Cover -- Half Title -- Title Page -- Copyright Page -- Table of Contents -- Preface -- 1: Design and Synthesis: Covalent Organic Frameworks -- 1.1 Introduction -- 1.2 Design and Synthesis -- 1.2.1 COF Synthesis in the Dynamic Covalent Chemistry Concept -- 1.2.2 Dynamic Linkages of Building Blocks -- 1.2.3 Topology and Geometry of 2D Porous Materials Containing COFs -- 1.3 Synthetic Methods of COFs -- 1.3.1 Solvothermal Synthesis -- 1.3.2 Ionothermal Synthesis -- 1.3.3 Microwave Synthesis -- 1.3.4 Mechanochemical Synthesis -- 1.3.5 Room-Temperature Synthesis 2: Crystallization and Structural Linkages of COFs -- 2.1 b-O Linkages -- 2.1.1 Boroxine-Linked COFs -- 2.1.2 Boronic Ester (Dioxaborole)-Linked COFs -- 2.1.3 Spiroborate-Linked COFs -- 2.1.4 Borazine-Linked COFs -- 2.2 Imine Linkages -- 2.3 Hydrazone Linkages -- 2.4 Azine Linkages -- 2.5 Squaraine Linkages -- 2.6 Imide Linkages -- 2.7 Phenazine Linkages -- 2.8 Triazine Linkages -- 2.9 Multihetero Linkages in One COF Skeleton -- 2.10 Perspectives and Challenges -- 3: Gas Adsorption and Storage of COFs -- 3.1 Gas Sorption -- 3.2 Physical and Chemical Adsorption -- 3.3 Brunauer-Emmett-Teller Theory 3.4 Hydrogen Gas Storage -- 3.5 Methane Gas Storage -- 3.6 Carbon Dioxide Gas Storage -- 3.7 Membrane Separation of COFs -- 3.7.1 Key Properties of COFs for Membrane Separation -- 3.7.2 Fabrication of COF-Based Membranes -- 3.7.2.1 Design principles -- 3.7.2.2 Blending -- 3.7.2.3 In situ growth -- 3.7.2.4 Layer-by-layer stacking -- 3.7.2.5 Interfacial polymerization -- 3.7.3 Gas Separation of COF-Based Membranes -- 3.8 Outlook and Conclusions -- 4: Heterogeneous Catalytic Application of COFs -- 4.1 Heterogeneous Catalysts of COFs for C-C Bond Coupling Reactions -- 4.1.1 Suzuki-Miyaura Reaction 4.1.2 Heck, Sonogashira, and Silane-Based Cross-Coupling Reactions -- 4.2 Chiral Heterogeneous Catalysts of COFs for Asymmetric C-C Bond Coupling Reactions -- 4.3 Heterogeneous Bimetallic or Bifunctional Catalysts of COFs -- 4.4 Heterogeneous Photo- and Electrocatalysts of COFs -- 4.5 Heterogeneous Catalysts of 3D COFs -- 4.6 Conclusions and Outlook -- 5: Energy Storage Applications of 2D COFs -- 5.1 2D COFs for Optoelectronics and Energy Storage -- 5.2 Semiconducting and Photoconducting 2D COFs -- 5.3 P-Type Semiconducting 2D COFs -- 5.4 N-Type Semiconducting 2D COFs 5.5 Ambipolar Semiconducting 2D COFs -- 5.6 Lithium-Ion Batteries Using 2D COFs as Electrodes -- 5.6.1 Battery Cathode Application -- 5.6.2 Battery Anode Application -- 5.7 Summary and Perspective -- 6: Biomedical Applications of COFs -- 6.1 Introduction of Biomedical Application -- 6.2 COF Properties of Biomedical Applications -- 6.3 Biomedical COF Applications -- 6.3.1 Drug Delivery -- 6.3.2 Photothermal and Photodynamic Therapy -- 6.4 Biosensing and Bioimaging -- 6.5 Other Biomedical Applications -- 6.6 Conclusions of Biomedical Applications -- Index
Rational synthesis of extended arrays of organic matter in bulk, solution, crystals, and thin films has always been a paramount goal of chemistry. The classical synthetic tools to obtain long-range regularity are, however, limited to noncovalent interactions, which usually yield structurally more random products. Hence, a combination of porosity and regularity in organic covalently bonded materials requires not only the design of molecular building blocks that allow for growth into a nonperturbed, regular geometry but also a condensation mechanism that progresses under reversible, thermodynamic, self-optimizing conditions. Covalent organic frameworks (COFs), a variety of 2D crystalline porous materials composed of light elements, resemble an sp2-carbon-based graphene sheet but have a different molecular skeleton formed by orderly linkage of building blocks to constitute a flat organic sheet. COFs have attracted considerable attention in the past decade because of their versatile applications in gas storage and separation, catalysis, sensing, drug delivery, and optoelectronic materials development. Compared to other porous materials, COFs allow for atomically precise control of their architectures by changing the structure of their building blocks, whereby the shapes and sizes of their pores can be well-tuned. Covalent Organic Frameworks is a compilation of different topics in COF research, from COF design and synthesis, crystallization, and structural linkages to the theory of gas sorption and various applications of COFs, such as heterogeneous catalysts, energy storage (e.g., semiconductors and batteries), and biomedicine. This handbook will appeal to anyone interested in nanotechnology and new materials of gas adsorption and storage, heterogeneous catalysts, electronic devices, and biomedical devices.