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.

Constructing heterojunctions between two semiconductors with matched band structure is an effective strategy to acquire high-efficiency photocatalysts. The S-scheme heterojunction system has shown great potential in facilitating separation and transfer of photogenerated carriers, as well as acquiring strong photoredox ability. Herein, a 0D/2D S-Scheme heterojunction material involving CeO2 quantum dots and polymeric carbon nitride (CeO2 /PCN) is designed and constructed by in situ wet chemistry with subsequent heat treatment. This S-scheme heterojunction material shows high-efficiency photocatalytic sterilization rate (88.1 %) towards Staphylococcus aureus (S. aureus) under visible-light irradiation (λ≥420 nm), which is 2.7 and 8.2 times that of pure CeO2 (32.2 %) and PCN (10.7 %), respectively. Strong evidence of S-scheme charge transfer path is verified by theoretical calculations, in situ irradiated X-ray photoelectron spectroscopy, and electron paramagnetic resonance.

Designing a 0D/2D S-Scheme Heterojunction over Polymeric Carbon Nitride for Visible-Light Photocatalytic Inactivation of Bacteria.

Covalent organic frameworks (COFs) as an emerging class of crystalline porous materials have received much attention due to their tunable porosity, modifiable skeletons, and atomically precise structures. Besides, COFs can provide multiple high-rate charge carrier transport (electron, hole, and ion) pathways, including conjugated skeletons, overlapped π electron clouds among the stacked layers, and open channels with a variable chemical environment. Therefore, they have shown great potential in electrochemical energy storage (EES) and conversion (EEC). However, in bulk COFs, the defects always impede charge carrier conduction, and the difficulties in reaching deep-buried active sites by either electrons or ions lead to limited performance. To overcome these obstacles, numerous research studies have been carried out to obtain COF nanosheets (NSs). This review first describes the preparation strategies of COF NSs via bottom-up and top-down approaches. Then, the applications of bulk COFs and COF NSs in EES and EEC are summarized, such as in batteries, supercapacitors, and fuel cells. Finally, key challenges and future directions in these areas are discussed.

Bulk COFs and COF nanosheets for electrochemical energy storage and conversion

Metal-organic frameworks (MOFs) are an interesting and useful class of coordination polymers, constructed from metal ion/cluster nodes and functional organic ligands through coordination bonds, and have attracted extensive research interest during the past decades. Due to the unique features of diverse compositions, facile synthesis, easy surface functionalization, high surface areas, adjustable porosity, and tunable biocompatibility, MOFs have been widely used in hydrogen/methane storage, catalysis, biological imaging and sensing, drug delivery, desalination, gas separation, magnetic and electronic devices, nonlinear optics, water vapor capture, etc. Notably, with the rapid development of synthetic methods and surface functionalization strategies, smart MOF-based nanocomposites with advanced bio-related properties have been designed and fabricated to meet the growing demands of MOF materials for biomedical applications. This work outlines the synthesis and functionalization and the recent advances of MOFs in biomedical fields, including cargo (drugs, nucleic acids, proteins, and dyes) delivery for cancer therapy, bioimaging, antimicrobial, biosensing, and biocatalysis. The prospects and challenges in the field of MOF-based biomedical materials are also discussed.

Metal-Organic Frameworks for Biomedical Applications.

Metal-organic frameworks (MOFs) have been widely recognized as one of the most fascinating classes of materials from science and engineering perspectives, benefiting from their high porosity and well-defined and tailored structures and components at the atomic level. Although their intrinsic micropores endow size-selective capability and high surface area, etc., the narrow pores limit their applications toward diffusion-control and large-size species involved processes. In recent years, the construction of hierarchically porous MOFs (HP-MOFs), MOF-based hierarchically porous composites, and MOF-based hierarchically porous derivatives has captured widespread interest to extend the applications of conventional MOF-based materials. In this Review, the recent advances in the design, synthesis, and functional applications of MOF-based hierarchically porous materials are summarized. Their structural characters toward various applications, including catalysis, gas storage and separation, air filtration, sewage treatment, sensing and energy storage, have been demonstrated with typical reports. The comparison of HP-MOFs with traditional porous materials (e.g., zeolite, porous silica, carbons, metal oxides, and polymers), subsisting challenges, as well as future directions in this research field, are also indicated.

Metal-Organic Framework-Based Hierarchically Porous Materials: Synthesis and Applications.

Air filtration has become an essential need for passive pollution control. However, most of the commercial air purifiers rely on dense fibrous filters, which have good particulate matter (PM) removal capability but poor biocidal effect. Here we present the photocatalytic bactericidal properties of a series of metal-organic frameworks (MOFs) and their potentials in air pollution control and personal protection. Specifically, a zinc-imidazolate MOF (ZIF-8) exhibits almost complete inactivation of Escherichia coli (E. coli) (>99.9999% inactivation efficiency) in saline within 2 h of simulated solar irradiation. Mechanistic studies indicate that photoelectrons trapped at Zn+ centers within ZIF-8 via ligand to metal charge transfer (LMCT) are responsible for oxygen-reduction related reactive oxygen species (ROS) production, which is the dominant disinfection mechanism. Air filters fabricated from ZIF-8 show remarkable performance for integrated pollution control, with >99.99% photocatalytic killing efficiency against airborne bacteria in 30 min and 97% PM removal. This work may shed light on designing new porous solids with photocatalytic antibiotic capability for public health protection. Personal protective air filtration masks are becoming increasingly desirable, but most commercial air purifiers have poor biocidal capabilities. Here the authors fabricate metal–organic framework-based air filters with both high particulate matter removal efficiencies and photocatalytic bactericidal properties.

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Metal-organic frameworks with photocatalytic bactericidal activity for integrated air cleaning.

Covalent organic frameworks (COFs) with well-tailored channels are able to accommodate ions and offer their conduction pathway. However, due to strong Coulombic interaction and the lack of transport medium, directly including lithium salts into the channels of COFs results in limited ion transport capability. Herein, we propose a strategy of incorporating low-molecular-weight polyethylene glycol (PEG) into COFs with anionic, neutral, or cationic skeletons to accelerate Li+ conduction. The PEG confined in the well-aligned channels retains high flexibility and Li+ solvating ability. The ion conductivity of PEG included in a cationic COF can reach 1.78 × 10-3 S cm-1 at 120 °C. The simplicity of this strategy as well as the diversity of crystalline porous materials holds great promise to design high-performance all-solid-state ion conductors.

Fast Ion Transport Pathway Provided by Polyethylene Glycol Confined in Covalent Organic Frameworks

Covalent organic framework (COF) films combine the processability of polymers with the porosity and atomic precision of crystalline porous materials, properties that are long-sought-after in electronics yet hard to realize. Herein, we prepared four flexible COF films with different alkoxy side chains via interfacial polymerization. The COF films exhibit an ultralow dielectric constant (κ=1.19±0.04 at 105  Hz), small dielectric loss ( 63 kV cm-1 ) and low leakage current (10-10  A cm-2 at 1 kV cm-1 ). They have considerable mechanical strength, and ability to withstand high humidity (RH 70 % for 10 days) and repeated bending (1000 times) without losing their dielectric properties. Extension of the alkoxy chains reduces the film's κ and enhances its moisture resistance, while incorporation of guest molecules further increase the κ value up to 43 times.

Flexible Films of Covalent Organic Frameworks with Ultralow Dielectric Constants under High Humidity

Two-dimensional covalent organic frameworks (2D COFs) are well-defined polymeric sheets that usually stack in an eclipsed mode via van der Waals forces. Extensive efforts have been made to manipulate interlayer interactions, yet there still lack a way to construct conjugated connections between adjacent layers, which is important for (opto)electronic-related applications. Herein, we report an interlayer topological polymerization strategy to transform the well-organized diacetylene columnar arrays in three different 2D COFs (TAPFY-COF, TAPB-COF, and TAPP-COF) into conjugated enyne chains upon heating in the solid state. The resultant COFs (COF-P) with retained high crystallinity possess broadened absorption bands and narrowed band gaps. The newly formed conjugated chains provide extra charge carrier pathways through direct π-electron delocalization. As a proof-of-concept, after topological polymerization, the conductivity of the TAPFY-COF film achieves 2.8 × 10-4 S/cm without doping, and the photothermal, photoacoustic, and oxygen reduction catalytic performance of TAPP-COF is significantly improved.

Jie Li

Papers

Bulk COFs and COF nanosheets for electrochemical energy storage and conversion

Metal-organic frameworks with photocatalytic bactericidal activity for integrated air cleaning.

Fast Ion Transport Pathway Provided by Polyethylene Glycol Confined in Covalent Organic Frameworks

Flexible Films of Covalent Organic Frameworks with Ultralow Dielectric Constants under High Humidity

Construction of Interlayer Conjugated Links in 2D Covalent Organic Frameworks via Topological Polymerization.