Bo Wang - Hybrid Metal-Organic Framework and Covalent Organic Framework Polymers

Chapter 1

Introduction

Yuanyuan Zhang

a Advanced Research Institute of Multidisciplinary Science, Frontiers Science Center for High Energy Material, Advanced Technology Research Institute (Jinan), Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, P. R. China Email:

Porous materials with the advantages of high surface area, unique channels, and outstanding adsorption performance are essential for industry and daily life.

Employing the principle of reticular chemistry to design and construct frameworks with targeted topology is termed reticular synthesis, which often starts with rigid and directional inorganic and/or organic building units that are shape persistent during the reticulation process.

Reticular chemistry is first exemplified by MOFs, in which the organic linkers and metal ions or clusters (also known as secondary building units, SBUs) can be assembled via strong bonds in a designed manner. The SBUs are further reticulated with polytopic organic linkers, for example, carboxylates, leading to periodic open frameworks. Due to the flexible combination of the components, more than 100 000 structures have been developed and studied. The surface areas of MOFs are mostly in the range of 1000 to 10 000 m2 g1. All these unique traits make MOFs appealing for applications including gas storage and separation, catalysis, sensing, energy storage, etc.

Under the guidance of reticular chemistry, organic building units can be precisely arranged into periodically extended frameworks linked by covalent bonds, giving the second type of reticular material, COFs. The linkage chemistry has expanded to over 20 reactions, and typical linkage types include boroxine, boronate eater, amide, imine, etc. Organic building units ranging from rigid molecules to flexible units have been utilized for COF construction, such as arenes, coordinated strings, and large macrocycles. These highly ordered organic materials feature low density, large pore size, high surface area, and good thermal stability, showing great potential in the fields of gas storage, optoelectronics, catalysis, electronic devices, and so on.

Although MOFs and COFs exhibit great potential in a wide variety of fields, there are drawbacks limiting their full potential and further industrial applications. For example, some reticular materials show limited stability and cannot withstand the harsh conditions of practical working scenarios. In addition, these crystalline materials are mostly obtained in the form of powder that is insoluble or non-meltable, hindering further shaping into desired forms. To achieve optimal performance and satisfy the requirements from various application areas, it is of significance to introduce new features and functions into reticular materials. Controllable integration of MOFs and COFs with other functional materials offers a powerful way to endow them with special morphology, properties, and functionalities. The rationally constructed composites or hybrids could combine the merits of the components, and even show new traits and superior performance as a result of collective and/or synergistic effects. Considerable efforts have been made to hybridize MOFs and COFs with various functional materials (e.g. polymers, metal nanoparticles, metal oxide, carbon materials, biomolecules) in sophisticated structures, and these hybrids are promising for broad applications including catalysis, separation, energy storage and conversion, biomedicine, etc.

Reticular materialpolymer hybrids in particular attract extensive attention. With the rapid advancement in this field, reticular materialpolymer hybrids have shown great potential for separation technology, sensing, biomedicine, energy storage, and conversion.

Owing to the significance of reticular materialpolymer hybrids and the rapid development in this field, a book offering a comprehensive and useful source of information and progress on this topic is highly desired. With critical contributions from experts working in this field, this book contains eight chapters and starts with a brief background and overview of the theme. In Chapter 2, Seth M. Cohen and his colleague review the synthesis, properties, and characterization strategies of polyMOFs, a distinct class of MOFpolymer hybrid materials. In the following chapter, Takashi Uemura et al. discuss the progress regarding the polymer@MOF with focus on the synthesis, recognition, and hybridization methods. Jianrong Li et al., in Chapter 4, provide a comprehensive review of the synthetic approaches applied for the hybridization of MOFs and polymers based on their respective MOF/polymer interactions. The progress in MOF/polymer composite membranes, as well as their separation applications, is described by Yanshuo Li and colleagues in Chapter 5. Bo Wang et al. then summarize the applications of MOFpolymer hybrids in electrochemistry, toxic chemical protection, and biomedicine. In Chapter 7, Xiao Feng et al. present an elaborate review of COF chemistry including design concepts, synthetic strategies, and characterization methods, as well as the applications of COFs. In the last chapter, Wei Zhang and colleagues highlight the recent development of COFlinear polymer composites, with an emphasis on their synthetic approaches and emerging applications.

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