Covalent organic frameworks (COFs) are an emerging class of crystalline porous polymers with highly tuneable structures and functionalities. COFs have been proposed as ideal materials for applications in the energy-intensive field of molecular separation due to their notable intrinsic features such as low density, exceptional stability, high surface area, and readily adjustable pore size and chemical environment. This review attempts to highlight the key advancements made in the synthesis of COFs for diverse separation applications such as water treatment or the separation of gas mixtures and organic molecules, including chiral and isomeric compounds. Methods proposed for the fabrication of COF-based columns and continuous membranes for practical applications are also discussed in detail. Finally, a perspective regarding the remaining challenges and future directions for COF research in the field of separation has also been presented.

Covalent organic frameworks for separation applications.

Covalent organic frameworks (COFs), which are constructed from organic linkers, are a new class of crystalline porous materials comprising periodically extended and covalently bound network structures. The intrinsic structures and the tailorable organic linkers endow COFs with a low density, large surface area, tunable pore size and structure, and facilely-tailored functionality, attracting increasing interests in different fields including membrane separations. Exciting research activities ranging from fabrication strategies to separation applications of COF-based membranes have appeared. This review analyzes the synthesis and applications of diverse continuous/discontinuous COF membranes, such as COF-based mixed matrix membranes (MMMs), COF-based thin film nanocomposite (TFN) membranes, and free-standing COF films. Special attention was given to pore size, stability, hydrophilicity/hydrophobicity and surface charge of COFs in view of determining proper COFs for membrane fabrication, along with the approaches to fabricate COF-based membranes, such as blending, in situ growth, layer-by-layer stacking and interfacial polymerization (IP). Moreover, applications of COF-based membranes in gas separation, water treatment (deaslination and dye removal), organic solvent nanofiltration (OSN), pervaporation and fuel cell are disscussed. Finally, we illustrate the advantages and disadvantages of COF-based membranes through a comparison with MOF-based membranes, and the remaining challenges and future opportunities in this field.

Covalent organic frameworks for membrane separation.

Covalent organic frameworks (COFs) for environmental applications

Sustainable and affordable supply of clean, safe, and adequate water is one of the most challenging issues facing the world. Membrane separation technology is one of the most cost-effective and widely applied technologies for water purification. Polymeric membranes such as cellulose-based (CA) membranes and thin-film composite (TFC) membranes have dominated the industry since 1980. Although further development of polymeric membranes for better performance is laborious, the research findings and sustained progress in inorganic membrane development have grown fast and solve some remaining problems. In addition to conventional ceramic metal oxide membranes, membranes prepared by graphene oxide (GO), carbon nanotubes (CNTs), and mixed matrix materials (MMMs) have attracted enormous attention due to their desirable properties such as tunable pore structure, excellent chemical, mechanical, and thermal tolerance, good salt rejection and/or high water permeability. This review provides insight into synthesis approaches and structural properties of recent reverse osmosis (RO) and nanofiltration (NF) membranes which are used to retain dissolved species such as heavy metals, electrolytes, and inorganic salts in various aqueous solutions. A specific focus has been placed on introducing and comparing water purification performance of different classes of polymeric and ceramic membranes in related water treatment industries. Furthermore, the development challenges and research opportunities of organic and inorganic membranes are discussed and the further perspectives are analyzed.

A Review on Reverse Osmosis and Nanofiltration Membranes for Water Purification.

Metal/covalent–organic framework (MOF/COF) membranes have attracted increasing research interest and have been considered as state-of-the-art platforms applied in various environment- and energy-related separation/transportation processes. To break the trade-off between permeability and selectivity to achieve ultimate separation, recent studies have been oriented towards how to design and exploit ultrathin MOF/COF membranes (i.e. sub-1 μm-thick). Given great advances made in the past five years, it is valuable to timely and systematically summarize the recent development and shed light on the future trend in this multidisciplinary field. In this review, we first present the advanced strategies in fabricating ultrathin defect-free MOF/COF membranes such as in situ growth, contra-diffusion method, layer-by-layer (LBL) assembly, metal-based precursor as the pre-functionalized layer, interface-assisted strategy, and laminated assembly of MOF/COF nanosheets. Then, the recent progress in some emerging applications of ultrathin MOF/COF membranes beyond gas separation is highlighted, including water treatment and seawater desalination, organic solvent nanofiltration, and energy-related separation/transportation (i.e. lithium ion separation and proton conductivity). Finally, some unsolved scientific and technical challenges associated with future perspectives in this field are discussed, inspiring the development of next-generation separation membranes.

Ultrathin metal/covalent-organic framework membranes towards ultimate separation.

Interfacial polymerization of covalent organic frameworks (COFs) on polymeric substrates for molecular separations

Unidirectional diffusion synthesis of covalent organic frameworks (COFs) on polymeric substrates for dye separation

Polyamide-based thin-film composite nanofiltration membranes are widely used for potable water decontamination, brackish water desalination and wastewater reutilization. However, enhancing the water permeance of the polyamide layer within the thin-film composite nanofiltration membrane still remains a great challenge, because of the relatively large thickness and high transport resistance of the polyamide layer produced by intractable interfacial polymerization. Herein, we reported a two-in-one strategy to prepare ultra-permeable nanofiltration membranes via covalent organic framework (COF) nanofiber scaffold mediated interfacial polymerization. The highly porous and hydrophilic COF nanofiber scaffolds enhanced the controlled release of amine monomers, leading to ultrathin polyamide layers. Also, the relatively smooth COF nanofiber scaffolds can be spontaneously evolved into rugged and uneven architectures during interfacial polymerization, providing rough substrates for enlarging the actual areas of polyamide layers. Therefore, the increased areas of polyamide layers were employed as additional water permeable domains. Arising from the synergetic effect of the ultrathin and increased water permeation domains, the produced membranes exhibit exceptional nanofiltration performance with a water permeance of up to 31.1 L m-2 h-1 bar-1 and a Na2SO4 rejection rate of about 95%, outperforming most other nanofiltration membranes. This highly accessible technique opens a new avenue for the design and engineering of ultra-permeable thin-film composite nanofiltration membranes, highlighting its great potential in providing clean water.

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Ultra-permeable polyamide membranes harvested by covalent organic framework nanofiber scaffolds: a two-in-one strategy

Covalent organic frameworks (COFs) are expected to provide exceptional permselectivity in molecular separations because of their stable, uniform, molecular-sized pore channels. To realize the super...

Rui Wang

Papers

Interfacial polymerization of covalent organic frameworks (COFs) on polymeric substrates for molecular separations

Unidirectional diffusion synthesis of covalent organic frameworks (COFs) on polymeric substrates for dye separation

Ultra-permeable polyamide membranes harvested by covalent organic framework nanofiber scaffolds: a two-in-one strategy

Layer-by-Layer Synthesis of Covalent Organic Frameworks on Porous Substrates for Fast Molecular Separations

Secondary Growth of Covalent Organic Frameworks (COFs) on Porous Substrates for Fast Desalination