Covalent organic frameworks (COFs) are a class of crystalline porous organic polymers with permanent porosity and highly ordered structures. Unlike other polymers, a significant feature of COFs is that they are structurally predesignable, synthetically controllable, and functionally manageable. In principle, the topological design diagram offers geometric guidance for the structural tiling of extended porous polygons, and the polycondensation reactions provide synthetic ways to construct the predesigned primary and high-order structures. Progress over the past decade in the chemistry of these two aspects undoubtedly established the base of the COF field. By virtue of the availability of organic units and the diversity of topologies and linkages, COFs have emerged as a new field of organic materials that offer a powerful molecular platform for complex structural design and tailor-made functional development. Here we target a comprehensive review of the COF field, provide a historic overview of the chemistry of the COF field, survey the advances in the topology design and synthetic reactions, illustrate the structural features and diversities, scrutinize the development and potential of various functions through elucidating structure-function correlations based on interactions with photons, electrons, holes, spins, ions, and molecules, discuss the key fundamental and challenging issues that need to be addressed, and predict the future directions from chemistry, physics, and materials perspectives.

Covalent Organic Frameworks: Design, Synthesis, and Functions.

Covalent organic frameworks (COFs) are crystalline porous polymers formed by a bottom-up approach from molecular building units having a predesigned geometry that are connected through covalent bonds. They offer positional control over their building blocks in two and three dimensions. This control enables the synthesis of rigid porous structures with a high regularity and the ability to fine-tune the chemical and physical properties of the network. This Feature Article provides a comprehensive overview over the structures realized to date in the fast growing field of covalent organic framework development. Different synthesis strategies to meet diverse demands, such as high crystallinity, straightforward processability, or the formation of thin films are discussed. Furthermore, insights into the growing fields of COF applications, including gas storage and separations, sensing, electrochemical energy storage, and optoelectronics are provided.

Covalent Organic Frameworks: Structures, Synthesis, and Applications

This Review focuses on research oriented toward elucidation of the various aspects that determine adsorption of CO2 in metal–organic frameworks and its separation from gas mixtures found in industrial processes. It includes theoretical, experimental, and combined approaches able to characterize the materials, investigate the adsorption/desorption/reaction properties of the adsorbates inside such environments, screen and design new materials, and analyze additional factors such as material regenerability, stability, effects of impurities, and cost among several factors that influence the effectiveness of the separations. CO2 adsorption, separations, and membranes are reviewed followed by an analysis of the effects of stability, impurities, and process operation conditions on practical applications.

CO2 Capture and Separations Using MOFs: Computational and Experimental Studies

Impact of air pollution on the burden of chronic respiratory diseases in China: time for urgent action

Metal–organic frameworks (MOFs) have received much attention because of their attractive properties. They show great potential applications in many fields. An emerging trend in MOF research is hybridization with flexible materials, which is the subject of this review. Polymers possess a variety of unique attributes, such as softness, thermal and chemical stability, and optoelectrical properties that can be integrated with MOFs to make hybrids with sophisticated architectures. Hybridization of MOFs and polymers is producing new and versatile materials that exhibit peculiar properties hard to realize with the individual components. This review article focuses on the methodology for hybridization of MOFs and polymers, as well as the intriguing functions of hybrid materials.

Hybridization of MOFs and polymers

Covalent organic frameworks (COFs) have attracted growing interest by virtue of their structural diversity and tunability. Herein, we present a novel approach for the development of organic rechargeable battery cathodes in which three distinct redox-active COFs were successfully prepared and delaminated into 2D few-layer nanosheets. Compared with the pristine COFs, the exfoliated COFs with shorter Li+ diffusion pathways allow a significant higher utilization efficiency of redox sites and faster kinetics for lithium storage. Unlike diffusion-controlled manners in the bulk COFs, the redox reactions in ECOFs are mainly dominated by charge transfer process. The capacity and potential are further engineered by reticular design of COFs without altering the underlying topology. Specifically, DAAQ-ECOF exhibits excellent rechargeability (98% capacity retention after 1800 cycles) and fast charge–discharge ability (74% retention at 500 mA g–1 as compared to at 20 mA g–1). DABQ-ECOF shows a specific capacity of 210 ...

Exfoliation of Covalent Organic Frameworks into Few-Layer Redox-Active Nanosheets as Cathode Materials for Lithium-Ion Batteries

Environmental challenges especially air pollution (particulate matter (PM) and toxic gases) pose serious threats to public health globally. Metal–organic frameworks (MOFs) are crystalline materials with high porosity, tunable pore size, and rich functionalities, holding the promise for poisonous pollutants capture. Here, nanocrystals of four unique MOF structures are processed into nanofibrous filters (noted as MOFilter) with high MOF loadings (up to 60 wt %). The MOFilters show high PM removal efficiencies up to 88.33 ± 1.52% and 89.67 ± 1.33% for PM2.5 and PM10, respectively, in the hazy environment, and the performance remains largely unchanged over 48 h of continuous filtration. For the first time, the interactions between such porous crystalline material and particulate pollutants were explored. These thin MOFilters can further selectively capture and retain SO2 when exposed to a stream of SO2/N2 mixture, and their hierarchical nanostructures can easily permeate fresh air at high gas flow rate with t...

Preparation of Nanofibrous Metal–Organic Framework Filters for Efficient Air Pollution Control

A powerful roll-to-roll hot-pressing strategy for mass production of metal-organic framework (MOF)-based filters (MOFilters) using various MOF systems with ranges of substrates is presented. Thus-obtained MOFilters show superior particulate matter removal efficiency under desired working temperatures. Such versatile MOFilters can be scaled up and purposely designed, which endows MOFilters with great potentials in both residential and industrial pollution control.

Roll-to-Roll Production of Metal-Organic Framework Coatings for Particulate Matter Removal

Membrane technology has attracted tremendous attention in the field of gas separation due to its low cost and energy consumption. Polymer membranes are used in some industrial-scale gas separation processes, however, they often suffer a trade-off between permeability and selectivity. To overcome this limitation, porous materials with molecular sieve properties have been combined with polymers to give membranes with enhanced gas separation performance. Metal–organic frameworks (MOFs) are nanoporous materials possessing ultrahigh porosity, large surface area, structural diversity and rich functionalities, which make them promising candidates for gas separation. This review primarily focuses on the fabrication methods of MOF–polymer composite membranes including MOF-based mixed-matrix membranes (MMMs) and polymer supported MOF membranes. Recent progress in MOF membrane fabrication, incorporating the challenges and difficulties faced, are presented. Furthermore, corresponding solutions and strategies are given in detail to offer instructions to fabricate membranes with ideal morphology and performance.

Challenges and recent advances in MOF–polymer composite membranes for gas separation

Pollutant treatment is critical in modern society and often requires tedious workup and expensive facilities. By virtue of structural diversity and tunability, metal–organic frameworks (MOFs) have shown promise in pollutant control. We herein report a powerful templated freeze-drying protocol for the fabrication of multifunctional MOF hollow tubular structures for both air and liquid contaminants filtration. Various hollow tube systems (e.g., “Janus”, “coaxial” and “cellular”) are produced. Specially, a multilayer coaxial MOF hollow tube is prepared for highly efficient capture of mixed inorganic–organic liquid contaminants with >94% filtration efficiency. Further, a “cellular” hollow tube with low pressure-drop (12 Pa, 10 cm s–1) is applied in particulate matter filtration with high efficiency (>92%). Given the rich structural and functional diversities, this protocol might bring MOFs into industrial applications to remediate environmental problems.

Shuai Yuan

Papers

Exfoliation of Covalent Organic Frameworks into Few-Layer Redox-Active Nanosheets as Cathode Materials for Lithium-Ion Batteries

Preparation of Nanofibrous Metal–Organic Framework Filters for Efficient Air Pollution Control

Roll-to-Roll Production of Metal-Organic Framework Coatings for Particulate Matter Removal

Challenges and recent advances in MOF–polymer composite membranes for gas separation

Facile Fabrication of Multifunctional Metal-Organic Framework Hollow Tubes To Trap Pollutants.