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Author: Sergio J. Garibay
Publisher:
ISBN: 9781267080295
Category :
Languages : en
Pages : 173
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Book Description
Metal-organic frameworks (MOFs) are a hybrid class of porous materials that are comprised of metal clusters and bridging organic ligands. The modular nature these materials makes them suited for chemical strategies aimed at fine-tuning their structure and function. Significant efforts have been spent on developing MOFs for novel applications through the use of functionalized ligands. However, incorporation of functional groups on the ligands can introduce steric, solubility, and metal-coordinating characteristics that can interfere with MOF formation. By targeting the organic linking component of the a prefabricated MOF one can utilize various organic reactions to transform it into a new MOF with altered functional groups and thus different physical and chemical properties. The work in this thesis explores the development of functionalized MOFs through both prefunctionalization and postsynthetic modification (PSM) approaches on a variety of MOFs. In Chapter 2, the use of chiral tris(dipyrrinato) metalloligands was examined in an attempt to introduce chiral functionality into a set MOFs with distinct topologies realized through the use of a racemic analogue. The results further exemplify the difficulties associated with the functionalized linker strategy and suggest that PSM offers a more viable functionalization route. In Chapter 3, the versatile nature of the PSM approach is demonstrated with the successful incorporation of chiral, amine protected, and free carboxylic acid groups into an amine functionalized framework through the use of anhydrides. In Chapter 4, the scope and limitation of a multi-step PSM approach termed tandem PSM is discussed. A set a diverse multifunctional amide and urea MOFs were realized through tandem PSM. While there have been many studies investigating MOFs as heterogeneous catalysts, most examples utilize unsaturated metal sites. In Chapter 5, the utilization of carboxylic acid functionalized MOFs as a solid state Brønsted acid catalyst for the methanolysis of small epoxides is demonstrated. The use of PSM and moreover MOFs for commercial applications is limited by the chemical instability of many frameworks. Chapter 6 presents the synthesis of chemically robust frameworks and utilization of these materials in harsh PSM reaction conditions for the conversion of bromide groups to cyano groups.
Author: Sergio J. Garibay
Publisher:
ISBN: 9781267080295
Category :
Languages : en
Pages : 173
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Book Description
Metal-organic frameworks (MOFs) are a hybrid class of porous materials that are comprised of metal clusters and bridging organic ligands. The modular nature these materials makes them suited for chemical strategies aimed at fine-tuning their structure and function. Significant efforts have been spent on developing MOFs for novel applications through the use of functionalized ligands. However, incorporation of functional groups on the ligands can introduce steric, solubility, and metal-coordinating characteristics that can interfere with MOF formation. By targeting the organic linking component of the a prefabricated MOF one can utilize various organic reactions to transform it into a new MOF with altered functional groups and thus different physical and chemical properties. The work in this thesis explores the development of functionalized MOFs through both prefunctionalization and postsynthetic modification (PSM) approaches on a variety of MOFs. In Chapter 2, the use of chiral tris(dipyrrinato) metalloligands was examined in an attempt to introduce chiral functionality into a set MOFs with distinct topologies realized through the use of a racemic analogue. The results further exemplify the difficulties associated with the functionalized linker strategy and suggest that PSM offers a more viable functionalization route. In Chapter 3, the versatile nature of the PSM approach is demonstrated with the successful incorporation of chiral, amine protected, and free carboxylic acid groups into an amine functionalized framework through the use of anhydrides. In Chapter 4, the scope and limitation of a multi-step PSM approach termed tandem PSM is discussed. A set a diverse multifunctional amide and urea MOFs were realized through tandem PSM. While there have been many studies investigating MOFs as heterogeneous catalysts, most examples utilize unsaturated metal sites. In Chapter 5, the utilization of carboxylic acid functionalized MOFs as a solid state Brønsted acid catalyst for the methanolysis of small epoxides is demonstrated. The use of PSM and moreover MOFs for commercial applications is limited by the chemical instability of many frameworks. Chapter 6 presents the synthesis of chemically robust frameworks and utilization of these materials in harsh PSM reaction conditions for the conversion of bromide groups to cyano groups.
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: Kristine Kimie Tanabe
Publisher:
ISBN: 9781124543154
Category :
Languages : en
Pages : 249
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Book Description
Metal-organic frameworks (MOFs) are porous crystalline materials that are built from metal ions or metal ion clusters and organic ligands. There has been much interest in designing functionalized MOFs with enhanced host-guest interactions for potential applications in gas storage, catalysis, and separation. However, it has remained a challenge to synthesize functionalized MOFs directly through traditional MOF synthesis. This dissertation focuses on the development of postsynthetic modification (PSM) as a method for functionalizing MOFs. A systematic overview of PSM will be presented to highlight PSM as a general, versatile approach for enhancing the physical and chemical properties of MOFs. In the first half of this dissertation, IRMOF-3, an amino-containing MOF, is modified with a series of alkyl anhydrides, and the effects of reagent size on modification extent are explored. In the next chapter, other amino-containing MOFs systems (DMOF-1-NH2 and UMCM-1-NH2) are synthesized and modified using PSM. Through this study, PSM is shown to be a practical approach for functionalizing MOFs, and also indicates MOF topology can influence the modification outcome. The second half of this dissertation focuses on using PSM to develop MOFs for gas storage and catalysis applications. IRMOF-3, DMOF-1-NH2, and UMCM-1-NH2 are modified and tested for H2 storage. The MOFs are modified with certain functionalities (e.g., alkyl vs. aromatic) to determine if H2 uptake and heat of adsorption is improved. In a separate study, UMCM-1-NH2 is modified with metal binding substituents, and is metallated with different metal ions to generate a series of potential Lewis acid MOF catalysts. The metallated UMCM MOFs are tested for the Mukaiyama aldol reaction and for epoxide ring opening catalysis, and the catalytic results are presented. Lastly, a new functionalization technique, named postsynthetic deprotection (PSD), is introduced. Two new BDC ligands are synthesized with photolabile protecting groups and are incorporated into MOFs. The MOFs are then exposed to UV light, which results in the removal of the photolabile groups to produce MOFs with free, uncoordinated hydroxyl groups. This is the first example of using light to unmask functionalities in a MOF, and presents a novel route for obtaining MOFs with more complex functionalities.
Author: Maciej Damian Korzyński
Publisher:
ISBN:
Category :
Languages : en
Pages : 217
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Book Description
Metal-organic frameworks (MOFs) have established themselves as some of the most versatile materials available, with applications ranging from gas sorption to separation to sensing to catalysis. With a large abundance of structural motifs published to date, research efforts have shifted towards further framework elaboration via post-synthetic modification (PSM), a method to alter the chemical structure of preformed MOFs. The secondary building units (SBUs) of MOFs, which are commonly small inorganic clusters, have been particularly interesting targets for this synthetic approach. The aim of this thesis is to further our understanding of how metal cations interact with these inorganic nodes. Additionally, the node functionalization approach is used to synthesize novel catalysts for the olefin metathesis reaction. In Chapter 1, the reader is introduced to post-synthetic modification of MOFs with a focus on early transition metal species. A review of pertinent literature is presented. Chapter 2 describes how a desire to challenge the limits of the well-precedented cation exchange process led to a serendipitous discovery of a long-sought binding mode in the iconic MOF-5 system using NbCl4(THF)2 as a precursor of niobium. In Chapter 3, attention shifts from fundamental studies to the development of new catalysts for olefin metathesis, a process that to (late has been not been extensively studied in MOFs. After a short introduction about the traditional olefin metathesis catalysis, the prospect of using the inorganic nodes of MOFs as supports akin to the classical platforms used in heterogeneous catalysis is explored. Chapter 4 expands the concepts developed in the previous chapter to rhenium oxide-based olefin metathesis, which is unique compared to catalysis using molybdenum and tungsten oxide systems.
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: 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: Ali Morsali
Publisher: John Wiley & Sons
ISBN: 1119792045
Category : Science
Languages : en
Pages : 226
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Book Description
METAL-ORGANIC FRAMEWORKS WITH HETEROGENEOUS STRUCTURES A unique book that sheds light on Metal-Organic Frameworks complex systems that often display behaviors that surprise and cannot be easily described. In this book, MOF-based heterostructures technology with key characteristics is completely analyzed and the current state-of-the-art is discussed. The authors focus on the complex heterostructures promoted by MOFs with advantage of their recent new advances for various applications with particular emphasis on their design. As an extension of the design and synthesis, the shaping technology of heterostructure MOFs is also of great significance to the future practical applications in industry (adsorption/desorption, gas storage, catalysis, conductivity, optical activity) of this class of complex porous materials. As this unique book covers all of the aspects of complexity in MOFs with heterogeneous structures, it serves as an essential reference to the concepts of introducing complexity to designing the future new platforms of materials with advanced and superior properties. This important compact book provides the reader with: The principal aspects of heterogeneity that produce complexity in MOFs, their effects in the structure chemistry, performance and applications The effects of complexities on the structure of metal-organic frameworks The roles of complexities on metal-organic frameworks applications Explanation of synthesis strategies of the complex heterostructure MOFs. Audience This book will be beneficial for chemists, materials engineers, advanced postgraduate and graduate students, researchers and specialists who are working in the area of materials design and their chemistry, porous crystalline materials, coordination polymers, hybrid and functional materials, as well as industry professionals, such as those working on selective catalysis and adsorption-separation, optics, gas capture, processes of biological and pharmaceutical.
Author: Christopher S. Satterfield
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Book Description
Molecular architecture involves the assembly of molecular building blocks to form supramolecular structures and the decoration of their interiors. The evolution and gathering of molecular building blocks into supramolecular constructs include examples such as co-crystals, micelles, nanoparticles, etc. These cases offer novel and advantageous pathways for research in supramolecular chemistry, however, a class of materials known as metal-organic frameworks (MOFs) materials has emerged as a prime candidate for molecular construction and interior design. MOFs are highly tunable materials because they can be synthesized from a wide range of metals cations and organic linkers. The organic linkers can also be functionalized after the MOF material has been synthesized through a process known as post-synthetic modification (PSM). These materials can be synthesized using two different organic linkers, resulting in a mixed-ligand MOF. If these ligands are modifiable and react independently, the resulting MOF structure will be orthogonally functionalized. Upon PSM we hypothesize that our porous, mixed-ligand MOF will contain homogenous bifunctionality as a blueprint for the construction of a uniformly orthogonally functionalized MOF. The synthesis of the first metal-organic framework, KSU-1, is the first of its kind to be developed at Kansas State University. PSM strategies used in this research show successful functionalization of each organic linker leading to uniform bifunctionality throughout our material. Characterization studies commonly used with MOFs verifies the synthesis and PSM of KSU-1.
Author: David Farrusseng
Publisher: John Wiley & Sons
ISBN: 3527635866
Category : Science
Languages : en
Pages : 415
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Book Description
An international and interdisciplinary team of leading experts from both academia and industry report on the wide range of hot applications for MOFs, discussing both the advantages and limits of the material. The resulting overview covers everything from catalysis, H2 and CH4 storage and gas purification to drug delivery and sensors. From the Contents: - Design of Porous Coordination Polymers/Metal-Organic Frameworks: Past, Present and Future - Design of Functional Metal-Organic Frameworks by Post-Synthetic Modification - Thermodynamic Methods for Prediction of Gas Separation in Flexible Frameworks - Separation and purification of gases by MOFs - Opportunities for MOFs in CO2 capture from flue gases, natural gas and syngas by adsorption - Manufacture of MOF thin films on structured supports for separation and catalysis - Research status of Metal-Organic Frameworks for on-board cryo-adsorptive hydrogen storage applications - Separation of xylene isomers - Metal-Organic Frameworks as Catalysts for Organic Reactions - Biomedical applications of Metal Organic Frameworks - Metal Organic Frameworks for Biomedical Imaging - Luminescent Metal-Organic Frameworks - Deposition of thin films for sensor applications - Industrial MOF Synthesis - MOF shaping and immobilisation A must-have for every scientist in the field.
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.
