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Author: Corinne An-Li Allen
Publisher:
ISBN: 9781321361650
Category :
Languages : en
Pages : 171
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Book Description
Metal-Organic Frameworks (MOFs) are porous coordination polymers with the potential to excel in catalysis and gas storage/separation. This dissertation will first discuss relevant types of MOFs, their characteristics, and previous functionalization methods. To fully gauge the utility of MOFs, novel materials with tunable properties are required as are appropriate design strategies to create these materials. Of specific interest is MOFs embedded with secondary metal binding groups. Chapter 2 will discuss a mild method to incorporate these functional groups into MOFs. The utilization of photocleavable protecting groups, a nitrobenzyl ether masking an aryl hydroxyl group, allows for the liberation of secondary metal binding sites upon photoirradiation. By combining mixed MOF systems with photochemical and chemical modification methods, multifunctional materials can be accessed from a single starting MOF. Exploration of new postsynthetic modification reactions is explored in Chapter 3. Initial studies focused on a radical initiated photochemical-click reaction to modify a terminal alkene with a free thiol to create a thioether. Depending on the chemical stability and pore size of the MOF material, this reaction was moderately successful at best. Additionally, optimization proved to be difficult due to the number of chemical species present during the course of the reaction. A simpler click Diels-Alder cycloaddition was studied as an alternative route to modify a terminal alkene embedded inside the MOF. The cycloaddition was found to proceed only if there was sufficient space available within the MOF pores and around the alkene moiety. Finally, in Chapter 4, chemically crosslinked organic ligands are studied to probe the tolerance of certain MOFs for geometrically restricted components. Extended oligomeric ligands based on these criteria are also discussed. Even using ligands with up to four organic struts tethered together, the canonical IRMOF structure can still be formed. This indicates that the limitations of coordination polymers are much less stringent than originally thought.
Author: Corinne An-Li Allen
Publisher:
ISBN: 9781321361650
Category :
Languages : en
Pages : 171
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Book Description
Metal-Organic Frameworks (MOFs) are porous coordination polymers with the potential to excel in catalysis and gas storage/separation. This dissertation will first discuss relevant types of MOFs, their characteristics, and previous functionalization methods. To fully gauge the utility of MOFs, novel materials with tunable properties are required as are appropriate design strategies to create these materials. Of specific interest is MOFs embedded with secondary metal binding groups. Chapter 2 will discuss a mild method to incorporate these functional groups into MOFs. The utilization of photocleavable protecting groups, a nitrobenzyl ether masking an aryl hydroxyl group, allows for the liberation of secondary metal binding sites upon photoirradiation. By combining mixed MOF systems with photochemical and chemical modification methods, multifunctional materials can be accessed from a single starting MOF. Exploration of new postsynthetic modification reactions is explored in Chapter 3. Initial studies focused on a radical initiated photochemical-click reaction to modify a terminal alkene with a free thiol to create a thioether. Depending on the chemical stability and pore size of the MOF material, this reaction was moderately successful at best. Additionally, optimization proved to be difficult due to the number of chemical species present during the course of the reaction. A simpler click Diels-Alder cycloaddition was studied as an alternative route to modify a terminal alkene embedded inside the MOF. The cycloaddition was found to proceed only if there was sufficient space available within the MOF pores and around the alkene moiety. Finally, in Chapter 4, chemically crosslinked organic ligands are studied to probe the tolerance of certain MOFs for geometrically restricted components. Extended oligomeric ligands based on these criteria are also discussed. Even using ligands with up to four organic struts tethered together, the canonical IRMOF structure can still be formed. This indicates that the limitations of coordination polymers are much less stringent than originally thought.
Author: Ali Morsali
Publisher: John Wiley & Sons
ISBN: 1119640431
Category : Science
Languages : en
Pages : 256
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Book Description
Owing to the extensive interest in construction of functional metal organic frameworks (FMOFs), this book discusses the roles of functional groups on the structure and application of metal organic frameworks (MOFs). The contents of the book are classified based on the structural and chemical properties of organic functions, in order to make readers able to compare the different effects of each function on the structure and application of the MOFs. In each chapter, the chemical properties of applied functional groups are gathered to give deeper insight into the roles of organic functions in the structure and application of MOFs. In the function-application properties, the authors discuss how a functional group can dominate the host-guest chemistry of the MOFs and how this host-guest chemistry can expand the effectiveness and efficiency of the material in different fields of applications. Finally, function-structure properties are discussed. In function-application properties, it is discussed how a functional group can affect the topology, porosity, flexibility and stability of the framework. The features of this subject are novel and are presented for the first time.
Author: Hermenegildo García
Publisher: John Wiley & Sons
ISBN: 3527809120
Category : Science
Languages : en
Pages : 534
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Book Description
Focusing on applications in separation, adsorption and catalysis, this handbook underlines the importance of this hot and exciting topic. It provides an excellent insight into the synthesis and modification of MOFs, their synthesis on an industrial scale, their use as CO2 and chemical warfare adsorbers, and the role of defects in catalysis. In addition, the authors treat such new aspects as biocatalysis and applications in photocatalysis and optoelectronic devices.
Author: Sujit K. Ghosh
Publisher: Elsevier
ISBN: 0128146346
Category : Science
Languages : en
Pages : 465
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Book Description
Metal-Organic Frameworks for Environmental Applications examines this important topic, looking at potential materials and methods for the remediation of pressing pollution issues, such as heavy-metal contaminants in water streams, radioactive waste disposal, marine oil-spillage, the treatment of textile and dye industry effluents, the clean-up of trace amounts of explosives in land and water, and many other topics. This survey of the cutting-edge research and technology of MOFs is an invaluable resource for researchers working in inorganic chemistry and materials science, but it is also ideal for graduate students studying MOFs and their applications. - Examines the applications of metal-organic frameworks for the remediation of environmental pollutants - Features leading experts who research the applications of MOFs from around the world, including contributions from the United States, India and China - Explores possible solutions to some of today's most pressing environmental challenges, such as heavy-metal contamination in bodies of water, oil spills and clean-up of explosives hidden in land and water - Provides an excellent reference for researchers and graduate students studying in the areas of inorganic chemistry, materials chemistry and environmental science
Author: Leonard R. MacGillivray
Publisher: John Wiley & Sons
ISBN: 1118931580
Category : Science
Languages : en
Pages : 1210
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Book Description
Metal-Organic Frameworks (MOFs) are crystalline compounds consisting of rigid organic molecules held together and organized by metal ions or clusters. Special interests in these materials arise from the fact that many are highly porous and can be used for storage of small molecules, for example H2 or CO2. Consequently, the materials are ideal candidates for a wide range of applications including gas storage, separation technologies and catalysis. Potential applications include the storage of hydrogen for fuel-cell cars, and the removal and storage of carbon dioxide in sustainable technical processes. MOFs offer the inorganic chemist and materials scientist a wide range of new synthetic possibilities and open the doors to new and exciting basic research. Metal-Organic Frameworks Materials provides a solid basis for the understanding of MOFs and insights into new inorganic materials structures and properties. The volume also reflects progress that has been made in recent years, presenting a wide range of new applications including state-of-the art developments in the promising technology for alternative fuels. The comprehensive volume investigates structures, symmetry, supramolecular chemistry, surface engineering, recognition, properties, and reactions. The content from this book will be added online to the Encyclopedia of Inorganic and Bioinorganic Chemistry: http://www.wileyonlinelibrary.com/ref/eibc
Author: Ali Maleki
Publisher: Springer Nature
ISBN: 3031186753
Category : Technology & Engineering
Languages : en
Pages : 344
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Book Description
This book presents a both detailed and comprehensive look at metal–organic frameworks (MOFs), a relatively new class of materials with a broad application potential. The beginning chapters focus on introducing the requisite fundamental knowledge of MOFs with respect to their classification, synthesis, functionalization approaches, and various other physiochemical facets such as structural morphology and coordination chemistry. The remaining chapters cover an array of diverse applications, from areas such as energy storage and environmental remediation, to drug delivery, biosensing, and tissue engineering. Featuring chapters dedicated to the design of novel MOF structures, as well as theoretical calculations via density functional theory and machine learning techniques, this book targets a wide readership of both academic and industrial researchers interested in an in-depth understanding of the latest MOF structure–function relationships, as well as their deployment in a wide variety of coordinated engineering applications.
Author: Jay Singh
Publisher: CRC Press
ISBN: 1000862798
Category : Science
Languages : en
Pages : 335
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Book Description
Due to the structural flexibility, large surface area, tailorable pore size and functional tenability, metal-organic frameworks (MOFs) can lead to materials with unique properties. This book covers the fundamental aspects of MOFs, their synthesis and modification, including their potential applications in different domains. The major focus is on applications including chemical, biosensors, catalysis, drug delivery, supercapacitors, energy storage, magnetics and their future perspectives. The volume: Covers all aspects related to metal-organic frameworks (MOFs), including characterization, modification, applications and associated challenges Illustrates designing and synthetic strategies for MOFs Describes MOFs for gas adsorption, separation and purification, and their role in heterogeneous catalysis Covers sensing of different types of noxious substances in the aqueous environment Includes concepts of molecular magnetism, tunable magnetic properties and future aspects This book is aimed at graduate students, and researchers in material science, coordination and industrial chemistry, chemical and environmental engineering and clean technologies.
Author: Noelle Ruiz Catarineu
Publisher:
ISBN:
Category :
Languages : en
Pages : 119
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Book Description
Described in this dissertation are a range of methods for expanding the complexity of materials in the class of metal-organic frameworks (MOFs). From their discovery in the mid-1990's until today, metal-organic frameworks have largely been built from a narrow set of building blocks: symmetric, aromatic, carboxylates and first row transition or rare earth metals. While much work has been devoted to investigating the scope of their possible applications, more fundamental understanding of their chemistry is needed for the full potential of this class of materials to be realized. In addition to their crystallinity and porosity, the primary reason for the success of metal-organic frameworks in fields ranging from gas storage to catalysis stems from their inherent tunability. Metal-organic frameworks, in contrast to other porous materials such as zeolites, are modular in that they are built from discrete organic and inorganic components and can therefore be tailored to specific purposes. Increasing the attainable complexity of these materials allows for greater optimization toward existing applications and for exploring previously undiscovered areas. Complexity in solid-state materials is introduced through heterogeneity of composition or distribution. For metal-organic frameworks, this heterogeneity is manifested either in the backbone composing the underlying network or in the functionalities exposed to the pore space. Both approaches are investigated in this dissertation. Heterogeneity of the backbone rests in the diversity of the organic and inorganic building units. Heterogeneity of the pore space is provided by functionalization of organic and inorganic structural building units without altering their structural properties. Chapter One presents an introduction to rational design of metal-organic frameworks encompassing the context and background for this work. The building block approach provides control of metal-organic framework structure, stability, and functionality. Both inorganic and organic building units are available for modification. Variations in linker length, geometry, and connectivity correlate with changes in the extended structure. Choice of coordinating group is another element of control. Much remains to be investigated in terms of linkage type in metal-organic frameworks by exploring new coordinating groups. Concerning the metal components, the multifarious clusters and chains serving as secondary building units (SBUs) have implications for the structure, stability, and function of these materials. The identity of the metal ions comprising these secondary building units impacts these aspects as well. Heterogeneity of metal-organic framework backbones has been achieved in mixed linker and mixed metal systems. Strategies to achieve pure phases of materials with mixed components include synthesis from a mixture of starting materials as well as post-synthetic modification. Inside heterogeneous pore spaces, desired functionalities coordinate to the metals of the frameworks or are sidechains of the organic linkers. An analysis of the structure and property implications of constructing metal-organic frameworks from heterotopic linkers, meaning those linkers with non-identical coordinating groups, had not been reported. The lack of investigation in this area was the impetus for the research presented in Chapters Two and Three. Chapter Two describes the design, synthesis, and characterization of a heterotritopic linker for metal-organic frameworks. This compound bears a carboxylic acid, catechol, and pyridone and was not known in the literature. The original and optimized synthetic routes are given. The linker is synthesized reproducibly on gram scale in three steps with a single column chromatography purification. The analytical data for this linker are given, including the mass spectrometry, one-dimensional and two-dimensional nuclear magnetic resonance, and infrared spectra. The reasoning behind the choice of metrics and coordinating groups is described. Chapter Three details the synthesis, structure elucidation and refinement, and properties of a metal-organic framework constructed from a heterotritopic linker and zinc(II), termed MOF-910. Despite the asymmetry of the linker, MOF-910 is both highly crystalline and symmetric. Synthetic conditions for crystallization of the heterotritopic linker with zinc(II) required an added base, such as triethylamine. The material is highly porous with a Brunauer-Emmett-Teller surface area of 2,120 m2 g-1and hexagonal channels 21 Å in diameter. The material is remarkably thermally and chemically stable for a zinc-based metal-organic framework. Integrity of the framework is maintained up to 320 °C and under acidic and basic aqueous conditions. The catechol moiety undergoes oxidation to the corresponding semiquinone during the metal-organic framework synthesis. The electron paramagnetic resonance spectrum indicates a ligand-centered radical. Chapter Four concerns the applications and reticular chemistry insights uncovered by MOF-910. One focus is the prediction and control of structure of metal-organic frameworks through lower symmetry and heterotopic linkers. The process for reducing MOF-910 to its underlying topological network is explained. The tto (ttriangles. tetrahedra, octahedra) net, of which MOF-910 is the first representation, is described. The tendency of heterotopic linkers to form helical secondary building units is investigated. The dependence of helical pitch on the distance between the most proximal coordinating groups in asymmetric polytopic linkers is discussed. The contributions of these discoveries to the field of reticular chemistry are stated. The electrochromic and gas adsorption behavior of MOF-910 are described as well. Treatment with a mild oxidant converts colorless crystals to bright red with no change in structure discernible by single-crystal X-ray diffraction and no change in surface area. Exposure to a mild reductant causes red crystals to lose color. Chapter Five focuses on functionalization of metal-organic frameworks constructed from tetrakis(4-carboxyphenyl)porphyrin and zirconium(IV) clusters. The introduction of functionality through the organic ligand is described in MOF-525 and MOF-545. Since the porphyrin core is not involved in structure formation of these metal-organic frameworks, additional reactive sites were installed in these frameworks by coordination to the porphyrin pyrroles. The synthetic conditions for constructing zirconium(IV) metal-organic frameworks with porphyrin linkers bound to aluminum(III), chromium(III), manganese(III), iron(III), cobalt(III), nickel(II), copper(II), and zinc(II) are reported. The synthesis of the aluminum(III) and chromium(III) linkers is given. The activation conditions for these generally difficult to evacuate mesoporous materials are listed. The ability of these metalated porphyrin materials to capture toxic gases is reported.
Author: Anish Khan
Publisher: Materials Research Forum LLC
ISBN: 1644900424
Category : Technology & Engineering
Languages : en
Pages : 426
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Book Description
Because of their nanoporous structures and ultra-high surface areas Metal-Organic Framework Composites (MOFs) are very interesting materials. The book focusses on the following applications: gas capture and storage, especially molecular hydrogen storage; performance enhancement of Li-ion batteries; gas separation, nano-filtration, ionic sieving, water treatment, and catalysis; sustainable renewable energy resources, electrochemical capacitors, including supercapacitors, asymmetric supercapacitors and hybrid supercapacitors; biomedical disciplines including drug delivery, theranostics; biological detection and imaging; nanoparticle photosensitizers for photodynamic therapy (PDT) and photothermal therapy (PTT). Keywords: MOF Materials, Hydrogen Storage, Renewable Energy Applications, Lithium Batteries, MOF-Quantum Dots, Clean Energy, Nanoporous MOFs, Supercapacitors, Therapeutic Applications, Biosensing, Bioimaging, Phototherapy of Cancer, Gas Separation, Nano-filtration, Ionic Sieving, Water Treatment, Drug Delivery, Theranostics; Nanoparticle Photosensitizers, Photodynamic Therapy (PDT), Photothermal Therapy (PTT).
Author: E. Gaigneaux
Publisher: Elsevier
ISBN: 0080540740
Category : Technology & Engineering
Languages : en
Pages : 1150
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Book Description
It has become a tradition that every four years, the Université Catholique de Louvain and the Katholieke Universiteit Leuven jointly organize a symposium devoted to the scientific bases for the preparation of heterogeneous catalysts. These meetings bring together researchers from academia and industry and offer a forum for discussions on the chemistry involved in the preparation of industrial heterogeneous catalysts. This volume containing the Proceedings of the 8th International Symposium on Scientific Bases for the Preparation of Heterogeneous Catalysts consists of papers summarizing most of the 139 oral communications and posters selected by the international scientific committee, composed of 27 experts in the field of catalyst preparation, holding an industrial or academia appointment.The contributions focus on the aspects of catalyst preparation. The main topics are: new approaches in catalyst preparation; advanced preparations of nanoporous and mesoporous catalysts; catalysts preparation for special performances and purposes; catalysts for environmental purposes; and molecular catalysis. Emphasis is put on the role that catalysis can play as an essential element of sustainable development.
