal-organic frameworks Metal-organic frameworks (MOFs) are generally a combination of some organic ligand and a metal ion leading to a porous assembly. The organic ligands can be bidentate, tridentate, or tetradentate. The properties of MOFs can be adjusted according to the application [15]. The porous structure gives them an extraordinarily large surface area and unique spatial topology. Due to their flexible nature, MOFs are used widely in water-treatment procedures. Wei et al. [16] have reported the removal of metal ions and other organic components using flexible MOFs [16]. The flexibility in MOFs

7 Recent advancement and development in MOF-based materials

O

77

OH

OH O

H3C

N H

O

Structure of Paracetamol

Structure of Acetyl salisylic acid (b)

(a)

OH

O

CH3

O

OH

O

O

OH

OH NH2

OH HO

H CH3

H N H3C

CH3

Structure of Tetracycline (c)

OH

Structure of Hydroquinone (d)

OH OH

α−Napthol

β−Napthol

(e)

(f)

Figure 7.3: Structures of common pharmaceutical compounds.

provides them far more supremacy than the conventional adsorbing materials such as zeolites and porous carbon [17]. Based on the action, MOFs provide three pathways to treat the waste. These are given below: – Adsorption – Photocatalytic degradation – Photocatalytic production of H2 [18]. These are illustrated in the figure below.

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Adsorption Adsorbed/trapped in the pores

Sunlight Photocataytic degradation

Clean water

Waste

CO2, H2O

Photocatalytic production of H2

Waste

Sunlight

Clean water CO2, H2

Figure 7.4: Pathways of action of MOFs.

Due to their unique properties, MOFs are applicable in many scientific fields such as the delivery of drugs/compounds, sensing, separation, and photocatalysis [19–21]. Hasan and Jhung [22] have shown the possible ways of interaction between the pollutant and MOFs in the following diagram [22].

7.2.1 MOFs for the removal of pharmaceutical waste MOFs are used to treat pharmaceutical waste for a long time now. Different types of pharmaceutical waste require different MOF assemblies. Treatment of pharmaceutical waste is rather complex. Efficient removal of pharmaceutical waste has been a constant challenge for scientists. Several techniques have been devised for the successful removal of pharmaceutical waste for sewage and wastewater. These techniques include membrane separation, biodegradation, advanced oxidation process, adsorption, and so on. Adsorption via chemically engineered MOFs is preferred due to economical procedures, high efficiency in removal, and less production of secondary pollutants [20].

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MOFs

:X

H+

Hydrophobic MOF

79

Water molecule

Hydrophobic adsorbate

MOFs

X

H–

Acid-Base interaction –

+ +

MOFs

Hydrophobic interactions

δ+

– Adsorbates

+

–

+

δ– X

H

MOFs

δ– H

δ+

δ– X

δ–

δ+

–

+

δ+

–

–

+ –

MOFs

MOFs

+

H

X δ+ X

δ

δ

δ– H

Adsorbates

–

+

–

+ Electrostatic interaction

Hydrogen bonding

Figure 7.5: Interaction between MOFs and adsorbates [22, 23].

To develop MOFs for the removal of pharmaceutical waste, several parameters are to be kept in mind. One of which is the interaction between the waste particle and the adsorbing MOF. Some of the common interactions include acid–base interaction, hydrophobic or electrostatic interaction, hydrogen bonding, pi–pi interactions, and metal bridge forming [21].

7.2.1.1 Removal of antibiotics by MOFs Antibacterial drugs constitute a major portion of pharmaceutical waste. The first antibacterial drug to be degraded with the help of MOF (ZIF-8) was oxytetracycline [19]. The efficient removal of an antibiotic tetracycline was performed over a magnetic nanocomposite of chitosan and covalent organic frameworks as shown in Figure 7.6. It was also confirmed that the coexistence of hydroxyl and amino groups of chitosan

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as well as the phenyl group of carbon organic framework increased the adsorption capacity for the tetracycline [24]. OH

O

OH

O

O

OH NH2 OH HO

H CH3

H N H3C

CH3

Tetracycline

Reuse

Adsorption over Chitosan film

clean water

UV or Photodegradation

Figure 7.6: Adsorption of tetracycline over chitosan film [25].

Dimetridazole is efficiently removed by MIL-53(Al), prepared by Peng et al. [26]. Different concentration of the dye is adsorbed differently over the MOF. The incorporation of aluminum increases the adsorption capacity of MIL-53 up to 467.3 mg/g [26, 27]. An antibiotic named sulfachloropyridazine is significantly removed by the copper-based MOF [24, 28]. Another copper-based MOF, copper glutamate [Cu(Glu)2(H2O)].H2O] removes ciprofloxacin from the wastewater with great efficiency. Olawale et al. [29] showed that copper glutamate removes 61.35 mg of ciprofloxacin 1 g of copper glutamate at pH 4 at 25 °C [25, 30].

7.2.1.2 Removal of lipid-lowering drugs To efficiently remove lipid-lowering drugs like bezafibrate, fenofibrate, and clofibrate, a magnetic composite Fe3O4@Fe-BTC, consisting of an iron-based MOF combined with iron-benzene tricarboxylic acid (Fe-BTC) was synthesized by Mendez et al. [31]. The incorporation of magnetic nanomaterials enhances the adsorption

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ability of Fe3O4@Fe-BTC through pi–pi interactions as well as acid–base interaction. The adsorption efficiency ranges from 80% to 100% [31]. There are many MOFs that are being studied for the removal of pharmaceutical wastes. Some MOFs have outstanding adsorbing properties. Material of Institute Lavoisier MIL-101 is one of the most prominent MOFs used for pharmaceutical waste treatment. It is the framework of chromium–benzene dicarboxylate, CrO3(F/ OH)-(H2O)2[C6H4(CO2)2]. It efficiently removes clofibric acid as well as naproxen from the pharmaceutical waste by adsorbing them to its surface [28].

7.2.1.3 Removal of anti-inflammatory drugs A nanocomposite MOF named MOF-199/CNTs, synthesized by Wang et al. [30], has been studied to efficiently remove certain inflammatory drugs including ibuprofen, ketoprofen, and naproxen. The presence of carboxylate groups efficiently increases the binding ability of MOF and ibuprofen through hydrogen bonding and pi–pi interactions. The interactions of MOF-199/CNTs with naproxen and ketoprofen are quite complicated. However, the complex interaction increases the adsorption of anti-inflammatory drugs over MOF [30]. Salicylic acid and acetylsalicylic acid are efficiently removed from the wastewater using a zirconium-based MOF from the University of Oslo (UiO) series of MOF. UiO-66NH2 is a magnet MOF that significantly removes salicylic acid and its derivative [32].

7.3 Recent advancement and development The development in MOFs has never stopped. To improve the action capabilities of MOFs for the removal of pharmaceutical waste, many innovations have been made. MOFs functionality can be improved by various techniques. The development in MOFs can be classified into the following categories.

7.3.1 Insertion of metal–ligand coordination in MOFs Caffeine is a prominent drug present in pharmaceutical waste. The daily consumption of coffee in the world is around 1.6 billion cups per day according to the International Coffee Organization. Although caffeine is beneficial for human health, its increasing concentrations in the waste are causing a great risk to the environment and life. To remove it from the wastewater, novel MOF was synthesized by Olawale et al. [29], which is [Ni (II)(Tpy)(Pydc)].2H2O (synthetic scheme shown in Figure 7.7).

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When this MOF is subjected to caffeine removal, it shows excellent adsorption. About 1 g of the MOF adsorbs 95.02 mg of caffeine [29].

N

N O

O

+

O

N OH

N Ni

N

O

.H2O

N OH

Pyridine-2,6-dicarboxylic acid

N

N

2,2',6'',terpyridine

O

O

[Ni (II)(Tpy)(Pydc)].2H2O

Figure 7.7: Structures of reactants of [Ni(II)(Tpy)(Pydc)].2H2O.

The adsorption of caffeine on [Ni (II)(Tpy)(Pydc)].2H2O is due to the immediate interaction between the binding sites present on the surface of MOF and caffeine. It only takes 60 min for the MOF to be completely saturated by caffeine compound at a concentration of 40 ppm. The graph (Figure 7.8) shows the adsorbed concentrations of caffeine per cycle run. Acidic pH (4) favors the adsorption rate. At this pH, the adhesion of the caffeine on [Ni (II)(Tpy)(Pydc)].2H2O is faster, which may get slower on pH greater than 4 when hydrogen ions are in less concentration. Toxicity tests suggested the presence of negligible amounts of nickel ions in the reaction mixture which is not taken as a risk. This also supports the reusability of [Ni (II)(Tpy)(Pydc)].2H2O [29]. Ciprofloxacin is an antibiotic used commonly around the world. To remove its increasing concentration in wastewater, the MOF of chromium fumarate was synthesized by Kurtulbas et al. [33]. Igwegbe et al. [34] reported iron-based MOFs such as Fe3O4/C and Fe-MCM-41 for the removal of ciprofloxacin [34].

7.3.2 Addition of functional groups To increase the adsorption properties of MOFs, functional groups can be incorporated into the organic ligands. An iron-based MOF, MIL-53(Fe) was functionalized with functional groups as amino, nitro, or bromide reported by J. Yu et al. [35]. MIL-101 has also been functionalized with an acid and a base group. Ethylenediamine was used to fabricate an (–NH2) in MIL-101 to form ED-MIL-101. Aminomethane sulfonic acid was used to impart sulfonic group (–SO3H) to form AMSA-MIL-101. The incorporation of the amino group significantly increased the adsorption capacity of MIL-101 for the naproxen [30, 34]. It was observed that adsorption capacity was maximum for the MIL-

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Caffeine removal (%)

100

98.4

96.8

1

2

96.5

96.4

95.9

95.7

3

4

5

6

83

80

60

40

20

0

Cycles Run Figure 7.8: Caffeine removal by [Ni (II)(Tpy)(Pydc)].2H2O [29].

101-OH which is 185 mg/g at 25 °C [30, 35]. Urea and melamine have also been incorporated into MIL-101 and named them Urea-MIL-101 and Melamine-MIL-101. It was observed that on the addition of urea and melamine the surface area was reduced due to the insertion of large species and alterations in the structure during fabrication but Urea-MIL-101 and Melamine-MIL-101 showed maximum adsorbing capacities for antibiotics such as nitroimidazole because of the presence of –NO2 group which significantly increases the formation of hydrogen bonding of MOF with the adsorbate [30, 36]. It was reported that functionalization of MIL-53(Fe) prominently increases the adsorption of tetracycline. The maximum adsorption capacities for amino, nitro, and bromo MIL-53(Fe) were observed as 271.8, 272.6, and 309.6 mg per gram respectively [35]. MIL-100(Fe) was also synthesized and used for the adsorption of a fluoroquinolone antibiotic, Levofloxacin by Chaturvedi et al. [36]. The mechanism for the adsorption of Levofloxacin over MIL-53(Fe) is shown in Figure 7.9.

7.3.3 Doping of MOFs Doping of transition metals in the MOFs also increased the adsorption capacity of MOFs for the pharmaceutical waste [37]. This is due to the reason that the added metal increases the surface area and pore size of the MOF and they also tend to impart valence electrons. Transition metals also increase the electrostatic interactions by altering

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MIL-100(Fe)

O OH N

O OH Hydrogen bonding O O HO

N

N

O F OH

Benzene tricarboxylix acid (BTC) linker

O

Levofloxacin

Figure 7.9: Adsorption of Levofloxacin over MIL-53(Fe) [36].

the electronegativity on the surface of MOFs [38]. Baeza et al. [39] synthesized a chromium-based MOF MIL-101(Cr) doped with nickel to remove paracetamol (N-acetyl-Paminophenol) from pharmaceutical waste. With the addition of nickel, the surface area of MIL-101(Cr) is decreased but the adsorption capacity is increased to five percent instead. It also increases acidic strength and forms pi complexing. The adsorption of MIL-101(Cr) alone is 1.87 mg/g but with the addition of nickel the adsorption capacity jumps to 10.52 mg/g. Nickel imparts valence electrons to the active sites of the MOF due to which the adsorption capacity for antibiotics is increased. Figure 7.10 shows the comparison of the adsorbed concentration versus the time graph for doped and undoped MIL-101(Cr) which confirms the efficiency of doping regarding the adsorption of pharmaceutical waste [39]. Doping also improved the performance of the MIL-53(Fe) for doxycycline reported by Xiong et al. [40]. The adsorption mechanism mainly contributes toward electrostatic forces of interactions and pi–pi interactions between the aromatic rings of doxycycline and adsorbate [40]. S. Sun et al. [41] synthesized copper-based ZIF-8 for the removal of tetracycline from pharmaceutical waste. Adsorption studies showed that the adsorption capacities for ZIF-8 for tetracycline were 65.5 mg/g while for Cu-ZIF-8 was 156.5 mg/g. It can be seen that there is an incredible increase of about 2.4 times in the adsorption capacity for Cu-ZIF-8 [41]. The presence of copper increased the availability of valence electrons. It reduces the surface area but increases the pore size which overall increases the adsorption of tetracycline over Cu-ZIF-8. Copper ions destroy the structure of MOFs [38]. Copper-Benzene-Tricarboxylic acid- has also been synthesized and functionalized with dopamine for the adsorptive removal of ibuprofen and acetaminophen. This MOF showed an excellent adsorption capacity of 187.97 mg/g and 125.45 mg/g for ibuprofen and acetaminophen respectively [42].

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11

Absorbed concentration (mg/L)

10 9 Ni-MIL-101-(Cr)

8

MIL-101(Cr) 7 6 5 4 3 2 1 0 0

50

100 150

200 250

300 350 400

450 500

550

Time (min) Figure 7.10: Absorbance of paracetamol by Ni-MIL-101(Cr) and MIL-101(Cr) [39].

7.3.4 Polymer coupling Polymer coupling is another method to improve the efficacy of MOFs. Several MOFs coupled with organic and inorganic polymers have been reported. Wang et al. [43] coupled MOF of UiO-66-(COOH)2, Zr (IV) based, with graphene oxide and carboxyl groups (Figure 7.11 shows the schematic diagram). After coupling, UiO-66-(COOH)2/ GO possesses the highest adsorption capacities of 131.65 mg/g. It is approximately six times higher than that of UiO-66-(COOH)2 as shown in graph Figure 7.12 [43]. To remove 2-naphthol from wastewater, the zeolite imidazole framework incorporated with wool was prepared by Abdalhameed and Emam [44]. ZIF@wool fabrication was made from different kinds of ZIFs including ZIF-8 and ZIF-67. ZIF-67@wool fabric showed higher absorbance as compared to ZIF-8. The higher absorbance is attributed to the increased active sites on ZIF-77@wool as shown in Figure 7.13 [44]. Chen et al. [45] used another polymer, chitosan, and fabricated it over UiO-66 to prepare composites of chitosan@UiO-66 foam with excellent adsorbing properties. It was then used to remove ketoprofen from wastewater. The adsorption process involves hydrogen bonding as well as pi–pi interactions [45].

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O

OH COOH

1,2,4,5-benzenetetracarboxylic acid (H4BTEC) UiO-66-(COOH)2 ZrCl4 Graphene Oxide(GO)

in situ growth

UiO-66-(COOH)2/GO

Schematic diagram of UiO-66-(COOH)2/GO formation process Figure 7.11: Formation of UiO-66-(COOH)2/GO [43].

7.3.5 Photocatalytic activity Certain oxides when fabricated with MOFs enhance the pharmaceutical waste removal by photodegradation. Novel nanocomposite consisting of carbon nanotubes and MOF-808 has also been synthesized. This MOF composite, CNTs/MOF-808 was used for the removal of drug carbamazepine. The installation of CNTs over MOF boosted the degradation of carbamazepine to 86.6% as compared to 68% of MOF808. Synthesis of this MOF composite now allows further progress toward the costeffective photodegradation of pharmaceutical wastes [43]. MIL-100 (Fe) when combined with a semiconductor like titanium oxide improves the adsorption capacity for tetracycline. After combining with the semiconductor TiO2, the degradation rate for tetracycline of MIL-100 (Fe) raises to more than 90%. The presence of a semiconductor produces an electron hole, which improves the degradation effect [38]. Following this, L. He et al. [46] synthesized MIL-101(Fe)/TiO2. It is a novel magnetic MOF, used for the photodegradation of tetracycline as shown in Figure 7.14. This magnetic MOF

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140

UiO-66-(COOH)2/GO UiO-66-(COOH) UiO-66/GO UiO-66

120

Adsorption capacity (mg/g)

87

100 80 60 40 20 0 0

10

20

30

40

50

Adsorption time (h) Figure 7.12: Comparison of adsorption capacities of UiO-66, UiO-66/GO, UiO-66-(COOH)2, and UiO-66-(COOH)2/GO [43].

degrades 92% of the antibiotic [46]. The reactions involved in the degradation are as under:

7.3.6 Green synthesis Increased interest in the use of MOFs for waste removal also comes with a cost. With recent developments and synthesis in MOF-based materials, the environment is also at great risk due to the toxicity from the metals and certain compounds. To overcome this risk, scientists are moving toward the green synthesis of MOFs [47]. The green synthesis of MOFs can be attributed to certain aspects as described in the Figure 7.15.

7.3.6.1 Less hazardous solvents Diethylformamide and dimethylformamide are the most commonly used solvents for the synthesis of MOFs as they tend to impart a significant acid–base character to the MOF [49]. However, they also cause a lot of toxicity due to the presence of amine groups [48]. That is why the use of hazard-free solvents is necessary. Some examples of less toxic and less hazardous solvents are methyl lactate, derivatives of glycerol, water and dimethyl sulfoxides [50, 51].

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400 350 300

ZIF-8@Wool ZIF-67@Wool Wool

Qt (mg/g✶h)

250 200 150 100 50 0 0

20

10

30

40

50

60

time (h) Figure 7.13: Adsorption of 2-napthol by wool, ZIF-8@wool, and ZIF-67@wool [44].

e– Conduction band e–

Degraded products

Fe3+

Tetracycline

Fe2+

Solar light Fe3+

·OH

Ti4+ O2 –OH

h+ Valence band +

O2–

Ti3+

Fe3+ Fe4+

Fe3+

Tetracycline

Degraded products Figure 7.14: Photodegradation of tetracycline by MIL-101(Fe)/TiO2 [46].

Using water as a green solvent, several MOFs have been synthesized in an ecofriendly process. Zirconium-based MOFs have been synthesized in aqueous media by Chen et al. [52]. Supercritical liquids such as high-temperature water and super critical carbon dioxide can also be used for the synthesis of MOFs [48]. Ionic liquids

89

etal Low toxic m

cts du pro byus rdo aza sh Les

salts

7 Recent advancement and development in MOF-based materials

Green applications

Eco-friendly linkers Green synthesis

Gre en sol ven ts

ses ces pro nt icie eff

Cos t effi cie ncy

y erg En

ts duc pro e l ab rad deg o i B

Figure 7.15: Aspects of green synthesis [48].

present another choice for suitable solvents. Not all ionic liquids can be regarded as green solvents. Some ionic liquids including methylimidazolium are toxic [53]. Some suitable ionic liquids are listed below in Figure 7.16. A bioderived green solvent called cyrene has also been employed for the green synthesis of MOFs. It can be obtained from biomass [54].

7.3.6.2 Nontoxic metals Sustainable synthesis also promotes the choice of less toxic metals for eco-friendly MOF synthesis. Some less toxic metals and their counter salts for the synthesis of least toxic MOFs are given below in Figure 7.16 [48]. MIL-53(Fe) is an efficient adsorber of pharmaceutical waste. MIL-53(Fe) does not show a good adsorption in the visible range which limits its activity. To enhance its photocatalytic character, some metal is incorporated in the structure of MOF. Due to the extraordinary properties of the copper metal, such as nontoxicity, high stability, catalytic advancement, cost-efficiency, and high adsorption rate, a new bi-metallic MOF has been synthesized by Chatterjee et al. [55] under the title of MIL 53(Fe-Cu). This MOF was confirmed to adsorb ciprofloxacin with maximum adsorption of 190.4 mg/g. Degradation percentage of ciprofloxacin by MIL 53(Fe-Cu) under UV-light and visible light was 74.48% and 57.88%, respectively [55].

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Methodologies for green synthesis of MOFs Ionic liquids

Choice of solvents Recommended green solvents

Cations

Water

Ammonium

Isopropyl alcohol

Phosphonium

Methanol/Ethanol

Imidazolium

Acetone

Pyridinium

Supercritical CO2

Pyrrolidinium

Non-toxic metals Anions

Halogens Hexaflourophosphate Tetrachloroaluminate Triflate Acetate, Sulfate

Zinc Iron Copper Calcium Magnesium Potassium Zirconium Manganese

Counter ions Acetates Carbonates Sulfates Hydroxides Acetylacetonates Oxides

Figure 7.16: Methodologies for the green synthesis of MOFs.

7.4 Conclusion Pharmaceutical waste cannot be eliminated once and for all as there will always be a need for medical/pharmaceutical supplies. However, their toxicity can be reduced with the help of advanced or conventional technologies. Adsorption of pharmaceutical waste is a conventional method but with progress in technology, adsorption methodologies have been changed. MOFs have been used to remove pharmaceutical waste for a long time now. Almost all types of drugs and hazardous compounds can be treated with the help of suitable MOF. Scientists have been working to make the process more feasible by bringing innovations in the MOFs. Recently, structures of MOFs have been modified with the help of several methodologies including, fabrication of functional groups, polymers, and semiconductors. Green synthesis of MOFs is also a considerable aspect toward the success of MOFs. Pharmaceutical waste treated with eco-friendly MOFs proves that there can be a coexistence between scientific technology and nature.

References [1] [2] [3] [4] [5]

Smith, C.A.J.J.o.t.P.S.o.W., Managing pharmaceutical waste. 2002. 5: p. 17–22. Kümmerer, K., Pharmaceuticals in the environment: Sources, fate, effects and risks. 2008: Springer Science & Business Media. Kolpin, D.W., et al., Pharmaceuticals, hormones, and other organic wastewater contaminants in US streams, 1999− 2000: A national reconnaissance. 2002. 36(6): p. 1202–1211. Smale, E.M., et al., Waste-minimising measures to achieve sustainable supply and use of medication. 2021. 20: p. 100400. Taoufik, N., et al., Removal of emerging pharmaceutical pollutants: A systematic mapping study review. 2020. 8(5): p. 104251.

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[6] [7] [8] [9]

[10] [11]

[12] [13] [14] [15] [16]

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[23] [24]

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Aqmar-ur-rehman, Rana Rashad Mahmood Khan✶, Hoorish Qamar, Ramsha Saleem, Yussra Naeem, Ayoub Rashid Ch., Aqib Adnan, Muhammad Pervaiz

8 Future prospective of metal-organic frameworks for pharmaceutical wastes Abstract: To date, metal-organic frameworks (MOFs) have been used in a variety of fields, including sensing, separation, storage, and catalysis. Pharmaceutical wastes are considered a major reason for contamination of water due to their occurrence in excess all around us. MOFs have been studied in the removal of pharmaceutical wastes, but some major drawbacks such as toxic metals, small surface area, production of secondary pollutants, and high cost have hindered their applications. Our study highlights the major challenges and future perspectives including possible solutions to said problems of MOFs in pharmaceutical waste treatment. Various strategies may enhance the applicability of MOFs in biomedical and industrial applications. MOFs have played a vital role in real-life experiences.

8.1 Introduction This chapter discusses the challenges and possible solutions regarding the treatment and disposal of pharmaceutical waste by metal-organic frameworks (MOFs). It also emphasizes the future perspective of MOFs and their activity in pharmaceutical waste removal.

8.1.1 Pharmaceutical waste Outdated, contaminated, or unused prescriptions, over-the-counter pharmaceuticals, as well as wastewater and chemical sludge generated during the manufacturing process, are all examples of pharmaceutical waste. To significantly reduce the negative impact on nature, extensive care and safety measures should be taken when disposing and treating the waste. Pharmaceuticals and personal care products, which include medicines, pesticides, cosmetics, and cleaning products, have developed into one of ✶

Corresponding author: Rana Rashad Mahmood Khan, Department of Chemistry, Government College University, Lahore, Pakistan, e-mail: [email protected] Aqmar-ur-rehman, Hoorish Qamar, Ramsha Saleem, Yussra Naeem, Ayoub Rashid Ch., Aqib Adnan, Muhammad Pervaiz, Department of Chemistry, Government College University, Lahore, Pakistan https://doi.org/10.1515/9783110792607-008

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the most important industries in the world. Factors of environmental pollution pose a major threat to the safety of drinking water [1]. Proper implementation of management guidelines for hazardous waste (including household medicines) will drive the Medical Waste Management Market Trend by 2028. Various initiatives encourage law enforcement officials to collect domestic remedies following Pertinent Laws, such as the Drug Enforcement Agency’s (DEA) National Prescription Drug Take-Back Day. Such endeavors, along with the burgeoning incidence of coronavirus epidemics, could promote the implementation of drug production waste management strategies. However, the consequences of improper drug disposal, as well as the high cost involved in waste processing, can stymie industry growth over the entire launch period [2]. The first nationwide discovery of the prevalence of pharmaceuticals and other organic waste pollutants in surface water, including pharmaceuticals, was announced in March 2002 by the United States Geological Society. Some of the sources of pharmaceutical wastes are shown in Figure 8.1.

No longer required by public

IV Preparations

Expired pharmaceuticals

waste generated during manufacutring

Discontinued drugs

pharmaceutical waste sources

Partially used vials and syringes

Compounding of drugs

Figure 8.1: Composition of pharmaceutical wastes.

Patients’ personal medicatons

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8.1.2 Composition of pharmaceutical waste Pharmaceutical waste composition: There are two primary streams of pharmaceutical waste in terms of waste management. (1) Pharmaceutical waste, including unused or obsolete medicine, as well as caps and syringes, which individuals have created at home and primary care centers. The stream also includes medicines for cattle and pets. (2) Pharmaceutical waste is generated by hospitals and other healthcare and research establishments. Numerous studies have shown that improper pharmaceutical waste disposal can have negative effects on the environment and human health. Pharmaceutical chemicals, for example, are found in sewage and treatment plants, as well as in rivers, groundwater, drinking water, and lakes [3]. Composition and origin of some pharmaceutical wastes are shown in Table 8.1. Pharmaceutical wastewater contains waste from pharmaceutical businesses, homes, and hospitals that pollute the environment. Various types of pharmaceutical wastes are shoen in Figure 8.2. Pharmaceutical waste from households and medical facilities contaminates the water bodies. To remove pharmaceutical waste, high technology methods are devised. There are many methods used conventionally and non-conventionally as shown in Figure 8.3. Many MOFs have been synthesized with efficient activities. MOFs are named according to the area of discovery, or their structures [14]. Adsorption of pharmaceutical wastes on MOFs has been shown in Figure 8.4. Because of the high resistance of adsorbent to restoration and the high regenerative capacity, it can be regarded as a viable choice for DOC removal as shown in Figure 8.6. As a result, further in-depth research is required in this field. Figure 8.7 shows some future prospects of MOFs. Table 8.1: Composition and origin of some major pharmaceutical wastes [4–8]. Waste description

Process origin

Composition

Process liquors

Chemical synthesis

Contaminated solvents

Infectious/ medical wastes

R&D, manufacturing operations, off-spec products

Vials, blood products, biomass, human or animal specimens

Combustion Products

Thermic fluid heater and boilers

Oxides of nitrogen, carbon compounds, boiler blowdown, sediments, and cooling tower sludges

Packaging material

Packaging operations

Wood, plastic, cardboard, foam products

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Table 8.1 (continued) Waste description

Process origin

Composition

Used chemical reagents

R&D activities

Solvents, miscellaneous chemicals, radioisotopes, and acid/base wastes

Miscellaneous wastes

Maintenance operations

Vacuum pump oil, paint stripping wastes, cleaning solvents, trash, spent fluorescent lamps, leftover accessories and paints, and waste lube oils

Spent ethylene dioxide

Sterilization operations

Ethylene oxide

Volatile organic compounds

Drums and chemical storage tanks

Solvents

Spillages

Laboratory operations

Heavy metals and miscellaneous chemicals

Leftover raw material containers

Unloading of materials Drums/bags, plastic bottles into equipment processing

Spent fermentation broth

Fermentation operation

Contaminated water

8.1.2.1 Who regulates disposal of medical waste? The US Environmental Protection Agency is the main body that controls and regulates the disposal of pharmaceutical waste. Additional regulatory bodies are – DEA – Department of Transportation – Fish and Wildlife Services

8.1.2.2 Pharmaceutical waste in solid form Products used with pharmaceutical residues are referred to as solid pharmaceutical waste. Some examples are – Sharp tools such as scalpels, needles, and syringes – Pill bottles, blister packs, liquid medicine containers, and ointment tubes – Contaminated products including gloves, masks, bandages and IV bags, and tubing – Drug delivery devices like autoinjectors, inhalers, and nebulizers

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8.1.2.3 Pharmaceutical waste in liquid form –

–

Liquid pharmaceutical waste is produced due to various processes carried out by liquid pharmaceutical waste production facilities. Chemically treated sludge and polluted solvents are examples of this waste. Unused liquid pharmaceuticals are often classified as pharmaceutical waste.

8.1.2.4 Common compounds in pharmaceutical waste Chemical compounds present in pharmaceutical waste are generally classified into hazardous and nonhazardous categories. 8.1.2.4.1 Hazardous chemicals Such chemicals which pose deadly effects on the health of living organisms are included in the list of hazardous chemicals. Some of the examples are given below. – Dioxin – Xylene – N-butyl alcohol – Ethyl acetate – Acetone – Toluene – Arsenic trioxide – Nicotine 8.1.2.4.2 Nonhazardous Waste that is not necessarily completely harmful when released into the environment. Even “nonhazardous” waste can have negative health and environmental consequences. As a result, it still requires careful handling and a safe, specific disposal process. For example: – Medications available over the counter – Contraceptives – Hormones – Antibiotics

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hazardous

Liquid form

SOLVENT

Pharmaceutical waste

Solid form

Non-hazordous

Figure 8.2: Types of pharmaceutical wastes.

8.1.3 Treatment of pharmaceutical waste Pharmaceutical wastes from households and medical facilities contaminate the water bodies. To remove pharmaceutical waste, high-technology methods are devised. There are many methods used conventionally and nonconventionally. Some of the methods are autoclaving, incineration, physical removal, chemical removal, advanced oxidation processes, and adsorption over membranes or MOFs [4]. Pharmaceutical wastes removal generally includes either adsorption or degradation. Photocatalytic degradation has been proved the most efficient method to degrade pharmaceutical wastes, that is, TiO2 semiconductors were used in the degradation of paracetamol. Modern research focuses on the development of materials with nanoproperties [9]. There are several nanomaterials used to remove pharmaceutical wastes, for example, carbon nanotubes [10], graphene oxide (GO) sorbents [11], nanomembranes, for example, chitosan [12], and MOFs [13].

8.1.3.1 Metal-organic frameworks MOFs are nanomaterials synthesized from a metal and an organic ligand. Ligands most prominently contain donor atoms like oxygen and nitrogen. MOFs have wide areas of applications owing to their unique characters. Many MOFs have been synthesized with efficient activities. MOFs are named according to the area of discovery, or their structures [14]. MOFs have been widely used in a variety of applications, including gas absorption, conductivity, sensors, isolation, and catalysts, due to their advantages. There are several benefits to using MOFs to absorb pharmaceutical waste [15].

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Figure 8.3: Treatment methodologies for pharmaceutical waste treatment.

Adsorption

Metal Organic Framework(MOF)

Pharmaceutical Waste

Green environment

Figure 8.4: Adsorption of pharmaceutical waste over MOFs.

8.1.3.2 Pharmaceutical waste treatment by MOFs Activated carbon, zeolites, and clay minerals have all been used to absorb pharmaceutical waste from wastewater [16]. However, the absorption capacity of these conventional absorbers is often limited, especially at low target molecular concentrations. Due to excellent features of MOFs, such as high and adjustable porosity, structural flexibility, and ease of post-synthetic change, MOFs have recently emerged as a new generation of porous materials [8]. MOFs have a higher loading capacity of pharmaceutical

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waste because of their higher porosity, open metal sites on abundant functional groups (e.g., OH, NH2), and charges. MOFs provide strong interactions with pharmaceutical waste, such as electrostatic interactions, hydrogen bonding interactions, and facilitate the tuning properties of holes (e.g., hole size, hole size, and hydrophobicity) [5]. Antibiotics’ presence in our ecosystems has been linked to chronic ecotoxicity and the development of antibiotic resistance in the bacterial species, both of which can disrupt the ecological balance of our ecosystems and drastically limit antibiotics’ therapeutic efficacy against infections. Adsorption with MOFs has emerged as a feasible alternative to current technology for removing antibiotics from water [17]. Several MOFs have been used to treat pharmaceutical wastes including antibiotics such as tetracycline. MIL-101 removes tetracycline by adsorption as shown in Figure 8.5 [18].

H2N +

OH

O OH

OH

O

H

H

H H N

HO

OH

Tetracycline

OH HO O HO

Adsorption

N

MIL-101

Pi-Pi interaction

O HO

HO

MIL-101

O

O NH2

Figure 8.5: Adsorption of tetracycline over MIL-101.

When the starting content of the tetracycline is 50 mg/L, Fe-MIL-101 has 96.6% removal efficiency. Under the same conditions, Fe-MIL-100 and Fe-MIL53 have removal effectiveness of 57.4% and 40.6%, respectively. The impact of concentration, adsorption period, and the tetracycline composition on the degradation has been investigated. Even after three photocatalytic degradation cycles, Fe-MIL-101 remains stable and reusable [18]. Because of the high resistance of adsorbent to restoration and the high regenerative capacity, it can be regarded as a viable choice for DOC removal. The kinetics procedure on the MIL-53(Fe) is quick and could be represented with the pseudosecond-order equation. Langmuir isotherm model fits data of the equilibrium adsorption nicely. Because the adsorbent of the MOF is extremely paramagnetic, it may be effectively separated using the external magnetic field. The adsorbent has been recycled six times, with renewed adsorbent retaining most of its initial capacity. The conclusions show that the synthesized adsorbent is effective at removing the doxycycline from the aqueous solutions. Using an external magnetic field, the adsorbent may be easily removed from the solution [19].

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Fe–O

O–Fe O–Fe

Fe–O O HO

OH

+ H2N

O

OH

H O N

OH

Pi-Pi interaction

Adsorption mechanism

H

H OH

OH

N O

H MIL-53(Fe)

NH2

Doxycycline OH

OH

O

OH

OH

O

Figure 8.6: Adsorption of doxycycline over MIL-53(Fe).

8.2 Future perspective MOFs deploy themselves in various fields. Their applications are increased as their development is increased. Studies have shown that some MOFs are not environmentally friendly. Certain characteristics of MOFs including synthesis through the hazardous solvent, choice of the toxic metal, and noneconomical method sometimes make the use of MOFs eco-friendly. The solvents used commonly for the synthesis of MOFs are nonrenewable. Synthesis through renewable solvents such as supercritical solvents and ionic liquids provides a new direction toward the MOF application. Water has also been used for the synthesis of MOFs, but the synthesis time is very large. To avoid such a hectic procedure, high-temperature water and other supercritical liquids can be substituted as they promise an efficient activity [20]. Pharmaceutical wastes have also been degraded by using photocatalysts, that is, titanium-based photocatalysts reveal efficient properties in the degradation of paracetamol. The high bandgap of TiO2 hinders its applications because it requires UV to degrade. To tackle this problem, MOFs-based photocatalysts may prove helpful in degradation of pharmaceutical waste. MIL-MOFs have also shown photocatalytic degradation under visible light [21]. ZIF8 is the only Photocatalytic MOF that is efficient in the degradation of acetaminophen yet [22]. Photocatalytic MOFs may occur as reliable pharmaceutical waste removal treatment shortly by eliminating drawbacks of using photocatalysts or MOFs alone. Although, MOFs are porous structures like hybrid crystals with a wide range of commercial applications based on different and controllable features such as high specific surface area, selective absorption/diffusion, low density, and excellent diversity. To synthesize such MOFs, a process known as high throughput synthesis is required. In this process bulk quantities of MOFs can be synthesized within hours which is not readily available which hampers the novel applications of MOFs. Aqueous or nonaqueous methods of MOFs preparations also have drawbacks as it is more timeconsuming and eliminate the efficiency of MOFs [9]. One possible way to overcome this

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hindrance is with the use of autoclaves such as the synthesis of Urea-MIL-101(Cr)@AC, which is used for the removal of sulfacetamide. This prospect can be studied further to make the best of the synthesis process [23]. MOFs often have their pore size in the micropore range, which reduces the efficient activity of MOF. This requires developing MOFs with the pore size in the mesoporous range. Extensive studies are ongoing to develop such MOFs [11]. Moreover, efficient removal of pharmaceutical waste requires a small particle size. The synthesis process must be managed to tackle the problems during the development of MOFs. Currently, MOFs that are water-stable include metal carboxylate, metal azo salts combined with ligands, and hydrophobic MOFs. Structural stability and small size are still the major challenge of these MOFs in real-life applications causing poor recovery, poor hydraulic efficacy, and low mechanical power. To overcome these challenges, studies have confirmed that the adsorption capabilities of MOFs can be improved by the fabrication of certain groups [24]. Efforts are being done to replace powdered forms of MOFs with fibrous materials, membranes, hydrogels or aerogels, macroscopic beads, and spheres by using fabrication techniques [25]. Further studies should be done focusing on the functional groups which may prove helpful in the removal of pharmaceutical wastes. Similarly, several fabrications can be done through various groups such as semiconductors and polymers. As mentioned by Ma et al. [26], the particle size of MOFs is controlled by the addition of appropriate contents of acids and basic groups [26]. Most MOFs consist of rather expensive transition elements. Employing such MOFs in treatment procedures also requires great financial assistance. Either the synthetic choice for MOFs should be economical or the treatment procedures should be cost-friendly. This will open a new gateway toward the development of efficient MOFs as the modern world is moving toward functionalized nanotechnology. Most of the MOFs are recyclable such as ZIF-8 [27], as they are regenerated after the treatment procedures. Many pharmaceutical compounds tend to destroy the MOFs during the removal process. This lowers the applicability of MOFs in the treatment procedures. This led scientists to a point where they need to synthesize such MOFs which are persistent in the presence of every possible compound with a high percentage of reusability. Powdered MOFs are not recyclable because they disperse in water causing secondary pollution [28]. Regeneration of MOFs is important as it tends to prevent the occurrence of secondary pollution. To develop such MOFs, scientists have suggested that MOFs should be composited with aerogels. This will increase the surface area enhances the porosity. Due to the hydrophobic nature of aerogels, secondary pollution is avoided. This future aspect also prevents the use of powder MOFs [28]. An excellent aerogel composite of ZIF-8 and reduced graphene oxide (GO) has been prepared previously by Mao et al. [29]. This will direct the progress in the removal of pharmaceutical wastes efficiently [29].

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Another major concern is the industrial production of the MOFs. As most of the MOFs require critical conditions to be synthesized that cannot be achieved ordinarily. The focus should be on better methodologies and cost-effectiveness. If there are some cost-effective and easy handling methods to synthesize MOFs, we can use them effectively and excessively against pharmaceutical waste. Furthermore, many novel MOF adsorbents must still be fabricated, with eager and enduring research interests into the landmark advancements for promising applications, so that the options of supplemental laboratory, medicative, commercial, and ecologic MOF uses can be brought to the forefront. Likewise, whenever new MOFs with better performance are discovered, many of the MOFs always are disregarded. Most MOFs’ experimentation attempts and operating costs are frequently squandered or underappreciated because of this. These MOFs, on the other hand, can be recycled and/or changed to provide even greater pollutant removal benefits. As a result, further in-depth research is required in this field. In addition, many pre- or post-synthetic alteration procedures alter pore characteristics, which complicate their further applications. Some specific techniques, such as the hydrophobic surface treatment, may be worth further exploration to solve these concerns. Experiments can also be rationally integrated with the computational design to produce new framework materials with great stability and specific features. Furthermore, there seem to be no systematic examinations of the MOF mechanical stability, which is an important feature in their industrialization. Certain approaches, like the single-crystal X-ray diffraction investigation and the theoretical calculation, may be useful in determining the mechanical stability of MOFs [6].

8.3 Conclusion MOFs are used for the removal of different types of wastes including pharmaceutical wastes. Several MOFs have been synthesized to overcome pollution through pharmaceutical waste. Different types of wastes are treated with different compounds. Many MOFs have been developed in recent years to remove pharmaceutical waste. MOFs can be modified with the help of different methods to increase their efficacy. A lot must be done regarding the alteration of their structure and properties. It is important to analyze the preparation method of MOFs, the use of metals and solvents in them. The previous study highlights some challenges in the way of MOFs including small pore size, small surface area, degradation of MOF, high cost, and so on. We have suggested some efficient ways to overcome these difficulties. Photocatalytic MOFs may prove advantageous in pharmaceutical waste treatment as photocatalysts enhance the efficacy of MOFs. A lot of strategies should be adopted for regeneration and reusability of the MOFs to enhance their applicability in real-life experiments because it seems the need of our future. MOFs are paving

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Figure 8.7: Future Prospects in MOFs.

their way in biomedical and industrial applications prominently. So, it is the dire need of the near future to fulfill the demand for MOFs. For this purpose, it is necessary to use a different strategic approach to make MOFs eco-friendly and economical. Fabrication of MOFs with other suitable metals, nanomaterials may eliminate the hindrances regarding small pore sizes and small surface area of MOFs.

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Huang, L., R. Shen, and Q. Shuai, Adsorptive removal of pharmaceuticals from water using metal-organic frameworks: A review. 2021. 277: p. 111389. Morone, A., et al., Removal of pharmaceutical and personal care products from wastewater using advanced materials. 2019. p. 173–212. Singh, N., et al., Medical waste: Current challenges and future opportunities for sustainable management. 2022. 52(11): p. 2000–2022. de Andrade, J.R., et al., Adsorption of pharmaceuticals from water and wastewater using nonconventional low-cost materials: A review. 2018. 57(9): p. 3103–3127. Rienzie, R., S. Ramanayaka, and N.M. Adassooriya, Nanotechnology applications for the removal of environmental contaminants from pharmaceuticals and personal care products. In Pharmaceuticals and personal care products: Waste management and treatment technology. 2019: Elsevier, p. 279–296. Ali, S., et al., Challenges and opportunities in functional carbon nanotubes for membranebased water treatment and desalination. 2019. 646: p. 1126–1139. Wei, Y., et al., Multilayered graphene oxide membranes for water treatment: A review. 2018. 139: p. 964–981. Bandehali, S., et al., High water permeable PEI nanofiltration membrane modified by L-cysteine functionalized POSS nanoparticles with promoted antifouling/separation performance. 2020. 237: p. 116361. Zhang, R., et al., Highly effective removal of pharmaceutical compounds from aqueous solution by magnetic Zr-based MOFs composites. 2019. 58(9): p. 3876–3884. Wang, Y., et al., Removal of pharmaceutical and personal care products (PPCPs) from municipal waste water with integrated membrane systems, MBR-RO/NF. 2018. 15(2): p. 269. Qian, Y., F. Zhang, and H.J.A.F.M. Pang, A review of MOFs and their composites‐based photocatalysts: Synthesis and applications. 2021. 31(37): p. 2104231. Aljeboree, A.M. and A.N.J.J.o.P.S. Alshirifi, Adsorption of pharmaceuticals as emerging contaminants from aqueous solutions on to friendly surfaces such as activated carbon: A review. 2018. 10(9): p. 2252–2257. Ariffin, M. and T.S.T.J.E.m. Zakili, Household pharmaceutical waste disposal in Selangor, Malaysia – Policy, public perception, and current practices. 2019. 64(4): p. 509–519. Wang, D., et al., Simultaneously efficient adsorption and photocatalytic degradation of tetracycline by Fe-based MOFs. 2018. 519: p. 273–284. Naeimi, S. and H. Faghihian, Application of novel metal organic framework, MIL-53(Fe) and its magnetic hybrid: For removal of pharmaceutical pollutant, doxycycline from aqueous solutions. Environ Toxicol Pharmacol, 2017. 53: p. 121–132. Al Obeidli, A., et al., Recent advancements in MOFs synthesis and their green applications. 2021. Abdelhameed, R.M. and H.E.J.J.o.c. Emam, Design of ZIF (Co & Zn)@ wool composite for efficient removal of pharmaceutical intermediate from wastewater. 2019. 552: p. 494–505. Fan, G., et al., Rapid synthesis of Ag/AgCl@ ZIF-8 as a highly efficient photocatalyst for degradation of acetaminophen under visible light. 2018. 351: p. 782–790. Zhou, Q. and G.J.I. Liu, Urea-functionalized MIL-101 (Cr)@ AC as a new adsorbent to remove sulfacetamide in wastewater treatment. 2020. 59(26): p. 12056–12064. Ibrahim, A.O., et al., Adsorptive removal of different pollutants using metal-organic framework adsorbents. 2021. 333: p. 115593. Huang, W., et al., Laccase immobilization with metal-organic frameworks: Current status, remaining challenges and future perspectives. 2020. p. 1–42. Ma, X., et al., Metal–organic framework films and their potential applications in environmental pollution control. 2019. 52(5): p. 1461–1470.

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[27] Song, L., et al., Repetitive in situ recycling of degraded metal-organic frameworks within nanocapsules. 2022. [28] Cheng, P., et al., Practical MOF nanoarchitectonics: New strategies for enhancing the processability of MOFs for practical applications. 2020. 36(16): p. 4231–4249. [29] Mao, J., et al., Constructing multifunctional MOF@ rGO hydro-/aerogels by the self-assembly process for customized water remediation. 2017. 5(23): p. 11873–11881.

Muhammad Yahya Tahir, Awais Ahmad, Rafael Luque✶

9 MOF – a promising material for energy applications Abstract: Metal-organic frameworks (MOFs) accumulated from metal-based protuberances with equivalent carbon-based linkers took much attention having the benefits of the unique internal surface area, tailored chemistry, versatile nature, high porosity, and small size with promising and intriguing characteristics. The synthetic scheme of MOFs can fix its structure and properties, by adjusting the synthetic parameters, for example, metal precursor, organic ligands, ion concentration, pH value, and temperature. Recently, one of furthermost vigorous investigate arenas is exploring energy application of MOF-derived constituents. In this chapter, our focus is on the recent progress of MOF-based materials for energy storage, fuel cells, electrochemical energy storage, and conversions. We also discussed challenges and opportunities in advanced energy application with MOF-derived materials.

9.1 Introduction In recent years, clean energy methodologies receive great attention due to environmental pollution, and shortages of resources resulted from excess usage of fossil fuels [1, 2]. In this esteem, a lot of auspicious technologies were adopted by using metal–organic frameworks (MOFs) as long-term energy storage, electric power generation’s energy carrier, and energy transportation toward long-distance area [3]. Due to the increasing demand of energy, various electrochemical energy storage and light harvesting systems are extensively used [4]. MOFs are assembled from nodes of metals and organic linkage. They possess high surface area and unvarying pore sizes when compared to mesoporous and outmoded microporous materials. Because of their versatile structure and high surface area, they show intriguing characteristics in the extensive range of submissions such as catalysis, separation, or sorption [5–9]. MOFs also play the role of host in the synthesis of metal oxide nanocomposites to generate MOF composites [10], as well as a precursor toward assembled MOF derivatives,

✶

Corresponding author: Rafael Luque, Departamento de Química Orgánica, Universidad de Córdoba, Campus de Rabanales, Edificio Marie Curie (C-3), Ctra Nnal IV, Km 396, Córdoba, Spain, e-mail: [email protected] Muhammad Yahya Tahir, Department of Environmental Science, Government College University Faisalabad, Punjab 38000, Pakistan Awais Ahmad, Departamento de Química Orgánica, Universidad de Córdoba, Campus de Rabanales, Edificio Marie Curie (C-3), Ctra Nnal IV, Km 396, Córdoba, Spain

https://doi.org/10.1515/9783110792607-009

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for example, carbon composite and porous carbon which possessed electrochemical conversion and storage [11, 12]. Currently, MOFs are applied in many energy applications, for example, physical methane and hydrogen storage, chemical storage of hydrogen, and electrochemical and solar energy conversion and storage [13–23]. MOFs are accumulated since metal-based bumps with equivalent carbon-based linkers took much attention having the benefits of the unique internal surface area, tailored chemistry, moveable voids, and exceptional crystal-like structure [24, 25]. However, the synthetic scheme of MOFs can fix its structure and properties, and synthetic parameters are metal precursor, organic ligands, ion concentration, pH value, and temperature. Different synthetic methods have been used to synthesize MOFs including microwave and hydrothermal techniques [26]. To functionalize the organic ligand, another emerging scheme is postsynthetic modification (PSM) [27]. Since the last two decades, moreover 20,000 MOFs have assembled besides examining on the basis of PSM and assembling tactic [28]. The sole besides desired crystal-like structure of MOFs help out in advanced energy applications. The most efficient characters of MOFs are high porosity and small size and could be obtained by paying attention during assembling [29]. The porosity and small size of MOFs causes the separation and adsorption of small molecules. It also purifies a large number of accessible active sites and allows diffusion. Whereas using lengthened organic linkers, we can increase the pore size to enlarge isoreticular assembly [30]. The most attracted attentions of MOFs are gas storage and electrochemical energy storage. This potentially useful application is attained by thermal transformation of MOFs into metal oxide and carbon in one-dimensional (1D) and two-dimensional (2D) morphologies [31]. The Co3O4@CoS, Co3O4@C, and Co3O4@CoP nanorods had efficaciously assembled by sulfurization, corrosion, carbonization, and phosphorylation reactions of ZIF-67/cobalt carbonate hydroxide nanorods [32]. The combined effect of abundant active sites, improved conductance, facile ion diffusion effective is due to MOF’s sole classified assembly, linked synergistic effect, and maintainable dispersal channel for mass carriage. KOH-assisted sonochemical conduct then updraft instigation of MOF derivative C nanorods assembled by graphene nanoribbons displayed efficient supercapacitor performance [33]. These materials are tangled in highly efficient O2 evaluation of electrocatalysis; for example, microrod arrays were synthesized from carbon-confined nickel–cobalt@NiCoO2 nanoparticles [32]. In this chapter, we have discussed many challenges and opportunities of MOFderived technologies. This chapter gives advantages to researchers to realistically design and progress MOF-derived constituents for energy applications, especially clean energy.

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9.2 MOF application as fuel cell The devices that have the ability to convert chemical energy into electric energy from oxidizers to fuels are called fuel cells. They are suitable for utilization of alternative energy source. Protons are fashioned by electron drawn from H2, and this reaction befell at the anode of hydrogen fuel cell. These electrons are transported to cathode via external circuit fabricating direct current [34]. While protons transferring to cathode, they have to cross the penetrable membrane to alter chemical hooked on electrical energy [35]. Consequently, efforts have been made to survey recent progress in advance fuel compartments [36].

9.3 Electrochemical energy conversion devices On the cathode of electrochemical energy adaptation strategies, O2 reduction reaction occurred [37–39]. Recently, many findings showed that replacement of metals than N atoms on permeable C can ignite oxygen reduction reaction [40, 41]. To endorse oxygen reduction reaction, a number of single metal atom-loaded C- and N-doped carbons owing to high surface area have been established. In this reaction, MOFs are used as sacrifice templates under thermal alteration. The oriented synthesis of carbon nanotube (CNT)-derived MOFs via pyrolysis reaction was done in 2017 [42]. In this research, a lot of CNT-assembled composites were manufactured via moderating the equivalent MOFs. These materials possessed debauched mass transport, highly active in electrocatalytic and best strain lodging. Other characteristics of these materials include suitable pore size dispersal, large surface area, vigorous framework, inland voids, and fitting doping. Moreover, the hierarchically porous N-doped metal-free oxygen reduction reaction’s catalyst synthesized by pyrolysis reaction of ZIF-8 followed with NH3 activation which also introduced optimized and mesoporous nitrogen species and enhanced the oxygen reduction reaction’s performance as compared to commercial Pt/carbon [43]. Novel procedures have been advanced for synthesizing metal/N-carbon materials on the basis of porous MOFs [44–48]. In situ, nonprecious metals besides nitrogen-doped carbon-based oxygen reduction reaction’s catalysts were manufactured via updraft handling of covalent organic polymers in 2017 [49]. By MOFs, the growth of covalent organic polymers was delimited, and it leads to high BET area with unvaryingly disseminated metal/nitrogen-active sites. It gained catalysts of 16 mV positive half-wave probably equated to benchmarked Pt/carbon. The fusion of porous Fe–Co alloy/N-doped carbon crates was made in 2018 by restricted pyrolysis strategy “MOF-in-MOF hybrid” [50]. A crate-shaped hybrid factualcontaining Fe–Co alloys was attained by the pyrolysis of Fe-OOH rod-encapsulated zinc-MOF@cobalt-MOF hybrids. In alkaline solution, the gained hybrid cages showed higher electrocatalytic

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presentation for the oxygen reduction reaction as it exhibited physical and compositional recompense.

9.3.1 Proton conduction Under massive dampness, anhydrous-state polymers are well organized, and they are the most prevalent contenders to proton-conducting materials [51]. Their wide applications are restricted as their usage temperature is lower than 80 °C and have high cost, urbane amalgamation methods [52]. MOFs have involved cumulative courtesy in proton conduction due to their massive designability and steady crystal-like spongy edifices [53]. The intermittent proton conducting hallways were caused due to bulk segment and smidgin boundaries [54, 55]. A sequence of 2D MOFs can summarize dissimilar absorptions of visitant H2O fragments and then show proton transmissions associated with dithiooxamide derivatives besides copper particles premeditated by Kitagawa and coworkers in 2002 [56]. Zinc-MPF was manufactured that was examined as solid state and proton conducting substance in 2009. The H2O-mediated proton directing MOF synthesized material showed slog professionally at less-slung temperatures ranging 20–80 °C and contingent on incidence of H2O molecules or else H2-bonding connections associate H2O. This type of MOF is a well-established proton conductor [57]. An anhydrous proton accompanying MOF which works overhead 100 °C temperature through swapping H 2 O with amphiprotic carbon-based molecule is also synthesized and is also a wellestablished proton conductor [58]. Other numerous approaches to sensibly design MOFs include the functionalization of the carbon-based organic ligands such as SO3H, COOH, OH, and dissimilar proton haulers within the holes of MOFs [59–62], the polymers [63], monoatomic transition metals, CNTs, graphene, and other suitable materials [64–66]. Lanthanide frameworks with Ln-PCMOF-5 had hired in place of proton showing constituents of [(Ln(H5L)(H2O)n](H2O), and this series of isomorphous was synthesized in 2017 [67]. Herein, L = 1,2,4,5-tetrakis phosphonic-methyl benzene, and Ln = Pr, La, Sm, Ce, Nd, Gd, Eu. They possessed quartz assembly and proton conductions for the lanthanide and Pr multiplexes that had sophisticated and further adherents of succession. Lanthanide contractions cause proton accomplishment ways and transform of unit cell dimensions. It has been proved by the Le Bail method appropriately that the crystallographic a-axis sideways network can remain mixed in augmentations fewer than 0.02 Å [68]. ZIF-8 (DNA@ZIF-8) was manufactured via a solid-confined renovation procedure and fusion of proton conductive crust erected solo-component DNA fragment [69]. DNA@ZIF-8 had supplementary probable to create the hydrogen bond links among the incorporated H2O iotas as the hydrophilic groups privileged the hollows of DNA iotas present. In addition, the methanol crossover is restrained by smaller

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size of DNA@ZIF-8 membrane. Moreover, during the water uptake regimen, crystalline assembly thwarts swelling. Moreover, underneath the active control, high proton conduction constituents were established via surface-mounted MoF as SURMOF-associated single azobenzene lateral assemblies burdened with proton directing guests [70]. A swapping amid with a high conductivity causes the materials to upgrade proton conductivity. It is instigated by reversible switch among the guest molecules containing 1,2,3triazole, light-induced trans–cis isomerization of the host framework and 1,4-butanediol. By short relative humidity, the proton conductivity of the proton-conducting constituents is imperfect. It leads to breakage of water-mediated H-bonding nets [71]. Physically flexible and chemically constant MOF BUT-8(Cr)A was manufactured in 2017. Its chemical composition had Cr3(µ3O) (H2O)3(NDC(SO3H5/6)2)3. This MOF was synthesized from a naphthalene-2,6-dicarboxylate organic linker. These linkers were ornamented with 4,8-disulfonaphthalene-2,6-dicarboxylatlate, rich sulfonic acid sites, and Cr3O(OH)(CO2)6 as tributary building units [72]. Steadiness of Cr3(µ3O) (H2O)3(NDC(SO3H5/6)2)3 confirmed via durable Cr–O pledges in the Cr3O (CO2)6 units. Physical elastic skeletons obtained by knee cap of the carboxylate functions and NH2 (CH3)2+ were subsidized to highest proton conductivities. It retains high proton conductivities unfluctuating in an extensive array of relative humidity and also temperature.

9.4 MOF as energy storage and conversion 9.4.1 Batteries One of the best energy storing and conversion expedient is battery, to provoke inordinate curiosity [73]. The H2O splitting side reactions of redox stream batteries and lowslung functioning voltage less than 2 V advance numerous amalgam methodologies [74]. Metal ions in batteries, which are also rechargeable batteries, transfer from negative electrode to positive electrode. These metal ions formerly originate back all through the charging and discharging procedures. The cathodal reactants (O2) are taken straight from the ordinary atmosphere, owning advanced energy compactness, hypothetically than that of metal ion batteries [75]. Sulfur by way of cathode and metal as per anode demonstrate curiously heavy capacitance in metal sulfur batteries. In pulverization of electrode, electrochemical possessions of metal sulfur batteries are still essential to examine [76]. The electrochemical responses take place at comparable electronic ingredients, for example, the electrodes (cathode and anode). These batteries possessed electrolytes which deliver conveyance of ions besides chunk electronic transmission. The expansion of novel kinds of supplies for batteries is highly

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required, and practical materials that are secondhand in these components administrate the presentation of devices [77].

9.4.2 Metal ion batteries Li-ion batteries have established steadily and their vigor thickness spreads to 250 Wh/kg active to now, whereas charges are successively on lowest level and they were commercialized in the early 1990s [78]. Here, we have mentioned some Li cathode in Table 9.1. For negative/anode electrode, graphite is mainly used, and for positive/cathode, layered oxides such as LiFePO4 and LiMn2O4 are commonly used. MOF has been settled as separators and electrode–electrolyte constituents in Liion batteries [79–81]. When MOFs are secondhand for the batteries, a model approach is adapted or composite MOFs with conductive ingredients [80, 81]. MOFs have completed inordinate charities toward the progress of Li-ion batteries (LIBs); in this esteem, this rummage sale is by way of precursors and then prototypes for C-based anodes [82–91]. MOFs were transmuted into diatom-like, hierarchical structures as a carbon-based material in 2018, through invitee enclosures besides highest temperature MOF–guest interface [92]. Through unassuming variations in chemistry of the MOF and guest, the sound structure of the carbon-based assemblies can be meticulous and gained assemblies to own sole recompenses for an active-charging LIB anode. Herein, we have mentioned some Li anode in Table 9.2. To endorse the Li+ transport kinetics amid the solid-state electrolyte, MOFs can also attend as electrolytes. Solid-like electrolyte present on ionic-liquid-impregnated MOFs amassed into rechargeable Li|LiFePO4 solid-state batteries. It revealed an outstanding electrochemical recital active loading of 25 mg/cm2 on extensive working temperature of −20–150 °C. Table 9.1: LiB cathode. Sample

MOFs

C⊃NiS

MOF-

HCSP⊂GCC

ZIF-

Capacitance (mAh/g) – 

Current density

Capacitance retention

Cycle number

Reference

 mA/g





[]

 mA/g





[]

−



[]

–

–

[]

NiSb⊂CHSs

Ni-MOFs

.

 mA/g

.

LFP/N-CNWs

MIL-(Fe)

.

, mA/g

LVP/P-C

V-MOFs



 C

.

,

[]

LVP@M-

MIL-

.

. C

.

,

[]

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115

Table 9.2: LiB anode. Sample

MOFs

Capacitance Current (mAh/g) density

Si@ZIF--N

ZIF-

,  mA/g

Sn@NPC

Sn-MOF

C/ZnO quantum dot

IRMOF-

Graphene/CoO

ZIF-

CoS@PCP/CNTs

ZIF-

, . A/g

ZnSNR@HCP

ZIF-

,  mA/g

CoO/CNT

ZIF-

, . A/g

TiO/C

MIL(Ti)

CCP

Capacitance Cycle Reference retention (mA h/g) number ,



[]

, . A/g



,

[]

,  mA/g

,



[]





[]

–

–

[]





[]

–



[]

  A/g



,

[]

Cu-Co-ZIF

  mA/g





[]

LiTiO/C

Ti-MOF

  mA/g



,

[]

CoO@N, S-C

Co-MOF

 , mA/g





[]

ZnO/C

MOF-





[]

 , mA/g

,  mA/g

9.4.3 Metal–sulfur batteries LIBs have the fewer capacity of marketable cathode ingredients, and they are achieving the consideration due to the quick progress of ionic batteries [111]. For the conservation-type cathode constituents, the high profusion in natural possessions, as well as low cost, sulfur is a well-thought-out as an auspicious contender due to high theoretical capacity [112]. There are three challenges faced by metal–sulfur batteries and these are like underprivileged electrode rechargeability, and inadequate amount competence occurs from the isolating nature of sulfur as well as solid lessening products [113]. The second challenge relates to the capacity dwindle occasioned from ferrying of numerous decipherable polysulfide intercedes to conclude among the anode as well as cathode 306. In the same way, the third challenge is related to the deprived controllability among electrolyte interface and metal [114]. Some issues that have been faced by the centrifuge for the metal–sulfur batteries were recognized and they can detach anode as well as cathode which thwart it from short circuit and also make available microchannels for diffusion off ions [115]. In Li–S batteries, a well-organized barricade known as Co9S8 Celgard was equipped for the lithium polysulfides, and they were derivatives from the cobalt-MOFs. They influenced perpendicular resonating

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nanoarchitecture as well as highest conductivity of electricity [116]. Co9S8 Celgard separator has showed the positive impact toward the attained batteries, that is, Li–S with preliminary precise capacity of 1,385 mAh/g afterward 200 sequences. Discriminate compensations of the cathode material-based metal sulfur batteries have also assisted as MOF materials. Between ion, electron, as well as electrode, huge permeability and explicit surface expanse have donated the conversation in them [117]. Moreover, MOF can also synchronize with sulfur species like lithium, oxysulfide, lithium sulfide, as well as sulfur and they owed to their unsaturated metal cores [118]. For sulfur fecundation in the Li–sulfur batteries, MIL-100 (Cr) has been cast off as congregation for this 19. In the case of MOF host, sulfur has been exploited and is inadequate through the low electrical conductivity [119]. In this esteem, MOF-based polymer as well as MOF-based carbon composites exhibited the greatest probability due to its highest electrical conductivity. To restrain sulfur in the Li–S batteries, in 2018, three MOFs like MIL-53, MIL-101, as well as PCN-224 have been introduced, which accompany discrete pore geometries composited with polypyrrole [120]. High-rate performance with explicit capacity, that is, 790 mAh/g, has been exhibited among polypyrroles in the PCN-224 composite holding cross-connected channels, and it has observed subsequently 400 cycle tests at 5.0 C/10.0 C, correspondingly. CNTs and carbon polyhedrons in the form of hybrid nanostructure as well as self-standing-permeable carbons had been encompassed via compounds, on the other way. CNTs are preferred all over the other composites, that is, HKUST-1, which is consequential from permeable carbon polyhedron as well as disheveled through peripheral CNTs [121]. Diffused as well as self-standing conductive background displayed an unresolved cycle with dimensional deterioration of 0.0054% apiece sequence which completed 500 sequences as well as volumetric dimensions of 960 Ah/L. Emotive and all-pervading CNTs have indicated that carbon polyhedrons exhibit huge aperture spaces as well as dynamic boundaries. So, it is contributive to the highest sulfur employment and unresolved electrochemical presentations. With the use of chemical vapor deposition, another composite like ZIF-8 had collective inside CNTs as self-supporting three-dimensional (3D)-permeable sulfur congregation for lithium/sulfur batteries, correspondingly [122]. Subsistence of dissimilar form of generally powder arrangement or thin-film conductors, in the ZIF-8@CNT, ZIF-8 assisted by means of sulfur host. Sulfur has restrained polysulfide intercedes through mutually physical imprisonment and chemical connection. And 3D-permeable assembly demonstrated huge precise capacity, areabased capacity, and cycling permanency.

9.4.4 Other batteries Some state-of-the-art batteries are based on MOF premeditated and established freshly. To understand this concept, here is an example coded in view of highest competence

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of carbon dioxide imprisonment and monodispersed vigorous metal positions for Li2CO3 disintegration. So, probable of a succession of MOFs as a permeable catalytic agent in the carbon dioxide electrodes has been acknowledged [123]. The emancipation capacity of 2,3 dioxido-1, 4-benzenedicarboxylate has been exhibited, and it is approximately 18,022 mAh/g at 50 mAh/g even though Mn(HCOO)2 reserved a very low charge potential, that is, around 4 V unfluctuating by 200 mAh/g aimed at completing 50 sequences. In additional exertion, an aqueous zinc polyiodide oxidation–reduction movement battery operation was conveyed, and it was equipped through dropping MIL-125-NH2 as well as UiO-66-CH3 on graphite caressed exteriors [124]. In redox reaction, MIL-125-NH2 improved graphene framework showed more efficiency than UiO66-CH3. In ZIB conductors, UiO-66-CH3 exhibited supplementary chemical stability rather than the other composite, that is, MIL-125-NH2. Moreover, MOFs as well as MOF-derived composite had likewise conveyed as per cathode of lithium/selenium batteries. Lithium/tellurium batteries are most versatile now a day’s [125, 126].

9.5 Supercapacitors Supercapacitors are also known as electrochemical condensers which have widespread concentration unpaid to their high influence compactness, debauched charge–discharge frequency, elongated life cycle, as well as environmental approachability [127, 128]. Flanked by the battery and conservative dielectric capacitors, supercapacitors play a significant role as well as well-thought-out as transitional in between them. Supercapacitors have been alienated into two types, that is, twofold layer electric capacitance as well as self-styled capacitance, and these are separated rendering to the energy packing mechanism. In electric double layer capacitor EDLCs, carbon and carbon-based materials have been used, which comprise corporeal adsorption as well as desorption of ions at the crossing point among an electrolyte as well as an electrode [129]. Among the electrode and electrolyte, metals with their oxides/conductive polymers have exposed pseudocapacitance behaviors through rescindable oxidoreduction reactions. With the use of MOF-based carbon composites like oxides of metals, sulfides of metals, as well as their amalgams, momentous revolutions of supercapacitors have been accomplished [130]. Carbon-derived MOFs have used supercapacitors in 2008, and results illustrate the brilliant presentation of electrochemical. On the other hand, nickel oxide nanomaterials were manufactured through strengthening of MOFs underneath air and also exhibited an unresolved electrochemical capacitance [131]. Amorphous synchronized polymer shells have been used to synthesize seven-layer nickel/cobalt oxide CNTs and have been done through quick thermal oxidation procedure in 2007 as in table 9.3 [132]. In contradiction of graphene and multishelled mesoporous carbon domain, oxide particles of nickel–cobalt unveiled excellent charge storage ability toward aqueous electrolyte and hybrid supercapacitors.

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Table 9.3: Supercapacitors. Sample

MOFs

HNC

ZIF-

.

.

.

,

[]

NPCF

ZIF-

.



.

,

[]

NCF

ZIF-

.



.

,

[]

HCCN

MIL--NH

.



–

,

[]

–



–

–

[]

.



–

–

[]



.



.

,

[]





.

,

[]

ZIF-@PZS-C ZIF- NPC WO/C

MOF- Zn-MOF

Capacitance (A/g)

Current density Capacitance (F/g) retention (F/g)

Cycle Reference number

MCG

Mn-MOF



Ni/C

Ni-MOF-







,

[]

MnOx-CSs

Mn-MOF





.

,

[]

On the large scale, submission of MOFs has limited the implementation of supercapacitors due to deprived conductivity status as well as chemical instability of MOF-derived materials [143]. Conducive MOF comparable Ni3(2,3,6,7,10,11hexaiminotriphenylene)2 and Ni3(HITP)2 have assisted by way of conductor constituent destitute of conductive essences as in EDLs during 2017. Since composition of the Ni3(HIPT)2 is composed of π-stacking interaction among 2D layers, it pierced via 1D cylindrical network of approximately 1.5 nm in diameter. Non-carbon-active materialderived EDLC exhibited huge surface area which standardized the capacitance of roughly 18 µF/cm2 as well as lessen comparable confrontation in sequences. Furthermore, the MOF-based maneuver exposed a midair capacitance which surpasses most of the carbon-based materials, as well as capacity maintenance superior than 90% concluded 10,000 series and this has been done in stroke with marketable devices. Since in 2018, ultrasmall composite, that is, hexaaminobenzene, has erected 2D MOF, and it laboring in place of highest presentation electrode in equally aqueous solutions (i.e., acidic and basic) [144]. Insignificant magnitude of HAB contributed MOF’s huge packing density and classified spongy assembly. It gives rise to high volumetric capacitances which is approximately 760 F/cm3 as well as highest area-based capacities, that is, over 20 F/cm2. It also unveiled exceedingly revocable oxidoreduction performances and admirable driving constancy.

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9.6 Solar energy harvest and conversion With minutest undesirable environmental impressions, solar irradiation is also known as free natural energy reserve and it turns out to be progressively momentous to address the indispensable complications in energy as well as environment [145]. Photocatalysis is determined through solar energy and is also well-thought-out as an operative passageway to renovate solar energy as well as it makes available a probable resolution for energy catastrophe and environment. Progressive submission of the photocatalysis is primarily engrossed on water noxiousness dilapidation, water excruciating, conservation of carbon dioxide, as well as carbon-based amalgamation [146–152]. Furthermore, collected lunar oomph might remain deposited electrochemically by way of modification in the Nernst potential of oxidoreduction electrolytes and also in chemical condenser of electrical compartment [153]. In cooperation with the abovementioned conducts, we can steadfastly encounter huge operative gathering. Its loading of astral energy as chemical energy is deprived of undesirable conservational influence [154] with respect to MOF by means of auspicious constituents for conservation of solar energy which stimulates widespread attention by the investigators [155, 156].

9.7 Photocatalytic hydrogen production In the research society, the progression of H2 from liquid in incidence of photocatalyst to simplify displacement of vestige energies has become question of this era. MOFs with their composites like [Ru2(1,4-BDC)2]n (1,4-BDC = 1,4-benzenedicarboxylic acid) were premeditated by way of photocatalyst aimed at persuading progression beginning liquid underneath radioactivity of evident sunlit 18. It can be voluntarily accustomed in the MOF assembly which has the uppermost engaged molecular detour of biological ligand for the purpose of exploiting the solar energy gathering. In addition, to the convinced positions, enthusiastic electron would be encouraged in place of metallic protuberance or else lowermost untenanted molecular detour location of carbon-based linker. Relocation detachment of photoexcited custody crystal-like assembly can be augmented, concluding supervisory peripatetic detachment as well as positions that resolute via the accumulating components. Spectroscopic study had revealed the data on ZIF-67-based mechanism of atomicscale-associated extraordinary commotion in the progression of hydrogen reaction. Rendering to the time-resolution ophthalmic outcomes as well as catalytic presentation, it had originated that electron transmission pathway somewhat more common than energy transference pathway as due to significant influence for hydrogen evolution reaction (HER) movement. The basic purpose is that electron pathway of HER has the three instructions of degree which are sophisticated than that of the energy transmission progression. The premeditated sample displays extraordinary commotion in

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the 40,500 µmol H2/g of HER. A self-healing organization had established, and it has encouraged through self-repairing apparatus of the ordinary photosystem II in floras, furthermore. Bipyridine embedded with UiO-type MOF has not only maintained HER but also extemporaneously refurbished the entrenched molecular catalytic agent as well as photosensitizer throughout photocatalytic hydrogen progression. Pt0.1-Ir-BUiO exhibited a moderately constant photocatalytic presentation deprived of colloidal establishment aimed at slightest 6.5 times and in standardized complement, molecular catalytic agent converted a colloid unbiased after 7.5 h [157]. Therefore, the incorporation of augmented MOF with purposeful materials unveiled prodigious aptitudes in photocatalysis. Introduction of the constituents has been functionalized as cocatalyst, sensitizer, as well as energy source to procedure heterostructures. They even also empower multifunction via single amalgam quantifiable [158]. Through the encapsulation of metal nanocomposites hooked on MOFs, accumulation of metal nanomaterials can be circumscribed. Single Pt molecules are magnificently restricted into MOFs that exhibit electron transmission from photosensitizer MOF into Pt acceptor for the construction of hydrogen via excruciating aquatic underneath noticeable sunlight irradiation [159]. Moreover, the cobalt molecule is realistically encapsulated privileged the coops of MOF-MIL-125-NH2 and its demonstrations the visible-light-driven catalyzing hydrogen atom construction. Thus, noble-metal-free amalgamated photocatalyst simplified the photoinduced custody transmission from MIL-125-NH2 to the cobalt(11) multifaceted as well as better-quality 3D charge parting, consequently, improving the photocatalytic effectiveness of hydrogen production, as suggested. Innumerable inanimate photocatalysts, that is, TiO2, zinc oxide, C3N4, as well as cadmium, have composited with MOF for observable light obsessed by catalyzing hydrogen manufacture and they can progress their considerable yield as well as solar oomph preservation. Above and beyond, sulfides of metals are observed as virtuous contenders for photocatalytic hydrogen manufacture unpaid to their durable preoccupation in discernible light section. Upright free metal, MOF derivative onion slicetype muffled and arranged Co4S3 had deep-rooted against cadmium nanocomposites for photocatalytic H creation [159]. Thus, assimilation of Co4S3 per cadmium subdivisions efficiently augmented charge departure. Improved Co4S3 and cadmium photocatalyst were directed toward boosted proportion of hydrogen construction with 12,360 µmol/h g underneath replicated irradiation of lunar sunlit.

9.7.1 Photocatalytic carbon dioxide reduction Universal warming has become unpaid to the disproportionate emission of the carbon dioxide from engrossed cumulative consideration [160, 161]. A superlative approach of tumbling as well as overwhelming the extreme CO2 has to photosynthesize carbon comprising chemical stuffs like methane, HCOOH, HCHO, and CH3OH, owing

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to compensations of little energy charge, huge effectiveness, and strong recycling capacity. Commonly, photosynthesis comprises three steps like physical adsorption, transmission charge at electrons and hovels, as well as photocatalytic adaptation and desorption [162]. In photocatalytic carbon dioxide lessening, carbon dioxide has frequently liquefied in carbon-based mass medium like acetonitrile as well as tetrahydrofuran [146], though thermodynamically unchanging assembly of CO2 fragment and endothermic development of lessening are prime to low carbon dioxide alteration frequency. However, the amount of exceedingly well-organized photocatalysts had established to progress conversion of carbon dioxide efficiency. MOF catalyst for photochemical CO2 decrease had manufactured through straight assimilation of a catalytic constituent, that is, [ReI(CO)3(dcbpy)Cl] (dcbpy = 2, 2′-bipyridine-5, 5′-dicarboxylic acid) hooked on UiO-67. In credits toward exceedingly chemical suppleness as well as exclusive ophthalmic and electrical rejoinders have obtained MOFs, they could satisfy harsh requirements. Furthermore, it had originated that highest photocatalytic commotion of MOF-Fe3 might be attained, fluctuating its compactness in the framework. Catalytic MOF elements can be spatially narrowed exclusive improved arena of electromagnetic which neighboring the silver plasmonic nanotubes. They also progress the presentation of photocatalysts toward carbon dioxide reduction underneath observable light irradiation.

9.7.2 Photovoltaic conversion Solar cells are correspondingly notorious as photovoltaic cells and they have apprehensions of the energy from easily obtainable sunlight as well as chances it had about the treasured electrical energy. So, this technology has been based on the nature of the elements like crystalline nature of silicon, gallium arsenide, cadmium telluride, indium gallium diselenide, perovskites, as well as therefore many others [163]. Conspicuously, MOF as well as their complexes and MOF derivatives are auspicious for substituting the outmoded photovoltaic constituents for their characteristics such as solid light harvesting facility, since obstructive character and low nonradiative transporter recombination tariffs have been observed. Furthermore, MOF-based constituents can likewise synthesize inadequacies of outmoded photovoltaic supplies toward convinced level, and these are following like high preliminary fixing amount, extensive reimbursement epochs. Then minor proceeds as well as low-energy adaptation frequency [164]. TiO2@ZIF-8 complexes had cast off by way of conductor constituents aimed at dye-sensitized solar cubicles in 2011 [165]. While in 2013, concluded layerthrough-layer tactic, two tinny flicks, that is, DA-MOF and L2-MOF of porphyrinbased MOF happening functionalized shells had manufactured designed for sunlit collecting as well as ultrafast movement of long-distance energy. The strategy empowers squashy microporous MOFs encompassing manageable free-base porphyrins, and it has legalized straight MOF integration of unmetalated porphyrins. Lately, 2D

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MOF film had made up a solution process that might substitute extensively cast-off vacuum-deposited indium tin oxide. Utmost of MOF-based constituents designed for solar cells are amalgamations of MOFs as well as their derivatives as conventional optical ingredients [160–162]. The situation had originated from electronic assembly of engendered transporting electron coverings through nTi-MOFs were additionally appropriate for charge injection and transmission since the perovskite to electrodes.

9.8 Electrochemical energy conversion and storage Prodigious exertions have finished near progress the alteration of electrochemical oomph and packing technologies, counting electrocatalysis of water, fuel cells, batteries then supercapacitors [166]. MOFs besides their composites/derivatives hold structures like huge definite surface area, highest permeability also assortment in configuration besides construction, tunable functionalities, which have auspicious for conversion of electrochemical energy and storing [167].

9.8.1 Electrocatalytic water splitting Operative energy adaptation strategies like fuel cubicles, metal–air batteries, water excruciating electrolyzers, as well as compartment electrolysis rely primarily on three significant factors like H2/oxygen development reactions and O2 reduction reactions. Nevertheless, these reactions are inadequate through the inflexible double oxygen bond development as well as lethargic proton joined from electron transmission subtleties. Universally, electrolytes have encumbered arranged substrata toward procedure electrodes, consenting admittance of reactants as well as proclamation of goods in fluid and vapor stages as well as overwhelming energy barricade at moderately low overpotentials. The overpotential has out-and-out price. The thermodynamically resolute lessening potential has triggered via the separation of electrodes. Electrocatalysts can diminute the overpotential of such responses underneath hug catalytic existing concentrations. Through assistance of MOFs, their composites as well as derivatives as per talented electrocatalysts and the swift expansion have been completed in the process of water electrolysis [168].

9.8.2 Electrocatalytic hydrogen evolution reaction (HER) Maximum well-known competent catalytic agent has founded on principled metals, and these reagents are restricted by their luxurious price. In this century, MOFs and their derivatives/composites have developed as per HER catalytic agent unpaid to

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their appropriate geographies, although their enhancements in catalytic motion and long-term constancy have been desirable. Fresh MOF-derived compounds have disclosed excessive capacities of HER in both alkaline/acidic solutions. Mn-incapacitated nickel oxide–nickel heterostructured arrangements had equipped through tempering a Mn–MOF–Ni–foam forerunner in sluggish environment, in 2018 [169]. Mn-doped Ni/NiO heterostructures through dissimilar nickel then nickel oxide limitations have accomplished highest commotion and also extraordinary long-term stability for HER together with nonaligned electrolytes too seawater naturally.

9.9 Opportunities and challenges toward practical applications Untroublesome crystalline besides permeable assemblies associate personalized configurations of MOFs and award them with the capability of methane as well as hydrogen storage. Thus, unrestricted amalgamation of MOFs associated functional apparatuses like metal-based nanocomposites, C and graphene on the basis of incarceration and their harmonious belongings permit them toward heightened catalytic actions in fluid chemical H2 storing, conversion in solar energy, as well as electrochemical energy storage besides alteration. Low organizational permanency of furthermost MOFs bounds their submissions in long-term and exacting circumstances like high bitterness, alkalinity, and then temperature. In accumulation, less electrical conductivity of maximum MOFs has undesirable impression on reaction kinetics as well as electron transfer degree in electrochemical responses. Supplementary exertions to progress the constancy and conduction of MOFs are predictable. In assessment with MOFs and their amalgams, MOF-derived nanocomposites together with porous carbon, metal oxide, metal/carbon compounds, as well as single-metal atomic carbon attained highest temperature pyrolysis, which own great amount of unprotected sulfur and nitrogen metals as well as vigorous midpoints by means of outstanding organizational steadiness and their electrical conductivity. They have extensive castoff as high-performance catalytic agent or their provisions in numerous thermocatalytic, photocatalytic, and electrocatalytic procedures unfluctuating on exacting environments. Nevertheless, improved charge of the complicated MOF forerunners and the multifaceted artificial performances frequently decrease monetary practicability of such MOF-derived nanocomposites. This ought to be renowned high-temperature pyrolysis that primes toward significant complications in accurately controlling microstructures of MOF-derived nanocomposites. Nevertheless, current momentous advancements have made in exact switch of the microstructures of MOF-derived nanocomposites like one-atom, two-atom, and metal-cluster compounds.

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9.10 Conclusion Investigation on the exploration of MOFs as podiums for energy applications is positively one of the most active topics between chemistry and materials community. MOFs possess unique internal surface area, tailored chemistry, versatile nature, high porosity, and small size with promising and intriguing characteristics. Recently, progress of MOFs and MOF-based materials for energy storage, fuel cells, electrochemical energy storage, and conversions get attention of researchers. Low electrical conductivity of MOFs has undesirable impression on reaction kinetics as well as on electron transfer degree in electrochemical responses. Furthermore, we should focus on clean energy applications of MOFs and explore their benefits in green chemistry as well.

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Sadia Muzammil, Awais Ahmad, Rafael Luque✶

10 Polymer-coated MOF for pharmaceutical waste removal Abstract: Pharmaceutical pollution has occurred as a decidedly anxious issue because of its antagonistic possessions. Preeminent concentrations of pharmaceuticals in aqueous media should be delimited to placate the prerequisite for the establishment of sparkling aquatic. Metal-organic frameworks with high precise superficial zone, welldisciplined permeable assembly, as well as facetious amendment can assist as auspicious adsorbents for the amputation of pharmacological impurities since aquatic. In this chapter, particular assemblage demonstrating steadfast approaches as well as perceptions to formulate the metal-organic frameworks (MOFs) derived constituents with higher water permanency index are given in detail. Furthermore, current evolution on the adsorptive amputation of medicinal contaminant by means of mushrooming and functional MOFs is also abridged in rapports of thoroughgoing capacity, steadiness period, as well as redeveloping aptitude. In the intervening time, to comprehend adsorption mechanism, associated connections together with synchronization with unsaturated position, pore-filling effect, hydrogen attachment, static, and π–π assembling are supplementary deliberated. To conclude, perilous perceptions with valuation of forthcoming investigation accentuating on engineering looked-for MOFs as well as launching structure-property associations to smooth imprisonment recital have been acknowledged.

10.1 Introduction Water adulteration has been ascending due to the population exploitation and industrialization [1]. On the human health and ecological system, it shows negative effect due to incipient organic impurities like pesticides, food additives, industrial compounds, by-products, as well as pharmaceuticals, and they have been hovering allembracing apprehensions [2]. In water system, antibiotic drugs, also known as incipient organic contaminants, are regularly found. From the polluted water, antibiotic drugs are imperious to abolish from this due to their complex noxiousness as well as augmented bacterial confrontation [3]. For contaminant amputation in the ✶ Corresponding author: Rafael Luque, Departamento de Química, Orgánica Universidad de Córdoba, Campus de Rabanales Edificio Marie Curie (C-3) Ctra Nnal IV, Km 396 Córdoba, Spain, e-mail: [email protected] Sadia Muzammil, Department of Environmental Science, Government College University, Faisalabad, Pakistan 38000 Awais Ahmad, Departamento de Química, Orgánica Universidad de Córdoba, Campus de Rabanales Edificio Marie Curie (C-3) Ctra Nnal IV, Km 396 Córdoba, Spain

https://doi.org/10.1515/9783110792607-010

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wastewater, adsorption technique has been accomplished because of its cost-operative remedy as well as its ease model and low energy ingesting [4]. Some materials like zeolite, mesoporous silica, and activated carbon also known as spongy materials are the outmoded antibiotics adsorbents and they have substandard adsorption properties like small uptake capacity, feeble obligatory affinity, as well as poor fussiness [5]. So, in the current years, the removal of antibiotics has achieved extensive attention, and for this purpose new porous adsorbents have been launched. For the building of the porous materials, metal-organic framework (MOF) is also known as innovative class for this and they established from the metal nodes of the inorganic as well as organic linkers through the synchronization contact [6]. MOFs have gigantic protuberant rewards like huge surface area, tunable aperture assemblies, as well as informal functionalization, and due to such properties, they behave as adsorbent for antibiotic removal. These unique properties clinch the interest of the scientist like Liu and his coworkers. To adsorb the antibiotic drug cephalexin from the water, they have used the zirconium-based MOF as an adsorptive [7]. Scientist equipped 100-MIL urea and melamine modified which have 442.48 mg/g adsorption capacity [8]. And it is an extremely competent adsorbent for the nitroimidazole antibiotics. Though in the case of the crystalline form, metal-based framework found as powders bounds their practical submission of the adsorption [9]. But in the case of stationary adsorption, it is very grim to discrete as well as reutilize powdery metalbased framework rather than in the case of the column adsorption MOF powders which slows down the columns. With the succor of the polymers, scientists figure metal-based framework hooked on macroscopic manners so that they can deliver these subjects [10]. In the construction of MOF powders, major obstacle has been faced by the polymer composite beads or metal-based framework. And these are manufactured by dipping the polymer as well MOF solution in the coagulation bath [11]. For the subtraction of the drug pollutant, a cost-effective chitosan medium has been equipped and for this purpose, zeolitic imidazole framework-8 and zeolitic imidazole framework-67 were cohesive [12]. Subsequent in the little consumption of the metal-based framework, the bead size is higher than several hundred micrometers. So, the MOFs in the core are grim to originate connection with the contaminants and they prerequisite an elongated diffusion detachment. Hence, to overcome such issues, evolving appropriate as well as well-formed expertise is exceedingly necessary. Pharmaceutical pollutants are flattering the incipient contaminant and these are frequently originated in the miscellaneous group of marines as well as sediment life [13]. Conspicuously, they are pertinent to amass in the marine life and posturing comparatively huge biological risk [14]. So, elimination of the pharmaceutical toxin from the milieu is a crucial measure to protect the hominoid strength as well as conservational protection. Isolated physiochemical possessions and little meditation arouse the encounters for the well-organized amputation of the assorted pharmaceuticals, and these are the daunting challenges for removal of the toxins from aquatic life [15]. Scientist reported that advanced oxidation processes like photocatalyst, membrane

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separation, organic treatment, as well as adsorption have distinguished consequence on the elimination of pharmaceuticals composites [16]. Adsorption technology is one of the best techniques for adulteration remediation and it has exclusive possessions like minute operational rate, high eradication competence, as well as lessening in the fabricating subordinate noxious contaminants [17]. Underneath explicit situations, retrieval of the poisons could be comprehended and it is signifying high auspicious latent. To manufacture the elongated and unremitting polymer fibers, electrospinning is cast-off for the fiber assembly and they produce the fibers in nanoscale as well as microscale (in diameters). During this process, fibers stack with each other produces a nonwoven membrane [18]. In the past few decades, electrospun polymer fibers have been cohesive with the metal-based framework forming it in a fiber form because they have the high permeability as well as informal preparation [19]. Among the impurities and the metal-based framework primes the interaction in the smaller fiber diameters as well as high permeability of electrospun, and they are associated with the higher polymer beads. These manufactured polymers and MOF electrospun fibers supplementary appropriate for contaminant amputation from the effluent. However, huge data is available on the polymer electrospun fibers used as adsorbent for the wastewater removal but there are so many issues that exist with this where they are overwhelming [20]. So, two ways are used to synthesis the MOFglazed polymer for excess amputation, that is, on the surface, in-situ MOFs veneer, and the other one is grounding of polymer-based electrospun filaments [21]. In the following techniques, MOFs encumbered in the fibers gradually hampers the commerce among MOFs and toxins. Metal-based framework also has the ability to admit adsorption spots in the contaminants. Secondary pollution exhibits through the coated metal-based framework because it easily falls out and condenses cycling constancy. Polymer-coated MOFs erected via polyvinyl polypyrrolidone (pore-forming mediator) and its sustenance are used in the MOF loaded material. Zeolitic imidazole framework-8 used in MOF material and polyacrylonitrile is used to load MOF material. Characterization and synthesis of ZIF-8 were sightseen to examine the adsorption ability of the tetracycline antibiotic, and it is used for the dynamic tetracycline removal.

10.2 MOF applications’ potential as alternative sorbent for pharmaceutical waste removal For the effectual amputation of the numerous pharmaceuticals like antibiotics, nonsteroid anti-inflammatory remedies, and veterinary drugs via water solution have a substitute derivative known as ion potential. Adsorption recital has been boosted up via overview of the explicit functional assemblage, amalgamation of mesostructure,

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heteroatomic fixing, and pyrolytic alteration stratagems. Also, combination of metalbased framework with nanocomposites led to enhancement of the adsorption capacity of the reaction and it also work to affluence the operation. Such results designate those techniques which are used to achieve the precise scheming of MOF as well as their byproducts with higher adsorption performance. And these ways are convenient in the surplus subtraction of pharmaceutical. With controlled structure and hydrolytic constancy of the metal-based framework, ascendable amalgamation is still a scientific challenge. Synchronized pharmaceuticals are instituted in the hands-on samples and they also have substantial impression on the removal proficiency as well as numerous environmental parameters. In the widespread assortment of MOF application, the ecotoxicological valuation of metal-based framework material is designated. Distinct measure should be executed to monitor since the existence of the metal ions and whether the metal ions would be percolated. Scientist report that the discharge of metal ions into hydrated solution caused by the use of the MOF-based adsorbents and they also claim that these are beneficial in the future prospective. MOF-based composites clinch the scientist’s interest due to their unique properties like elimination of the pharmaceuticals can be reinforced effectually through treating them with other chemicals like acetone, acetonitrile, methanol, ethanol, hydrogen chloride, as well as sodium hydroxide. To boost up the effect, these solutions are repeatedly used in amalgamation with each other and several methods have been used at laboratory to achieve to desired result. These methods are still suffering intricate artificial processes, high energy consumption, use of carbon-based solvents, as well as huge manufacturing charge. On the physiochemical properties like particle size and morphology of the artificial composites as well as preparation conditions have the incredible impact on it. They show their effects on large scale which ultimately leads to the adsorption performance. To overcome these issues, ionothermal processes, continuous operations, as well as utilization of water as solvent are the most wanted synthetic techniques of this era [22]. In the same way, single-step pyrolysis of the synthetic MOF’s derivatives is the most observed alternative method [23]. Reusability is highly subordinate with the cost in parallel with steadiness and adsorption performance. Hydrophobicity, synchronization, bonding between hydrogen, consequence of the pore size, electrostatic, as well as interaction between the π–π have been deemed dependable for the competent detention of pharmaceuticals via metal-based frameworks. Foremost interface depends on the property of the targeted contaminants like acidity, alkalinity, as well as neutral nature of the toxins, and it also depends on the water quality condition. Some other characteristics like pore size, surface area, charge density of surface, composition, as well as functional groups are also depending on the structure of the MOF. Relationship between the structure and property has not been clarified properly yet and it is also a big hurdle in the application of the MOF. Researcher put their efforts to find out the particular interaction mechanism of metal-based framework. Relationship between the MOFs at the

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molecular level was established via experimental and theoretical calculation, and it was used find the nanoscale pores as well as crystalline lattice. Practical application of the metal-based framework for the removal of the pharmaceutical waste from the environment should be further appraised. To access this goal, MOF-based materials faced some hurdles, that is, frequent contemporaneous compounds, inorganic ions, as well as liquefied organic matters end to end with microorganisms. These have antagonistic possessions on the adsorption owing to durable competitive and protecting effects. Another critical issue, that is, concentration in real water samples at tremendously low level and it is very low as associated to laboratory. Acute toxicity of the metal-based framework composites should be analyzed as well as evaluated comprehensively to meet the goals. It also addresses the enduring firmness underneath severe circumstances as well as low noxiousness and is indispensable to safeguard the extensive practical submission. Based on the available data, the structural commotion association can be unstated more straightforwardly and they assistance to indicate the appropriate/dependable constituents for forthcoming enquiry.

10.3 MOFs as a versatile platform for pharmaceuticals capture With high adsorption recital, to recognize the necessary constituents, it is imperative to comprehend the interaction mechanism intricate in the adsorption procedure. On previous information, it had been recommended that adsorption mechanism of the biological impurities over metal-based frameworks mostly encompassed electrostatic, hydrophobic, acid/base, π–π, bonding between hydrogen, as well as metal-bridging interactions [24]. In addition, it would also be suggestively exaggerated by the magnitude as well as form of the metal-based framework. This segment primarily distillates on the up-to-the-minute advancement of metal-based framework as well as their byproducts for the amputation of pharmaceutical waste.

10.3.1 MILs and their derivatives Intended for the adsorptive elimination of the pharmaceutical surplus and their vigorous assembly, current trainings have been perceived for their widespread submission of the MILs and their plagiaristic like pristine MILs (e.g., MIL-101, MIL-100, MIL-53, MIL-88, and MIL-68), MIL composites (like GO/MOF, CNT/MOF, and magnetic MIL), as well as permeable materials consequential from MILs.

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10.3.1.1 Pristine MILs Noteworthy hydrolytic stability of the Matériaux de l′Institut Lavoisier (MILs) made them as one of the furthermost eccentric metal-based frameworks for the remedy of pharmaceuticals. Scientist reported the direct use of the MOFs for the pharmaceutical waste from the water, and Cychoz as well as Matzger published their work in 2010 [25]. Adsorption performance of the furosemide and sulfasalazine indicated the feasible pertinency of the metal-based framework, remarkably. To investigate the best stability of the MILs, different composites like (Zn) MOF-177, (Cu) HKUST-1, (Zn) MOF-5, (Cu) MOF-55, (Cu) UMCM-150, (Zn) ZIF-8, as well as (Cr) MIL-100 have been used, the results indicate that MIL-100 (Cr) performs the best as well as has high stability index. In arrears to the accommodating obligatory collaboration with the following two composites, that is, furosemide and sulfasalazine were successfully captured through the MIL-100 (Cr) even at its low concentration. For elimination of the Naproxen and clofibric acid, two composites like MIL-101 (Cr) and MIL-100 (Fe) have been used and they have performed best [26]. In comparison with the acetyl, adsorption performance of the following two composites MIL-101 (Cr) and MIL-100 (Fe) showed the best results in the kinetic adsorption as well as in the capacity term. It is due to the strong electrostatic interaction between the metal-based frameworks and naproxen. MIL-101 (Cr) unveiled better performance than MIL-100 (Fe) due to its highest surface area, largest volume of the pore, as well as more available vigorous positions. Subsequently, Jun and his colleagues analyzed further the information on the adsorption of the roxarsone as well as acetylsalicylic acid. They found the adsorption capacities of the abovementioned two chemicals over the following composites like acetyl, zeolite Y, geothite, MIL-101 (Cr), MIL-53 (Cr), MIL-100 (Cr), MIL-100 (Fe), and MIL-100 (Al) [27]. Among organic arsenic compounds and water molecules, MIL100 (Fe) exhibited the peak of the adsorption capability as well as fastest kinetic response and it accredited to the other adsorption energy. To enhance the adsorption recital, numerous challenges like summary of mesoporous structure, precise functional group of insertion, as well as consumption of stretchy structure has been anticipated. Dou and his colleagues also revealed the results on the MIL-53 (Al) composite, he explained the adsorption capacity and kinetics of triclosan on the mesoporous and he also informed that MIL-53 (Al) was significantly boosted in assessment with microporous. At little concentration, that is, 1 mg/L, it is roughly about 4.4 times faster [28]. Additional of the functional groups like –OH, –NH2, and –SO3H have been observed as one more achievable procedure [29]. At the unsaturated locations, aminomethanesulfonic and ethylenediamine were amalgamated into the other composite’s minimal (MIL-101). Final product has been achieved for the removal of the pharmaceutical waste and materials like –SO3H as well as –NH2 were originated to be competent for naproxen and CA [30]. Highest removal efficiency has been exhibited in comparison with pristine MIL-101, AMSA-MIL-101, and ED-MIL-101 highlighted the

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greatest efficiency. It also explained the interaction of acid and base in between the basic group of the –NH2 as well as acid pharmaceuticals. It also explained the interaction of acid and base in between the basic group of the –NH2 as well as acid pharmaceuticals. [31]. Gao reported that in the adsorption properties of the carbamazepine, MIL-53 (Cr) 101.1 mg/g exceeded rigid MIL-101 (Cr) 13.5 mg/g significantly. This is due the flexibility in the structure of MIL-53 (Cr) and this is found in the most conceivable reason. However, rigid MIL-101 (Cr) negotiated its adsorption performance along with its unalterable structure and hydrophilicity. Powder diffraction analysis revealed the information on the transformation of the flexible MIL-53 (Cr) and it also gives the information on the simulated calculation. Investigation designates that throughout the adsorption process, conversion of composite from slender pore into large pore is owed to the amplification of the volume in cell and it also lessen binding energy rather than boosted aptitude of aquaphobic.

10.3.1.2 MIL composites Manufacturing of the metal-based frameworks composites is actually fascinating owing to improved water permanency and enhanced adsorption capacity; it happened due to the introduction of the function groups as well as consumption of stretchy assembly. In this esteem, Matériaux de l′Institut Lavoisier (MIL) has been united with chitosan, sodium alginate, MWCNT, metal nanocomposites, GO, and Fe3O4 [32]. To formulate MIL-101 (Cr) sodium alginate and MIL-101 (Cr) chitosan, MIL-101 (Cr) had been merged with sodium alginate as well as chitosan matrix in precisely [33]. For benzoic acid, ibuprofen, and ketoprofen, MIL-101 (Cr)/chitosan amalgam procedure has influenced advanced adsorption capacity as compared to sodium alginate, chitosan, as well as MIL-101 (Cr) sodium alginate. To analyze the adsorption process of pharmaceuticals, X-ray photoelectron spectroscopy and πenergy technique illustrate their adsorption process as well as it meticulous property through electrostatic/π-interactions. To restrain the copper/cobalt bimetal nanocomposites into pores of MIL-101 (Cr), double solvent procedures and aweinspiring reduction method has been introduced [34]. For tetracycline adsorption, CuCo and MIL-101 show highest capacity as associated to pristine MOFs and its almost about 140% increase. This augmentation had accredited toward the strong chemical bonding between copper and cobalt nanocomposites as well as in tetracycline molecules. Supplementary contributions have been pragmatic through other connections like acid/alkaline interface, π–π exchanges, pore/size selective adsorption, as well as forces between the hydrogen bonding. Magnetic metal-based frameworks have showed rapid response toward magnetic materials associated with merits of MOFs which show particular interest. To eliminate ciprofloxacin, composites of Ferus, that is, Fe3O4 @MIL-100 and Fe3O4 @MOF-235 have been synthesized and utilize it [35]. Consequential magnetic particles unveiled superparamagnetic property as

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well as excellent capture ability for the ciprofloxacin and its 322.6 mg/g. And this value is highly recommended as compared to other composites like acetyl/carbon nanotubes values. Results indicated that MILs-based amalgams showed the highest strength of the pharmaceuticals waste elimination.

10.3.1.3 MILs-derived materials To synthesize the conforming byproducts, numerous Matériaux de l′Institut Lavoisier (MILs) like MIL-53 (Fe) and MIL-88 (Fe) have been exploited as antecedents. For the carbon-in-pulp adsorption process, manufactured magnetic mesoporous carbon, that is, Fe3O4/C is constructed on carbonization of a mixed-valence MIL-53 (Fe) [36]. In result, Fe3O4/C indicated the mesoporous structure with largest precise surface area, that is, 908.2 m2/g. Fe3O4 nanocomposites were well-dispersed in the carbon matrix. Due to the highest magnetization saturation power of the composites, they can simply salvage via magnetic separation. Remarkably, carbon-in-pulp showed adsorption ability, that is, 868.6 mg/g as well as its amputation competence sustained after five cycles. Direct pyrolysis of the Zn-doped MIL-53 (Fe) established the preparation of magnetic carbon-αFe/Fe3C [37]. When it is compared with the pristine, magnetic carbon-αFe/Fe3C demonstrated a higher adsorption capacity, that is, 453 mg/g and it is due to high surface area, size of the pore, as well as total volume of the pores. For the competent imprisonment, adsorption mechanism investigation suggests that the electrostatic interface as well as pore filling effect and these are the protuberant influences of this. Additionally, remarkable work has been informed that tetracycline can be detached with a high efficiency even at low concentrations, and its concentration can be abridged to a comparatively small level.

10.3.2 Zeolitic imidazolate frameworks and their derivatives Zeolitic imidazole frameworks are classified into the MOFs and they are isomorphic with zeolites in topologically form. ZIFs are sturdily aquaphobic and constant; they are an auspicious contender for impurities amputation from aquatic as well as waste removal of pharmaceuticals.

10.3.2.1 Pristine zeolitic imidazolate frameworks For the subtraction of tetracycline from the aqueous medium, ZIF-8 nanocomposite has been used and it was synthesized in the methanol solution at room temperature [38]. The synthetic substantial materials have unveiled extraordinary adsorption capacity,

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that is, 930 mg/g. These synthetic materials show electrostatic as well as π–π amassing connections among ZIF-8 and tetracycline. For assessment of adsorption comportment in the direction of tetracycline, scientists put their efforts on it and they achieved different chemical as well as textural compositions of the following composites, which are, ZIF-8-Cube, ZIF-67-NO2, ZIF-67-Cl, ZIF-67-OAC, ZIF-67-SO4, ZIF-8-Octahedron, ZIF-8-Leaf, and ZIF-8-Cuboid [39]. From all the abovementioned composites, ZIF-67-OAC highlighted its highest adsorption peak that is, 446.9 mg/g. However, there is no symmetry between the adsorption capacities of the ZIFs and BET, and their surface area and pore volume does not correlative with each other. One-pot strategy has been used to reconnoiter the reimbursements of the engorged pore and streamline the preparation progression. In the same way, hierarchical permeable ZIF-8 associated with meso- and macropores was synthesized via consumption of polyelectrolyte in the arrangement of structure directive negotiators [40]. While comparison between surface areas of HpZIF-8-10 (D) had smaller mZIF-8-10, their adsorption capacities on the way to tetracycline as well as chloramphenicol were maximum. These were also emphasized on compensations of the classified absorbent assembly and they make accessible sites for adsorption which progresses mass assignment instantaneously. Results showed the extraordinary supports for the functional groups as well as their pore sizes which are essential for competent pharmaceutical surplus elimination.

10.3.2.2 Zeolitic imidazolate frameworks composites Zeolitic imidazole frameworks composites have positive attitude toward recyclability and affluence handling. Composites of ZIFs also succeed to the consistent structure. In this parameter, removal of the pharmaceutical waste following ZIFs-based composites has been used like MOF-resin, ZIF-8/GO, Konjac glucomannan, and ZIF-8-CS, as preferred adsorbents [41]. Synthesis of MOFs-CS composites were done by the means of integrating distinctive MOFs like ZIF-8, ZIF-67, Fe-BTC, and HKUST-1 into chitosan matrix. From the abovementioned composites, ZIF-8-CS unveiled highest adsorption capacity which was nearly about 495.04 mg/g and it was outstripping ordinary polymer-based tetracycline adsorbents. Electrostatic interaction, π–π stacking, and bonding between hydrogen as long as directing contributions and these analyses have been done via experimental characterization as well as density functional theory. Electrostatic interaction, π–π stacking, and bonding between hydrogen as long as directing contributions and these analyses have been done via experimental characterization as well as density functional theory. Composites like ZIF-8@SiO2@Fe3O4 have been consequent from DIY of ZIF-8 and also from SiO2@Fe3O4 and they prepare with the use of cetyltrimethylammonium bromide as with sodium laurate, these are template agents as well as used to prosper the salvage aptitude. Aperture size has been tunable through fluctuating the quantity of prototype negotiators. Adsorption capacity

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of the ceftazidime was about 74.25 mg/g and it was the highest compared to pristine ZIF-8, that is, 39.1 mg/g as well as it attains under optimal circumstances. Scientists manufactured the resonating structure of the natural kapok filaments comprising of cellulose along with lignin and it is an innovative self-boosted Pt-free magnetic micromotors (e.g., ZIF-8-c-Fe2O3/c-Al2O3/MnO2 (ZIF-8-M)) [42]. Self-propelled nanocomposites (e.g., ZIF-8-M) as well as metal-based frameworks revealed outstanding adsorption dimensions toward Congo red (i.e., 394 mg/g) and doxycycline (i.e., 242 mg/g) and these composites also have huge surface area with permeability. ZIF8-based micrometers were able to be boosted in the real-word effluent together with freshwater and adhesive tape water which are promoting for the impurity’s uptake, thought provoking.

10.3.2.3 ZIFs-derived materials Among innumerable established ZIFs, like ZIF-8 and ZIF-67, have been most expansively considered predecessors. By the use of distinct hybrid constituents, carbonized by-products through muffled construction can be attained predominantly underneath stringently meticulous circumstances. In addition, multimetallic MOFs which comprise of two or three metal ions have been operated to synthesis ZIFs consequential constituents with numerous metals or their oxides. To formulate porous carbons, ZIF-8 has been pragmatic as self-template [43]. Since surface area of the MOF’s consequent carbons at 1,000 °C (i.e., 1,855 m2/g) and it was roughly 1.73 epoch complex than that of virgin ZIF-8 (i.e., 1,073 m2/g). It is remarkable that adsorption measurements for ibuprofen as well as diclofenac sodium were respectively 320 and 400 mg/g. High presentation of the reaction primarily owing to the connections between the bonding exist in hydrogen, π–π exchanges as well as aquaphobic contacts could not be administrated out significantly. ZIF-8 derivative from permeable carbons are considered for the operative elimination of the ciprofloxacin as well as sulfamethoxazole [44]. Scientists put their interest on the ionic liquid containing ZIF-8-derived carbon and concluded that ZIF-8-derived carbon performed better rather than ZIF-derived carbons. Since, underwired presentation was accredited to the occurrence of higher nitrogen content in derived ZIF-8 carbon and it was indispensable for the development of hydrogen bonding with the marked pollutant. Introduction of the hollow structure leads to enhance the adsorption capacity of the MOF based derived materials [45]. On the other hand, for the adsorptive elimination of the tetracycline N-doped hollow porous carbons have been employed [46]. Some other composites like N-doped porous carbons, NHPC-1 and NHPC-2 have been obtained through the utilization of ZIF-8, resorcinol, as well as tannic acid and these were coated with ZIF-8 (ZIF-8@RF) and ZIF-8 (ZIF-8@TA) respectively, they were used prototypes. NHPC-2 has some properties which are related to its morphology like distribute its pore size properly as well as volume of the

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pore and it also has large amount of the nitrogen content. NHPC-2 also displays the number of defects with greatest adsorption performance toward tetracycline, that is, 518.1 mg/g and its 2.9 folds huge then that of N-doped porous carbon, that is, 180.2 mg/g. So, results indicate that π–π stacking, hydrophobic as well as hydrogen bonding were the foremost driving services for this composite. Furthermore, adsorption capacity of the NHPC-2 composites toward tetracycline persisted unaffected even after eight cycles. And it establishes the virtuous steadiness as well as recovering capability. In the case of the magnetic technic, it illustrated gigantic potential for handson submission unpaid to its informal operation. To eradicate the ciprofloxacin from the aqueous medium, pragmatic an intimate of vigorous magnetic nitrogen doped nanoporous carbon has been used in this assembly [47]. For the formulation of MNPCs have been achieved via single-step pyrolysis technique and in their synthesis composites of zinc oxide, dimethylimidazole, as well as Co (OH)2 used as antecedents [48]. Co-doping of the bimetallistic has exhibited harmonious advanced consequence on the superficial area as well as aperture construction of MNPC and it primes to progress the adsorbed capacity of ciprofloxacin. Molar ratio of the zinc/ cobalt has helped to regulator the magnetic properties as well as surface area of MNPCs and it occurs at fluctuating temperature pyrolysis. On MNPC-700-0.4, the optimum presentation has been accomplished with extraordinary capacity with 1,563.7 mg/g and it is primarily hooked on auspicious textural possessions like vast surface area, pore volume, blemishes in huge quantities, as well as structural property of nitrogen rich. To commitment with the ciprofloxacin, main driven forces have been exhibited. In accumulation to its virtuous recovering capability, this work demonstrates the auspicious probable of bimetallic MOFs-derivative constituents, which have synergistic possessions can take place.

10.3.3 Universitetet i Oslo (UiOs) and their derivatives UiOs are the archetypal MOF along with highest surface area and huge thermal permanency. Its permanency can be contingent on the metal oxide protuberance. So, it has been pragmatic as indispensable group of water constant MOFs. UiOs like UiOs-66, UiOs-67, and UiOs-68 have been cast-off extensively for imprisonment of abundant pharmaceuticals.

10.3.3.1 UiOs Numerous UiO-66 correspondences through the miscellaneous functional groups like –SO3H, –NH–, –NH2–, as well as COOH have been utilized for the eradication of pharmaceuticals [49]. To study the adsorption performance of UiOs, Hassan and his

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fellows studied the UiOs and their functional groups toward DCF [50]. And they concluded that both groups, that is, pristine as well as functionalized UiO-66s have been originate supplementary operative on the way to DCF uptake rather than AC in rapports of adsorption kinetics as well as measurements. Introduction of the functional group, that is, –SO3H occasioned in a conspicuous enhancement on the adsorption capacity which is approximately equal to 39.1 comparability to virgin UiO-66. One more functional group, –NH2, commanded to suggestively diminution and its decrease is almost about 43.9% conceivable associations together with electrostatic, π–π communication or acid/base interface might feature to the extraordinary presentation. MOF has morphological properties like surface area, adsorption ability, as well as hydrophobicity effect on the structural properties of the resultant MOFs. Some other belongings like amendment of function group, artificial condition, as well as instigation technique also have noteworthy consequence on it. Chloroform galvanized UiO-66 demonstrated a momentous sulfachloropyradazine adsorption dimensions, that is, 417 mg/g in evaluation to virgin UiO-66 [51] notably. MOFs-associated delimited pore sizes were synthesized via the use of tempered linker or acquaint with imperfection for the anticipation of smooth adsorption recital. Akpinar and his fellows detected that virtually 95% of CBZ was apprehended completed with UiO-67 within 2 min at concentration of 100 mg/L and 35% only over UiO-66, although [52]. With the regulator of the quantity of modulator, plentiful UiO-66 with unvarying misplaced linker imperfections were fictitious. Introduction of blemish not only associated the subsequent merchandise’s amended absorbency but also has constructive outcome on the formation of Zr–OH. It accelerated adsorption as well as advanced adsorption dimensions of ROX at the same time more rapidly. Conspicuously, adsorption equilibrium had concentrated since 240 min to 30 min, which ultimately enhanced the adsorption dimensions since 197 to 730 mg/g. For the competent amputation of pharmaceutical leftover, outcomes designated that involvement of aperture size end to end with hefty surface zone had dangerous. To possess a distinct construction with improved commotion, metal incapacitated amendment manufactures second metal, that is, cerium, cobalt, and manganese. These second metals have been used to formulate bimetallistic metallic organic framework and it is fascinating as well as auspicious approach [53]. The adsorptive amputation of tetracycline via cobalt-doped UiO-66 has been inspected instantaneously. This cobalt-doped UiO-66 composite discovered the contented heightened dimensions, that is, 224.1 mg/g and it is 7.6 epochs sophisticated rather than virgin UiO-66 composite. In the same way, the adsorption capacity of the tetracycline concluded manganese-doped UiO-66 had also significantly heightened in assessment to unembellished UiO-66. It had originated that supplement of manganese occasioned in higher BET superficial zone and aperture magnitude, which were auspicious for the subtraction of tetracycline concluded π–π stacking and hydrogen bond connections.

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10.3.3.2 UiO composites Composites which have crinkles fascinating as they advantageous to progress superficial zone as well as unprotected malfunctioning positions. The communication flanked by surface-assimilative and target pollutants that subsequently furrow the construction is accommodating to facilitate. Interested through this perception, scientists discovered that adsorption quantity of salicylic acid completed with per unit mass UiO-66 in furrow ornamented UiO-66@Fe3O4@UiO-66 had approximately 1.4 times that of virgin one [54]. Such enhancement had been done primarily accredited to the establishment of interlaced imperfections. By this the synchronization communication among salicylic acid as well as crumpled MOFs had augmented. Consequences contingent that crease structure on MOFs have a significant consequence on enhancing the adsorption presentation.

10.3.3.3 UiOs-derived materials Hu and his colleagues have established a prototype technique to synthesis a sequence of carbon-based constituents accompanying adjustable aperture magnitudes and these are consequential from Uio-66-NH2 [55]. Results designate that template collected with CTAB as well as sodium laurate had noteworthy consequence on the inventive assembly and it also permitted aperture magnitude intonation. Unsurpassed presentation has been attained through UC-0.1 that is, aperture magnitude 5.38 nm and it has an uptake measurement of 84.23 mg/g. Isothermal information and thermodynamical investigation have been based on the scrutiny of adsorption kinetic and the adsorption mechanism had observed as electrostatic and aquaphobic communications.

10.4 Other MOFs and their derivatives Some additional MOFs and their by-products associated with high water permanency have been pragmatic to adsorb pharmaceutical waste removals. For the removal of ciprofloxacin and tetracycline, MOF-5 shows positive response toward it [56]. Though the rejuvenation aptitude which is associated to comparative water compassion has not been assessed [57]. In derived MOFs, one more work which is accomplished on perfluorinated unveiled higher adsorption aptitude on the way to tetracycline outstanding to π−π stacking connections [58]. To eliminate a mass of pharmaceutical discards like SCP, DOC, NAP, FQ, ciprofloxacin, NOR, as well as diclofenac have been removed via HKUST-1. HKUST-1 has some characteristics which help to associate for the removal of waste like huge specific surface area, abundance of unsaturated, as

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well as sites of metals [59]. SCP clinches the interest of the scientist due to its amputation competence towards HKUST-1 composite [60]. This composite had accredited to the harmonious consequence of electrostatic, bonding among hydrogen, and π−π connections. Similarly, effectual eradication of the tetracycline has also been achieved with the help of Fe3O4 and HKUST-1. This removal efficiency has been led through the interaction between the hydrogen bonding, hydrophobic exchange, π−π stacking, as well as interactions amongst electrostatic. So, tetracycline with Fe3O4 and HKUST-1 has been reprocessed underneath the subordinate of a peripheral magnetic. Its reclaimed ability has been gained over 10 times through the use of ammonia and methanol in 99:1 v/v by way of eluent. Wang and his colleagues studied the adsorption pattern of antibiotics as well as organic explosives over two isostructural composites like Zr(IV) derived MOFs, BUT-12, and BUT-13 [61]. Relevant to this assessment, two composites, which are, BUT-12 and BUT-13, have disclosed the unsurpassed adsorption aptitude in repute in direction of nitrofurazone and nitrofurantoin. Ornidazole and CP exhibit extraordinary adsorption ability toward BUT-13 due to high hydrophobic pore surface, inspiringly. Jin prepared 3D isostructural MOFs PCN-124-stu (Cu) and it has high stability as well as substantial porosity, his work gained the interest of the other scientist [62]. PCN-124-stu (Cu) exhibited a largest dimension for the wellorganized encapsulation of FQs in evaluation to zeolite 13X as well as AC expectedly. It also has largest capacity in regard to other five common MOFs-MIL-101 (Cr), UIO-66, HKUST-1, MOF-74(Mg), as well as PCN-124. By the means of theoretical simulation, it was attested by this revenue. In accumulation to its large pore size, amide groups in framework and this framework underwired the interaction flanked by two hydrogen bonds with FQs. Quite a lot of PCNs like PCN-222, PCN-224, PCN-208, and PCN-206 were instigated to be an exceptional display place for the imprisonment of pharmaceuticals [63]. Three-dimensional carboxymethyl cellulose sodium aerogels has been used for the eradication of the tetracycline adsorptive refinement and it also used to confront the decisive questions of delicateness and precipitate feature of MOFs as well as this composite is also ornamented with Ni–cobalt–MOF [64]. Tetracycline has uninvolved virtually approximately 80% inside 5 min unpaid to furthering from exceedingly permeable assembly. The highest adsorption measurements, that is, 624.87 mg/g accredited to collaborative consequence of communication of tetracycline with functional group –OH over the Ni–Co-associated MOF@CMC. Tetracycline and metal ions in the nickel–cobalt MOF@CMC exhibit the establishment of multifaceted oxygen comprising functional groups. Quite a lot of other MOFs which are highly porous materials like MAF-6, bio-MOF-1, MOF-74, MOF-5, as well as HKUST-1 have been expansively used in the arrangement of inexpensive adsorbent for the amputation of pharmaceutical surplus by means of optimistic panorama [65]. In the presence of KOH, MAF-6 has been pragmatic as a predecessor to manufacture porous carbon [66]. For the adsorption of a variety of pharmaceuticals as well as personal care products like acidic ibuprofen, lightly acidic

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TCS, and oxybenzone have been used for this and to introduce these products; MAFderived porous carbons were investigated. And basic natures of DCF as well as atenolol were also used for this purpose. For all personal care products, CDM6-1000k performed the highest adsorption capacity rather than AC composite and it is notwithstanding of their acidity as well as basicity respectively. Dissimilar chemical configurations, adsorption mechanism has been accountable for the personal care products as well as wide-ranging by taking it as contemplation. At the end, latest investigation has been done thru similar group and it reports on amalgamation of nitrogen consisting carbon through carbonizing, that is, MAF-6 as well as it found in the melamine. Consequential absorbent carbons designated by means of CDM@M-6 has maximum absorbency end to end with ironic blemish as well as these imperfections can be straightforwardly adjusted through monitoring the quantity of melamine. Due to the incidence of durable bonding between hydrogen, composite like CDM@M-6 predominantly CDM in 0.25 amount @M-6 demonstrated wonderful presentation for adsorption of nitroimidazole. So, it is valuable and revealing that adsorption measurements of CDM (0.25) @M-6 for DMZ, menidazole, and metronidazole were greatest to the comparable adsorbents that described so far away.

10.5 Conclusion In supposition, current evolution of spread over the MOFs as well as their derivatives for therapeutic impurities amputation is overviewed. MOFs and their derivatives reveal reasonable presentation, that is, huge adsorption dimensions, quick adsorption dynamic, and benevolent reutilizing aptitude which is indicative of higher submission probable for applied submission. Even though development has been accomplished in this turf, claims of MOFs for medications deletion are tranquil in their early stages in assessment to unadventurous absorbent constituents, for example, AC or permeable silica. Supplementary consideration ought to be waged to the ascendable amalgamation and ecotoxicological valuation of MOFs-based constituents, as well as interface mechanism intricate among sorbents and mark complexes. With the unrelenting progress, MOFs have been unmistakably well-thoughtout to be a dependable substitute with delightful forthcoming for the exclusion of diverse impurities that are existing in definite aquatic media with a multifaceted matrix. The quick expansion and affluence of such new constituents in the ages to derive will be exhilarating to a bystander.

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[48] Huang, L., M. He, B.B. Chen, Q. Cheng, and B. Hu, Highly efficient magnetic nitrogen-doped porous carbon prepared by one-step carbonization strategy for Hg2+ removal from water. ACS Applied Materials & Interfaces, 2017. 9(3): p. 2550–2559. [49] Sarker, M., J.Y. Song, and S.H. Jhung, Carboxylic-acid-functionalized UiO-66-NH2: A promising adsorbent for both aqueous-and non-aqueous-phase adsorptions. Chemical Engineering Journal, 2018. 331: p. 124–131. [50] Hasan, Z., N.A. Khan, and S.H. Jhung, Adsorptive removal of diclofenac sodium from water with Zr-based metal–organic frameworks. Chemical Engineering Journal, 2016. 284: p. 1406–1413. [51] Azhar, M.R., H.R. Abid, V. Periasamy, H. Sun, M.O. Tade, and S. Wang, Adsorptive removal of antibiotic sulfonamide by UiO-66 and ZIF-67 for wastewater treatment. Journal of Colloid and Interface Science, 2017. 500: p. 88–95. [52] Akpinar, I. and A.O. Yazaydin, Rapid and efficient removal of carbamazepine from water by UiO-67. Industrial & Engineering Chemistry Research, 2017. 56(51): p. 15122–15130. [53] Cao, J., Z.H. Yang, W.P. Xiong, Y.Y. Zhou, Y.R. Peng, X. Li, and Y.R. Zhang, One-step synthesis of Co-doped UiO-66 nanoparticle with enhanced removal efficiency of tetracycline: Simultaneous adsorption and photocatalysis. Chemical Engineering Journal, 2018. 353: p. 126–137. [54] Yin, Y., M. Shi, Y. Ren, S. Wang, M. Hua, J. Lu, and L. Lv, Wrinkle structure on multifunctional MOFs to facilitate PPCPs adsorption in wastewater. Chemical Engineering Journal, 2020. 387: p. 124196. [55] Hu, X., T. Sun, L. Jia, J. Wei, and Z. Sun, Preparation of metal-organic framework based carbon materials and its application to adsorptive removal of cefepime from aqueous solution. Journal of Hazardous Materials, 2020. 390: p. 122190. [56] Gadipelly, C.R., K.V. Marathe, and V.K. Rathod, Effective adsorption of ciprofloxacin hydrochloride from aqueous solutions using metal-organic framework. Separation Science and Technology, 2018. 53(17): p. 2826–2832. [57] Yang, J., A. Grzech, F.M. Mulder, and T.J. Dingemans, Methyl modified MOF-5: A water stable hydrogen storage material. Chemical Communications, 2011. 47(18): p. 5244–5246. [58] DeFuria, M.D., M. Zeller, and D.T. Genna, Removal of pharmaceuticals from water via π–π stacking interactions in perfluorinated metal–organic frameworks. Crystal Growth & Design, 2016. 16(6): p. 3530–3534. [59] Wu, G., J. Ma, S. Li, J. Guan, B. Jiang, L. Wang, and L. Chen, Magnetic copper-based metal organic framework as an effective and recyclable adsorbent for removal of two fluoroquinolone antibiotics from aqueous solutions. Journal of Colloid and Interface Science, 2018. 528: p. 360–371. [60] Azhar, M.R., H.R. Abid, H. Sun, V. Periasamy, M.O. Tadé, and S. Wang, Excellent performance of copper based metal organic framework in adsorptive removal of toxic sulfonamide antibiotics from wastewater. Journal of Colloid and Interface Science, 2016. 478: p. 344–352. [61] Wang, B., X.L. Lv, D. Feng, L.H. Xie, J. Zhang, M. Li, and H.C. Zhou, Highly stable Zr (IV)-based metal–organic frameworks for the detection and removal of antibiotics and organic explosives in water. Journal of the American Chemical Society, 2016. 138(19): p. 6204–6216. [62] Jin, W.G., W. Chen, P.H. Xu, X.W. Lin, X.C. Huang, G.H. Chen, and X.M. Chen, An Exceptionally Water Stable Metal–Organic Framework with Amide‐Functionalized Cages: Selective CO2/CH4 Uptake and Removal of Antibiotics and Dyes from Water. Chemistry – A European Journal, 2017. 23(53): p. 13058–13066. [63] Huang, L., R. Shen, and Q. Shuai, Adsorptive removal of pharmaceuticals from water using metal-organic frameworks: A review. Journal of Environmental Management, 2021. 277: p. 111389.

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[64] Yang, W., Y. Han, C. Li, L. Zhu, L. Shi, W. Tang, and Z. Li, Shapeable three-dimensional CMC aerogels decorated with Ni/Co-MOF for rapid and highly efficient tetracycline hydrochloride removal. Chemical Engineering Journal, 2019. 375: p. 122076. [65] Van Tran, T., D.T.C. Nguyen, H.T.N. Le, H.L. Ho, T.T. Nguyen, V.D. Doan, and L.G. Bach, Response surface methodology-optimized removal of chloramphenicol pharmaceutical from wastewater using Cu3 (BTC) 2-derived porous carbon as an efficient adsorbent. Comptes Rendus Chimie, 2019. 22(11–12): p. 794–803. [66] An, H.J., B.N. Bhadra, N.A. Khan, and S.H. Jhung, Adsorptive removal of wide range of pharmaceutical and personal care products from water by using metal azolate framework-6derived porous carbon. Chemical Engineering Journal, 2018. 343: p. 447–454.

Maryam Adil, Awais Ahmad, Rafael Luque✶

11 MOF-derived nanocomposites for the removal of ciprofloxacin Abstract: Metal organic frameworks (MOFs) are type of absorbents having substantially strong bonds among metal ions and organic linkers. By means of vigilant assortment of ingredients, MOFs have high surface area, large pore volume, and exceptional chemical steadiness. MOFs with fundamental thermocatalytic commotion, as per hosts for the amalgamation of metal nanocomposite, as antecedents for the assembly of compound catalysts, and those vigorous in photocatalytic and electrocatalytic progressions are unsympathetically revised. MOFs are exceptional platforms to engender dissimilar nanocomposites, encompassing metals, oxides, or carbides entrenched in porous carbon medium. Adsorptive amputation of ciprofloxacin (CIP) using MOFs has been deliberated in this work. These MOF-derived nanocomposites proposition interdependence of properties like high crystallinities, inherited morphologies, untroublesome dimensions, and tunable textural properties. The recurrent recognition of antibiotics such as CIP in surface and drinking waters around the world has engrossed apprehension from innumerable investigators. Such existence is a suggestion that the refinement of water polluted by antibiotics is elsewhere the unadventurous treatment methods. Nanocomposites such as zeolitic imidazolate framework (ZIF)-8, ZIF-67, MIL-100/101, and MOF-5 were manufactured and used for CIP amputation from water. Research on fusion, structures, and properties of various MOFs has shown that they are auspicious constituents.

11.1 Introduction Antibiotics are consistently released into aquatic environments due to their ubiquitous usage, which is posing major risks to the environment and public health. Ciprofloxacin (CIP), an antibiotic which has been extensively used in the treatment of vaginal, joint, urinary, prostate, and also intestinal infections, is one of the drugs that is most commonly found in aquatic environments [1]. Regrettably, the low concentration of

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Corresponding Author: Rafael Luque, Departamento de Química Orgánica, Universidad de Córdoba, Campus de Rabanales, Edificio Marie Curie (C-3), Ctra Nnal IV, Km 396, Córdoba, Spain, e-mail: [email protected] Maryam Adil, Department of Environmental Science, Government College University Faisalabad, Punjab 38000, Pakistan Awais Ahmad, Departamento de Química Orgánica, Universidad de Córdoba, Campus de Rabanales, Edificio Marie Curie (C-3), Ctra Nnal IV, Km 396, Córdoba, Spain

https://doi.org/10.1515/9783110792607-011

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CIP in aquatic ecosystems might increase ecosystems’ antibiotic resistance and pose significant dangers to human health [2]. Accordingly, it would appear important to develop effective treatment methods to remove CIP from aqueous solutions. Moreover, trace levels of CIP residuals in groundwater are hazardous to those aquatic life [3] and that may develop into antibiotic-resistant bacteria, leading to a reduction in treatment effectiveness and a seeming rise in dangers to people’s health [4]. As a result, removing CIP from groundwater is considered to be critical. CIP removal practices and procedures often include enhanced oxidation [5], adsorption processes [6], photodegradation [7], as well biodegradation [8]. With respect to other technology performances, the adsorption process brings convenience, high efficiency, and a simple design, which has been implemented for CIP removal [9, 10]. Moreover, microbiological approaches seem to have inadequate responses as antibiotics rapidly destroy microorganisms. Reverse osmosis entails the acquisition of costly equipment [11]. Only adsorption merely permits contaminants to be retained on the inside of the adsorbent without medical evaluation [12]. Nevertheless, advanced oxidation processes (AOPs) can degrade persistent organic molecules into CO2 and H2O or transform them into further biodegradable and make them less hazardous chemicals [13]. Photocatalysis, as a sort of AOP, is often considered as the most promising method for refining organic chemicals due to its ease of being used, high performance, unlimited supply of catalyst materials, and limitless use of solar energy. Photocatalysis is used in wastewater treatment with many semiconductors that act as nanocomposites such as ZnO, TiO2, g-C3N4, CuO, Cu2O, CdS, Fe2O3, and Fe3O4. Nonetheless, individual semiconductor applications are often restricted due to low catalytic performance, a light area for small excitation, as well as difficulties in the catalyst recovering [14]. Due to their larger effectiveness over the sole semiconductors, double and triple composite resources have in recent times received a lot of attention. Cu2O/Fe3O4 nanostructures are the most appealing prospect for catalysis implementation for their exceptional catalytic action among photocatalytic composites across the visible region as well as sunlight, and also their ease of retrieval by the magnetic separation technique [15, 16]. Due to a tiny mass, catalyst nanoparticles (NPs) have a tendency to agglomerate in the form of enormous clusters, which result in the loss of particular surface region and the inability to sustain protracted catalytic efficacy. One viable solution is to consume catalyst supports that may immobilize the catalyst nanocomposites while also acting as an adsorbent for eliminating contaminants nearer to the catalyst centers [17]. Metal organic frameworks (MOFs) contain absorbent carbon collaboration polymers consists of transition metal multiplexes or the clusters linked through organic ligands that have piqued the interest of researchers for years in a variety of fields such as sensors, gas adsorption, as well as drug delivery, the catalysis, along with versatile capabilities, and extendable size, shape, and porosity [18]. MOFs have recently been employed effectively as endorses for immobilizing catalyst nanoparticles

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in various investigations: MOF maintained niobium catalysts, MOF provided Cu(II) and Cu(0) catalysts, and MOF assisted zinc(II) catalysts. Also said that the combining metal or metal oxide nanocomposites with MOFs increased their optical, physicochemical, and overall catalytic capabilities [19]. Due to its distinctive features such as the great porosities or chemical stability, as well as exceptional ligand–metal charge transfer, the design along with the production of MOFs has received a lot of interest in the ambient process arena. Furthermore, cobalt-based MOFs such as FexMn6–xCo4–N@C, Co3O4@MOFs, hollow spherical zeolitic imidazolate framework (ZIF)-67 and Eu2+/3+/complex@ZIF-67, as well as cotton@ZIF-67; hematite (α-Fe2O3), on the other hand, has been used in photodegradation processes owing to its small Eg (2.0–2.2 eV) along with efficient absorbing of visible light, but it performed poorly and had weak stabilities [20]. Furthermore, the authors’ earlier work and other investigators (Wu and Chen) have demonstrated that the combination of nanoscale ZIF-67 with magnetic particles may significantly improve pollutant degradation. The use of magnetic NPs in conjunction with the amalgamated catalyst which is cobalt-based demonstrates the synergic influence of iron (Fe) as well as cobalt (Co) metals in the successful stimulation regarding peroxymonosulfate (PMS) while also giving fresh insights into the removal of harmful contaminants. Through an approach to enhance higher absorption quantity and efficient adsorption processes for CIP removal, nanocomposite adsorbents, specifically porous adsorbent materials, had also gained extensive attention but porous nanocomposite adsorbents assure advantages such as higher ratio of surface to mass by volume, interparticle pore channel, and also involving others [21]. For instance, carbon nanocomposites formed through carbonization of ZIF-8 were applied as a significant adsorbent with regard to CIP removal [22]. The adsorbent’s strong recyclability as well as higher CIP adsorption capability which is of 416.7 mg/g are noteworthy. This is followed by the conclusion that reveals an intriguing usage of nanocomposites which are MOF-derived act as ecological pollution cleaning. Aside from the scientific discoveries in introducing new nanocomposites, specially MOF-derived nanostructures synthesis with composite as well as core–shell morphological features as that of an excellent activator for degradation of CIP. In comparison to the ZIF-67 and α-Fe2O3 NPs, the manufactured α-Fe2O3/ZIF-67 show excellent result for CIP removal, which is considerably superior [23].

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11.2 Substratum of MOF-derived nanocomposite synthesis Under the suitable circumstances, the straight pyrolyzation of MOFs could well produce “metal oxides as well as metal oxide/carbon composites along with extremely permeable carbons” [24]. The morphologically generated substances are determined through the morphology regarding the original MOFs utilized as precursors as well as sacrificial templates, pyrolysis temperature, and gas atmosphere, as well as other additional parameters.

11.2.1 Self-templated MOFs and external-templated MOFs MOF precursors are classified into two types: self-templated MOFs and external surface-templated MOFs [25]. The MOFs that are self-templated are pristine structures of MOF formed through the self-assembly with regard to metal ions or clusters as well as organic linkers. However, they are made up of only single or multiple metals as well as encapsulated metals, and also heteroatoms include nitrogen-, carbon-, sulfur-, and phosphorus-doped metals which are directly proceeded or altered through the post-synthesis action as well as impregnation and also ion/linker conversation. However, reticular structure establishes strong among strong interaction bonding between metal clusters and organic linkers to determine the morphological structure regarding these self-templated MOFs, which does not alter despite the inclusion of adsorbed species [25]. The morphologies of these self-templated MOFs can be easily replicated into MOF-derived nanocomposites. External-templated MOFs are typically made up of composite MOFs coupled with other substances. Following this, the automated mixing and in situ growth of MOFs rely on a help toward external template like “spherical SiO2 as well as layered-like g-C3N4, and also graphene oxide (GO).” So morphology of such MOF-derived nanocomposites is mostly determined by the morphological structure regarding the supportive external templates in this situation [26].

11.2.2 Zero-dimensional, 1D, 2D, and 3D nanocomposites MOFs derived all nanocomposites and are often categorized as 0, 1, 2, and 3 (dimensions). Even nanocomposites with either more spherical dimensions or less spherical dimensional shapes including polyhedral or hollow structures are categorized as 0D materials. Same as composites of structural forms including nanorods or nanotubes, as well as nanowires are designated as 1D nanocomposites. Similarly, nanoplatelets

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or nanosheets having nanometric range thickness are categorized as 2D nanocomposites, as well as structures such as nanodisks and nanocubes are categorized as 3D nanocomposites [27]. Initial investigations showed that MOFs degraded influences at high temperatures and diminished their morphologies, resulting in bland bulk materials [28]. Modern investigations, though, showed that if rationally generated MOF precursors used under controlled pyrolysis circumstances were selected, MOF-derived nanocomposites have a tendency to maintain the morphological structure of the MOF precursors [29]. Using the appropriate MOF precursors, a wide range of 0D, 1D, 2D, and 3D nanocomposites were obtained with strong fundamental basis along with chemical stabilities, desirable morphologies, and diverse surface functions. Furthermore, the resulting “nanocomposites’ crystallite sizes, morphologies, chemical compositions, atomic and weight percentages, and optimum crystalline phases” may be easily managed by modifying the pyrolysis parameters, which mainly include temperature as well as heating rate, and gaseous environment. In comparison to traditional methods for preparing photocatalyst and carbonization processing, MOF precursor method not only provides a simple way to regulate the derivative products but also has the added benefit of in situ approach that heads on alteration of the compositional, electronic, and more semiconducting properties, especially subsequent materials, ultimately critical for obtaining high-performance photocatalysts [30]. MOFs by means of metal as well as nonmetal adsorbed species as precursors, the ensuing nanocomposites act as in situ doped along with metals and also heteroatoms including N, C, S, and P adapt the energy band positions and electronic structures, as well as semiconducting properties, allowing for greater sunlight absorption and managed to improve charge separation. Surprisingly, the crystalline phases along with atomicity of metal oxides (TiOx, FeOx, CuOx, etc.) incorporated inside the carbon matrix toward MOF-generated nanocomposites may be changed in situ by manipulating the pyrolysis temperature with air environment to improve with higher efficiency of photocatalysis. Furthermore, porous carbons generated from MOFs may be designed and synthesized in situ having hydrophilic or else hydrophobic functional groups by varying during pyrolysis toward gas atmospheres [31]. In general, next to pyrolysis temperature greater than 350 °C, the regiment for MOF crystalline structures which have a tendency to downfall besides the metal clusters drive to convert them into metal composites, though almost carbon-based linkers have the tendency to change to vague or else incomplete graphitic structure-based porous matrices [32]. Target toward obtaining the MOF-derived nanocomposites more along with morphological phenomena includes chemical structure compositions and physical structural properties with basic parameters. (a) Metal ion reduction potential in MOFs proved by Das et al. gives evidence, indicating metallic ions in MOFs with such a reduction potential of −0.27 V or greater, including Co2+, Cu2+, and Ni2+, were synthesized into pristine metal NPs. Thermal

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decomposition in an inert atmosphere, regardless of the fact that some with a reduction potential just under –0.27 V, including Zn2+, Ti4+, Fe3+, and Al3+, formed metal oxides as nothing more than a result of interacting only with oxygen contemporary in organic linkers deeper down an inert gas atmosphere [33]. (b) The homogeneous dispersal as well as various particles of nanocrystals in MOFderived nanocomposites were significantly influenced by metallic ions with Tamman temperatures. The Tamman temperature, which would be just about half the melting point of the metal, is still the point during which atoms have quite enough energy for bulk diffusion and therefore can quickly agglomerate but also polymerize. Metal species interact and form the appropriate nanomaterials when MOF structures disintegrate at extremely high temperatures, including such metallic materials, oxides, metal sulfides, metal carbides, metal phosphides, and/or various composites available to the consumer. Simultaneously, the organic linkers decompose into carbon, functioning like a barrier that keeps metal species segregated as well as preventing bulk aggregation, culminating in a homogenous distribution of particles with just an overall carbon-based matrix.

11.3 Synthesis of various nanostructures from MOFs Inorganic materials for environmental and energy purposes include carbon-based porous materials, ionic metals, derived metal oxides, in addition to their multicomponent hybrids. Porous carbon resources can indeed be manufactured using a variety of synthetic methods, including hard templating and soft templating, depending on their intended applications. The frame precursors fill the voids prevailing in the organized solid prototype, which further remove the porous structure when synthesis is done in the hard templating adopted approach. Soft templating, on the other hand, entails more delicate physiochemical interfaces flanked by the source and the structural template, which further influence the self-assembled amalgamation to consent for greater control of the measurable characteristics [35]. Soft templating, as compared to hard templating, is able to make available a more effective strategy for the amalgamation of well-ordered and chaotic porous matrices. Porous materials are often manufactured by utilizing the solvothermal process in the soft templating pathway. Because of its relative simplicity and scalability, the process of solvothermal is adopted as the utmost recommended approach for important manufacturing. Aside from being employed for zeolite synthesis, the principle of solvothermal synthesis has also been used successfully for MOF synthesis. MOFs can function as a precursor in the framework of synthesizing different nanocomposites commencing MOFs, whereas the metal ion components extracting with inherent metal source to generate nanocomposites of metals ions were employed as a carbonbased source to generate nanoporous carbon [36].

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Overall, the specified structural MOF, such as Cu-BTC as well as MOF-5, implodes throughout the carbonization tempting process, although others involving ZIF8 and ZIF-67 provide an improved pattern toward direct establishment of special pores by means of allowing evaporative cooling of limited organic moisture content all through pyrolysis, arising in a springy pore system. Nonetheless, uniform dispersion of nanocomposite in respective moderate medium is anticipated. Following are some of the benefits of employing MOFs which act as a precursor or as a sacrificial template for the creation of diverse nanostructures. (a) The controlled calcination of MOFs enables the creation of MOF-derived nanocomposite along chosen topological consistencies and substantial characteristics. (b) The use of MOFs as templates helps decrease unwanted fundamental collapse of the structural framework throughout calcination since they typically exhibit structural robustness. (c) Enable for simple functional performance by means of additional heteroatoms and metal/metal oxides, increasing overall performance and efficiency. (d) MOF preparation may be done under moderate circumstances and using simple methods. MOF-derived nanocomposites feature smaller pore volume distributions, larger specific modified surface area, as well as more morphological variants involving nanoscales, hollow sphere-shaped structure, and hollow base polyhedrons, when linked to other nanocomposites. Progressive synthesis method helps in assisting the resolution of the potential inconsistency among electroactive processed material with 3D substrate and sustenance via certain novel development and degradative mechanistics approach. Ongoing research, though, aims at addressing besides to overcome constraints when employing MOF as templates. Approximately, of these restrictions, there is a loss of control over the size regarding pores of MOF-derived nanocomposites owing to a lack of information by means of MOF breakdown processes, as well as the need for considerably large calcination temperatures. Importantly, diverse topologies especially crystallographic stages, also porosities may be situated and created by submitting precursors regarding MOF of varying architectures and crystallinity toward involvement of different calcination temperatures. Many types of nanocomposites are produced by specific thermally treated MOF precursors. It is also worth noting that the ion exchange approach has reemerged as an alternative to heat treatment for the creation of different nanostructures from MOF precursors, despite the fact that the ion-exchange process required additional chemicals and experimental procedures that synthesized nanocomposite on or after this scheme displayed several intriguing features [36].

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11.4 Ciprofloxacin CIP (having the chemical formula C17H18FN3O3) is also known as a fluoroquinolone antibiotic having the second peer group comprising a similar drug’s quinolone structure as well as a piperazine moiety. Hence, it was presented commercially in the 1980s time period while it has since become the upmost prevalent antibiotics used in hospitals, having sales beyond $1 billion according to the report analysis by the end of the 1990s. Eventual CIP is extensively used in cooperation with human as well as veterinary medicine, besides it now ranks fourth in the European antibiotic marketplace. In reality, according to a recent European study, CIP accounts for 73% consumption of second fluoroquinolones, with a regular dose ranging from 0.39 to 1.8 per 1,000 persons. CIP as an antibiotic is often identified as such antibiotic is found in wastewater treatment amenities and raw drinking water, by concentrations ranging from 11 to 99 g/L and 0.032 g/L, respectively. Moreover, it is found in hospital wastewater with concentrations of about 150 g/L, lakes with concentrations around 6.5 mg/L, and pharmaceutical industry discharges with concentrations ranging from 31 to 50 mg/L. Furthermore, CIP is one of the top ten high-priority drugs found in aquatic environments [37].

11.5 Ciprofloxacin consequence on living organisms and the environment Residual material of CIP found in the aquatic ecosystem poses certain risks and not only affects just humans but also other creatures. Veracity is the inherent danger associated with antibiotic discharge which is still not completely understood. Besides having a negative impact on the quality of water due to existence of CIP in ecosystem, its able to modify the dimensions of high superficial area where soil properties like soil mineral deposits and metal oxides headed to control the bioavailability then kinesis of other impurities and nutrients due to induced physical properties. In the case of organisms, CIP discharge into the environment may cause chromosome alterations in local bacteria, primarily to the work on increasing the CIP-resistant strains [38]. As a result, greater doses of CIP would have been necessary to suppress infectious diseases or, in certain situations, preclude the treatment of bacterial infections, posing an obvious risk to public health. It could even hasten the mortality of microorganisms used in wastewater cleanup. CIP can also cause temporary variations in the activity of microbial communities, which may be connected to their production, even at low concentrations. Additional impacts have been observed, including toxicological effects on unintended infections, changes in the structure, and spread of

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algal communities. Water that contains CIP may cause vomiting, tremors, nausea, headache, diarrhea, as well as agitation in people. Additional documented side effects include stomatitis, leukopenia, skin condition, and immune system impairment Furthermore, the existence of CIP interacts with photosynthetic processes and potentially causes morphological abnormalities in higher plants [39].

11.6 General idea of strategies for CIP mitigation This section discusses the many mitigating measures utilized for CIP. It allows to demonstrate about the relevant adsorption process and also it provides benefit over additional CIP mitigation methods, thus confirming the emphasis of study. Nanofiltration, ultrafiltration, hyperfiltration, and microfiltration are ultrafiltration methods that employ highly porous barriers made of metallic, ceramic, or polymerized resources in order to eliminate tiny constituent part, dissolved substances, and colloidal particles from liquid medium [40]. It was achieved that optimum rejection of >99% CIP next to 1 mg/L at 4.5 kg/cm2 by transmembrane layered pressure using ceramics with ultrafiltration membranes. Reverse osmosis membrane, however, effectively cleared almost all of the CIP facing a maximum refusal of 99.96%, which is greater than 90%. Because magnetic resins have appropriate magnetic separation properties, they have been widely employed as adsorbents in water treatment. Advanced oxidation with permeability volume techniques are sophisticated approaches toward pollution mitigation; and the higher efficiency of oxidation by hydroxyl radicals (-OH), sulfate radical ion (SO4–), and also azide radical ion (-N3) are generated throughout the whole processes. Increasing effectiveness of such oxidants seem critical to the performance of AOPs. When CIP concentrations are lower in water, researchers may employ ozonation, sonocatalysis, Fenton/electro- Fenton/photo-Fenton oxidation, hydrolysis, photodegradation, persulfate procedure, ultraviolet process [43], as well as photocatalytic degradation, along with combinations of the aforementioned technologies. As per Sayed et al. [44], poly(vinyl alcohol)-assisted TiO2/Ti sheet with PMS degraded 98.3% of CIP. Advanced oxidation with permeability volume techniques are sophisticated approaches toward pollution mitigation; those who take use of the higher efficiency of oxidation by hydroxyl radicals (-OH), sulfate radical ion (SO4–), and also azide radical ion (-N3) are generated throughout the whole processes. Increasing effectiveness of such oxidants seem critical to the performance of AOPs. When CIP concentrations are lower in water, researchers may employ ozonation, sonocatalysis, Fenton/electroFenton/photo-Fenton oxidation, hydrolysis, photodegradation, persulfate procedure, ultraviolet process [43], as well as photocatalytic degradation, along with combinations

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of the aforementioned technologies. As per Wu, Z., Y. Wang, Z. Xiong, Z. Ao, S. Pu, G. Yao, and B. Lai et al. [44], poly(vinyl alcohol)-assisted TiO2/Ti sheet with PMS degraded 98.3% of CIP. Some researchers in their research achieved a thorough going of CIP elimination of 99% by combining persulfate ion with nanocatalyst (ZnO), in addition to ultrasound next to a frequency of 60 kHz. By appropriate kinetic model presented information which was consistent with the pseudo-first-order model. Based on such findings, act as reasonable to conclude that AOPs are potential techniques for CIP decomposition in water. However, AOPs are costly and difficult to run, requiring additional energy, significant investment costs, and a highly skilled operator [45]. Even the EC method, which is a nice procedure, has been used for CIP mitigation. Xie, Z., W. Xu, X. Cui, and Y. Wang et al. [46] had a satisfactory result (90.34%), utilizing effective parameters including EC approach with pH 7.78 and having density of 12.5 mA/cm2 for the elimination of CIP from hospital wastewater through the use of an aluminum electrode. Furthermore, employing an iron electrode, >99% CIP remained decreased with pH of 7.5, extant density of 15 mA/cm2, as 60 mg/L of CIP. The efficient coagulant is formed by oxidizing a sacrificial anode material. The EC also uses energy, which is quite expensive; however, it might release hydrogen gas as just return compensates for the operating costs incurred during the EC procedure. Xu, B., S. Senthilkumar, W. Zhong, Z. Shen, C. Lu, and X. Liu et al. [47] discovered 28% degradation of CIP through an anaerobic sulfate-based reducing bacteria in sludge system having CIP concentration of 5,000 mg/L during the biodegradation process. In addition, Yap, M.H., K.L. Fow et al. [48] found that CIP employing an anaerobic chamber of bed reactor and also with an anaerobic organized sheet reactor yielded about 81–16% correspondingly. All these reactors performed similarly. Conversely, the attire structured bed reactor is owing to its low operational plus financial costs because it uses less sustenance material in the bed reactor. Data collected was further analyzed using a first mandate kinetic model, and the reactors operated there act as plug flow reactors. Trametes versicolor destroyed and removed about >90% CIP in designed malt extract having concentration of 2 mg/L CIP obtained when incubated for 7 days. Findings indicated the biological approach for CIP breakdown quite an effective outcome. Wastewater treatment methods are typically used waters with extremely high biological oxygen demand standards required to simply run the process and generally cost-effective. Often, this might be used when the biological oxygen demand/chemical oxygen demand ratio is more than 0.5 [49]. However, the disadvantages of this form of treatment include the length of time required for confinement (often days) and indeed the difficulty in disposing of the sludge. Another Fe–C microprocess of electrolysis observed is very successful, and partakes piqued the interest regarding many academics at relatively low cost or ease of use in recalcitrant organic wastewater treatment. At lower CIP concentration, Yu et al. [50] used a reformed biologically aerated filter method as in Fe–C microelectrolysis.

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11.7 MOF-derived zeolitic imidazolate frameworks (ZIFs) and MIL-100/101 ZIFs are a kind of MOF composed of cobalt and zinc metal ions containing organic compounds with imidazole linkers. Materials withstand wet and severe situations with ease. Because of their large specific surface areas, customizable porosity morphologies, as well as simple production processes, ZIFs have been extensively researched as such important MOFs throughout the last years. Lately, ZIF-8 and ZIF-67 are characterized as strong adsorptive species having the ability of CIP antibiotic removal and elimination. These nonporous materials, though, are challenging to remove as of wastewater and also have low stability in humid environments, restraining their applicability. As a result, an effective synthesis process designed for unraveling ZIF-type solid materials is widely required. In contrast to ZIF research, the strategy in addition to synthesis of magnetic nanocomposites is becoming resentful for the scientific community’s interest due to their high absorbency, magnetic channeling separation, and highly inexpensive and efficient properties. Nevertheless, several studies have also demonstrated cobalt- and iron-based nanocomposites, including FeOOH, CoFe2O4SAC, VC@Fe3O4, Mn/Fe3O4 cubes, Co-Al2O3 nanofiber, Co-N-PC, and La2CoMnO6, which may successfully stimulate. The current research team has recently succeeded in removing organic pollutants utilizing catalytic and photocatalytic techniques.

11.7.1 ZIF-8 catalysis and ciprofloxacin ZIF-8 carbon-based derivatives have greatest surface area, whereas Co-MOF-derived nanocomposites have the greatest specific capacitance. Nitrogen-coordinated ZIF is composed of zinc(II) ion with 2-methylimidazole linker to get tetrahedral units. Therefore, it provides more benefits in membrane separation, adsorption, and catalysis mechanism. Moreover, ZIF-67 contains the very identical zeolite structure as ZIF-8, but instead of zinc ions Zhang and colleagues formed a variety of compounds such as nitrogen porous carbon by combining with ZIF-8 made from zinc salts plus 2-methylimidazole along with carbon sources including urea, xylitol, and sucrose [51]. Addition of extra carbon sources formed a shielding layer around the structure to minimize the effect of nitrogen loss throughout carbonization processing. According to the work of Wang and its coworkers, ZIF-8 was glazed with multiwalled carbon nanotubes (MWCNTs); therefore, necklace-shaped structures were created in 2016. This mainly involves synthesis by stirring a solution of ZIF-8 plus MWCNTs about 24 h before processing at 800 °C for 3 h. As shown in the transmission electron microscopy, the absorbent carbons remained implanted continuously on surfaces of the crystalline structure of MWCNTs after carbonization. Especially

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comparison of core–shell structures with MWCNT-based core–shell structures in both MOF-derived C@MWCNTs shows more permeable surface areas for transportation of ions that do not agglomerate or restack. MOF-derived nanocomposites due to their enhanced properties such as high specific capacitance of about 326 °F/g at a form normalized current of 1 A/g results in the outstanding degree capability, and great cycling stability about 99.7% capacitance retention after 10,000 cycles. Researchers in their findings obtained that nanoporous carbon produced through direct carbonization of ZIF-8 might be utilized as an effective as well as reusable adsorbent for removing contaminants from water. Ibuprofen and diclofenac anti-inflammatory medications, sulfamethoxazole antibiotics, CIP antibiotics, copper ions from aqueous solution, and benzoylurea insecticides are some of the pollutants removed effectively from water by means of ZIF-8-derived nanocomposites. Ahmed’s and Li’s study groups together discovered that pyrolysis-specific temperature has a substantial influence on the porosity as well as adsorptive ability of ZIF-8 produced carbon materials for the removal of CIP antibiotics [52]. Although in comparison 1,000 °C is the optimal pyrolysis temperature for sulfamethoxazole removal, 700 °C was found to be the most effective for CIP removal. Interestingly, both studies indicated higher adsorption capacity than any other materials reported earlier in their sector. In the interim, the CIP adsorption capacity (417 mg/g) produced was more than that reported previously for graphene oxide (379 mg/g), microporous activated carbon (131 mg/g), and MWCNTs (206 mg/g). Additionally, Bakhtiari and colleagues demonstrated that the ZIF-8-derived nanoporous carbon created had a fivefold greater removal percentage than other activated carbon composites “including carbon cloth, granular activated carbon, powdered activated carbon and nitrogen-containing activated carbon” [53].

11.7.2 ZIF-67 catalysis and ciprofloxacin Zhang’s group documented ZIF-67 using calcination in which cobalt salts were mixed with 2-methylimidazole, at 450 °C for 30 min in air which is able to produce porous carbon hollow Co3O4 (rhombic dodecahedral) in 2014. Such hollow rhombic form ensured structural stability all through the charging or moreover discharging cycle, but extremely mesoporous Co3O4 allowed for easy electrolyte penetration as well as a comparatively large electroactive surface area. These features effectively boosted the total rate capacity and cycle life of hollow Co3O4 NPs. At a very high mass normalized current of 12.5 A/g, these nanocomposites have remarkable capacitance of 1,100 °F/g. Hu and colleagues pyrolyzed Se-doped ZIF-67 in 2016 to make CoSe NPs enclosed like a hollow carbon shell. Synthesis of CoSe@C demonstrated outstanding cycling in a repeated way by preserving a 91.6% removal rate (660 mAh/g) after 100 cycles at a mass normalized current of 100 mA/g, owing protection of structure in

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addition to charge transport channels obtainable by the hollow carbon matrix. Yu’s group, on the other hand, used an ion-exchange technique to transform ZIF-67 MOF into CoS2 hollow prisms [54]. In general, ZIF-67 hollow prisms used a rapid ionexchange approach, and then a sulfidation process to transform ZIF-67 into CoS4 bubble-like particles. Following that, a thermal treatment created crystalline hierarchical CoS2 prisms with multilayer hollow peripheries. The synthesized nanocomposite performed admirably as a negative electrode material due to their unique internal structures of hollow interior plus ultrathin shells, through high rate capability as well as long-term cycling stability. Based on the research findings, an inexpensive approach was employed to synthesize magnetic nanocomposite containing microporous ZIF-67 and Fe3O4NPs. Furthermore, the synergistic impact of Fe3O4NPs anchored on ZIF-67 on activating PMS for accelerating CIP degradation in long-term circumstances was revealed. Liu, Z., P. Sun, S.G. Pavlostathis, X. Zhou, and Y. Zhang et al. [55] used AOP to degrade antibiotics into low toxicity by-products for improving drinking water quality. The simple sol–gel approach was used to generate a nanocomposite based on cobalt ZIF-67 and Fe3O4 NPs in investigation. Fe3O4NP nanocomposite was employed as an appropriate platform for microporous ZIF-67 development, with the goal of creating an effective heterogeneous catalyst with magnetic separation for the activation of PMS to rapidly break down CIP antibiotics. The catalytic activity of the suggested nanocomposite was thoroughly examined using numerous operational parameters such as nanocatalyst and oxidant dose, starting pH, coexisting anions, and catalyst permanence. In addition, the scavenging method and electron spin resonance show that sulfate and hydroxyl radicals play an important part in the degradation process. The results indicate positivity that the ZIF-67/Fe3O4 nanocomposite is a greener and more viable solution for large-scale applications, and they provide novel insights into the removal of toxins from the environment. Hollow CO3S4 is developed from ZIF-67 for CIP elimination. When employing a pseudo-second-order kinetic model, the fixed findings had the greatest association coefficient (0.999) of the four distinct kinetic models. Furthermore, data revealed CIP chemisorption behavior on the hollow CO3S4 on the ZIF-67 surface, which was confirmed by Fourier transform infrared measurements. Two bands move to 1,269 and 1,710 cm−1 after adsorption by the MOF given to stretching of CeO and OeH distortion of the carboxyl group, and CeO broadening in the carboxyl group, correspondingly [56], and their peak points are diminished. This effect is thought to be caused by formation of complexes between both the CIP -COOH and the hollow CO3S4 on the ZIF-67 surface [57].

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11.7.3 MIL-100/101 catalysis and ciprofloxacin Considering MIL-101(Fe) as a characteristic MOF material with extraordinarily great porosity as well as confrontation to air, water, and various common solvents, it was preferred as a catalyst sustenance for filling Cu2O/Fe3O4 nano-based composite. In Doan’s 2021 investigation, the optimal conditions for CIP photocatalytic degradation were found to be 0.5 g/L of catalyst dose, pH 7, and CIP concentration of 20 mg/L. In ideal conditions, the degradation efficiency was 99.2% after 105 min of irradiation. Chemical trapping tests indicated that hydroxyl but also superoxide radicals played an important role in the CIP breakdown mechanism. As per findings of this investigation, the Cu2O/Fe3O4/MIL-101(Fe) nanocomposite was a very stable photocatalyst capable of successfully removing antibiotics from aqueous medium. After five cycles, the CIP deterioration efficiency reduced by just 6%, showing the good recycled content of Cu2O/Fe3O4/MIL-101(Fe) nanocomposites. To demonstrate the properties of metal framework structure along with iron oxide nanocomposite on CIP reduction from aquatic media, the method, isotherms, thermodynamics, and kinetics of CIP removal by Fe3O4 NPs, MOF-235(Fe), MIL-100(Fe), Fe3O4@MOF-235(Fe), and Fe3O4@MIL-100(Fe) were probed. The experimental approach was used to investigate the sorption capacity and kinetics. The factors influencing the adsorption behavior were tuned, including the stirring rate, contact duration, starting drug concentration, solution pH, ionic strength, and temperature.

11.8 Knowledge gaps regarding CIP According to the statement of work, many types of adsorbent materials have been explored for CIP adsorption. Adsorbent modification and the synthesis of composite adsorbent materials are presently being studied in order to attain high sorption capabilities. In recent research, sorption capabilities for CIP were shown to be larger than the adsorbent weight [58]. Investigation of alternative types of composite adsorbent and unique modification approaches is likely to push adsorption quality and process efficiency even further. The connecting effect occurs in heavy metal CIP competitive systems. Though several heavy metal ions have been studied, Fe(II) or Fe(III) has not been recorded in the literature. These would be found in soils; hence, knowing how they interact with CIP might assist in estimating how much CIP specific soil types can hold or discharge to groundwater. This information will be helpful to contaminant hydrology researchers. Researchers recently investigated hybrid processes for CIP adsorption that include other methodologies such as “photocatalytic degradation, Fentonoxidation, in situ oxidation, electrolytic enhancement, co-precipitation, catalytic oxidation, EC, sludge systems, and biological systems” [59]. Within approaching

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years, research into hybrid degradation, separation, and biological processes will also most certainly become more widespread. Simulation of neural networks and fuzzy inference systems toward CIP adoption has not been described. This seems to be an essential issue that has to be explored as environmental engineers move toward AI-based tools for problem solving. However, it is not disclosed how used adsorbent is disposed of. Different adsorbate types have been observed to benefit from techniques including such stabilization in cementitious materials as well as polymeric resins. Further research is required for CIP to comprehend its resilience in various matrices.

11.9 Conclusion The removal of CIP is performed by various photocatalysts as discussed earlier. It is possible to conclude that the implementation of photocatalytic-based treatment for CIP-polluted waters must be expanded from laboratory-scale experiments to actual wastewater treatment plants for further investigation. Throughout photodegradation experiments, properties like shape and surface area are important for implementation of catalysts. As just a result, additional research into photocatalysts with various morphologies as well as surface areas is yet another perfect option. Furthermore, contrasting results were obtained when CIP was removed using ZIF-67-derived hollow CO3S4, particularly in the presence of CaCl2. CIP adsorption rate dropped from 118 to 83.2 mg/g and from 118 to 18.6 mg/g when NaCl and CaCl2 concentrations (0–1 mol/L) increased. This discovery is thought to be due to Na+ or Ca2+ competing with CIP for active adsorptive sites, whereas the salt content also altered electrostatic interactions enabling CIP-MOF adsorption. At differing proportions, many forms of nanocomposites are originating in natural water along with wastewater. As a result, it is vital to assess the effects of nanocomposites on the elimination of CECs by MOF-derived nanocomposites. Liang et al. investigated the effects of humic acid on the removal of CIP by ZIF-67derived hollow CO3S4 at a concentration of 10 mg/L at pH 7. The findings revealed that the concentration of humic acid had no effect on the adsorption of the MOF nanocomposite for CIP, but the occurrence of humic acid hindered adsorption for the removal of CIP by a magnetic carbon composite. In the condition of humic acid in water, nanoporous carbons produced by carbonization of ZIF-8 were used to extract CIP. The observations did not reveal the initial hypothesis that CIP adsorption would diminish in the presence of humic acid due to increased competition for the MOF nanocomposite adsorption sites among CIP and humic acid. However, the data demonstrated that CIP absorption on the MOF nanocomposite increased as humic acid concentration increased (from 0 to 5 mg/L) and subsequently stayed

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practically constant at moderate humic acid levels (5–40 mg/L), likely due to diverse relationships among humic acid, CIP, as well as MOF. The first increase in adsorption is due to humic substances adsorption on MOF carbon composites. By generating hydrogen connections among several hydroxyl groups and the CIP amine, these would give greater adsorption sites. However, due to the restriction of carbon materials’ humic acid adsorption capability, any initial increase in humic acid concentration will be detrimental to the adsorption behavior of the MOF-NA, specifically even under the most neutral pH condition (pH 6). Some recent studies have found that MOF-NAs are efficient for the removal of organics and heavy metals, including various CECs, in a wide range of environmental applications. These data reveal that the characteristics of CECs and MOF-NAs, as well as the water quality circumstances, have a substantial impact on the removal/adsorption efficiency of CECs by MOF nanocomposite. The permeability volume and structure of MOF nanocomposite appear to be a crucial impact in adsorption efficiency, specifically when no specialized adsorption mechanism is available which excludes van der Waals interactions. In general, pH is among the most critical elements influencing adsorption capacity since it affects both the speciation of CECs and the functional groups of MOF nanocomposites. Only when the negative/positive charges of CECs and MOF nanocomposites vary, many significant electrostatic interactions occur. Furthermore, CEC adsorption may differ based on the kind and concentration of background anions and cations. Unlike activated carbon, NOM appears to improve the adsorption of certain CECs due to interactions between NOM, CECs, and MOF nanocomposites.

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Index amalgamation 112, 119, 120, 122–123, 139–140, 142, 151, 157, 159, 162 amputation 137–139, 141, 144, 148, 150–151, 157 antibiotic 51–52, 54–55, 60–64, 76, 79–80, 82–84, 87, 99, 102, 137–139, 150, 157–158, 164, 167–170 assisted 22, 24, 26, 40, 104, 110, 116, 118, 122, 137, 141, 159, 163, 165–166, 170 associate 112–113, 119, 123, 137, 139, 141, 143, 145, 148–150, 164 benzene 3, 22, 25, 53, 75 boosted 86, 120, 139–140, 142–143, 146, 168 bundles 38 catalysis 1, 5–6, 9, 21–27, 29–33, 35, 37, 47, 95, 109, 158, 167–170 Cathode 111, 113–117 charge 13–14, 26, 36, 102, 114, 117, 120–123, 140, 159, 161, 169, 172 cluster 1–2, 5, 9, 21, 29, 33, 36, 47, 158, 160–161 composites 4, 8–9, 23, 36–37, 47, 74, 75–76, 80, 85–86, 96–100, 102, 104, 109–114, 116–120, 122, 138–151, 158, 160–162, 168, 170–172 compounds 4, 13, 26, 29–30, 32, 41–42, 44, 47, 51–52, 54, 68, 76–78, 82, 87, 90, 99, 104–105, 116, 123, 137, 141–142, 157, 167 concentration 38, 52, 62–65, 68, 76, 80–82, 84, 101–102, 109–110, 117, 122, 137, 141, 142, 144, 148, 157, 164–166, 170–172 conjugated 35, 43, 51, 55, 60, 68 connect 2, 9, 13–15, 35, 43, 48, 52, 112, 116, 137–138, 143, 145, 146, 148–150, 164, 170, 172 constituents 51, 109–110, 112–115, 118–122, 137, 141, 146–147, 149, 151, 157, 165 controlled 8, 15–17, 30, 33, 35, 43–44, 48, 53–54, 98, 104, 113, 123, 140, 161–164 coordination 1–5, 8, 15, 21–22, 31, 37–38, 43, 81 cost 17, 29–30, 52, 87, 89, 95–96, 105, 112, 115, 140, 166

https://doi.org/10.1515/9783110792607-012

crowded 74 crystals 1, 4, 6–7, 9, 13–14, 21, 29–33, 35–36, 40, 43, 45–46, 48, 103, 113, 121, 123, 138, 141, 161, 167, 169 development(s) 5–6, 16, 29, 32, 36, 38, 40, 43–45, 47, 51, 59, 63, 66, 68, 73–90, 95, 100, 102–105, 121–122, 146, 151, 158, 163, 169 dispensed 53 dosage 55–59, 64 Drug 6, 22–23, 35, 37, 41, 43–44, 46–48, 51–55, 59–60, 62–65, 68, 74, 76, 78–81, 86, 90, 96, 98, 137–139, 157–158, 164, 170 dynamic 23, 116, 139, 151 economical 78, 104, 106 effects 8, 16, 33, 41–44, 47, 48, 51–54, 68, 73, 86, 97, 99, 102, 105, 110, 120–121, 137, 140–141, 144, 148, 158, 162, 164–171 environment 5, 8, 23, 25, 27, 36, 38, 42, 45, 51–53, 55, 59, 61, 66–68, 74, 76, 81, 87, 96–99, 103, 109, 117, 119, 123, 140–141, 157, 161–162, 164–165, 167, 169, 171–172 examine 16, 105, 110, 112–113, 139, 169 existence 8, 22–23, 74, 122, 139–140, 146, 151, 157, 164–165 extremely 21, 47, 102, 120, 138, 160, 162, 166, 168 facile 110 formed 1, 3, 6, 9, 13–17, 21–22, 29–32, 35–36, 38–40, 43, 48, 79, 82–83, 86, 139, 148, 159–160, 162, 166–167 frameworks 1–9, 13–18, 21–27, 29, 31–32, 35–37, 41–47, 73, 76–81, 85, 95–106, 109, 111–113, 117, 121, 137–146, 148, 150, 157–159, 162–163, 167–170 geometries 1, 3, 6, 8, 116 households 76, 96–97, 100 human 51–53, 55, 59–61, 63, 68, 74, 81, 97, 137, 158, 164 hydroxide 17, 35, 38, 110, 140

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inorganic 1–2, 5, 13, 16, 30–32, 36, 38–39, 43, 85, 138, 141, 162 interest 2, 13–14, 22, 24, 41, 87, 105, 138, 140, 143, 146, 149–150, 158–159, 166–167 intriguing 109, 124, 159, 163 magnetic 47, 79–81, 86, 102, 141, 143–144, 146–147, 150, 158–159, 165, 167, 169, 171 materials 1–4, 9, 13–14, 16–17, 21, 26, 29–32, 35–48, 52–54, 73–90, 100–101, 104–105, 109–124, 138–146, 149–150, 158–164, 166–172 Medical 8, 59, 76, 90, 96, 97–98, 100, 158 mesoporous 30, 35, 42, 104, 109, 111, 117, 138, 142, 144, 168 metabolized 52, 60, 61 Metal Organic frameworks 1–9, 13–18, 21–27, 29, 32, 35–36, 41–46, 73, 76–81, 95–106, 109, 137–138, 157–158 methods 6, 8, 17, 22, 24–26, 35–36, 39–43, 45, 48, 51–52, 59, 66, 68, 76, 85, 90, 97, 100–101, 103, 105, 109–110, 112–113, 140, 143, 157–158, 161–163, 165–166, 169–170 MOFs 1–9, 13–18, 21–27, 29–33, 35–48, 73–90, 95, 97, 100–106, 109–124, 137–151, 157–172 molecules 1–2, 5–6, 9, 15, 21, 23, 26, 31, 33, 35–37, 39–40, 42–43, 45, 47–48, 110, 112–113, 120, 142–143, 158 network 4–5, 21–23, 27, 112, 118, 171 Organic 1–6, 8–9, 13, 16, 21–24, 29–33, 35–36, 38–39, 42–43, 47–48, 54, 74, 76, 79–80, 82, 85, 96, 100, 109–113, 137–139, 141–142, 148, 150, 157–158, 160, 162–163, 166–167, 172 osmosis 158, 165 paracetamol 62, 65, 76–77, 84–85, 100, 103 percentage 8, 73, 89, 104, 161, 168 performance 5, 16, 32, 51–53, 79, 84, 105, 110, 111, 116, 118, 123, 140, 142–143, 146–147, 151, 158–159, 163, 165–166, 169, 171 pharmaceutical(s) 51–68, 73–90, 95–106, 137–151, 164 porosity 1, 4, 13, 16, 18, 23, 44, 47, 101–102, 104, 109–110, 124, 150, 158, 167–168, 170

produce 13–15, 17, 35, 39, 42, 46, 51, 68, 86, 99, 105, 139, 160, 163, 168, 171 properties 1–3, 5, 9, 13–18, 21–24, 29–30, 36, 39–40, 42, 47, 55, 76, 78, 81–82, 85, 89, 102–103, 105, 109–110, 138, 140, 143, 146–147, 157, 161, 164–165, 167–168, 170–171 protection 76, 138, 141, 168 raising 52, 86 recording 170 redevelop 137 removal 40, 47, 51–52, 59, 66–68, 73–90, 95, 97, 100, 102–105, 137–151, 157–172 review 23, 36, 47 scientist 4, 27, 73, 76, 78, 87, 90, 104, 138, 140, 142, 145–146, 149–150 solutions 4–5, 7–8, 17, 26, 38–39, 42, 45, 48, 95, 102, 111, 118, 122–123, 138–140, 144, 158, 167–170 stability 2, 7, 16, 22–23, 29–30, 32–33, 36, 38, 40, 45, 47, 89, 102, 104–105, 117, 123, 142, 150, 159, 161, 167–171 Sterilization 98 strategies 13–16, 37–38, 41–43, 47, 51, 95–96, 105–106, 111, 121–122, 145, 162, 165–167 structure 1–6, 8–9, 13–17, 21–24, 27, 29–30, 33, 35–43, 46, 48, 51, 55–59, 76–77, 82–84, 89–90, 97–101, 103–105, 109–110, 114, 122, 137, 140–149, 157, 160–164, 166–170, 172 symmetry 3–4, 43, 145 synthesis 1, 6–8, 16–17, 21–22, 24–27, 29–30, 32, 35, 37–42, 44, 73–74, 86–90, 97, 103–104, 109, 111, 139, 145–147, 149, 159–160, 162–163, 167–170 technique(s) 2, 6–8, 15, 17, 21, 25, 32–33, 39, 42–43, 66–67, 78, 81, 104–105, 110, 138–140, 143, 147–149, 158, 165–167, 169, 171 temperature 6, 8, 25, 30, 35–36, 39–40, 44–45, 48, 109–110, 112–114, 123, 144, 147, 160–163, 168, 170 tendency 158, 161

Index

tissues 37, 45 transition 14, 22, 24, 31, 83, 104, 112, 117, 158 usage 22, 24, 74, 109, 112, 157, 159 utilization 21, 26, 35, 40, 42, 48, 111, 140, 143, 146–147, 160, 162, 165–168

validness 4 variations 1–3, 23, 25, 39–40, 60, 114, 163–164 Veterinary 51, 54, 59, 61, 139, 164 vicinities 74

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