RESUMEN
Nanosheets derived from two-dimensional covalent organic frameworks (2D COFs) are increasingly desirable in various fields. While breakthroughs in the chemical and physical delamination of 2D COFs are rising, precisely regulating the growth of the COF nanosheets has not been realized yet. Herein, we report an effective strategy of polymer-manipulated crystallization to accurately control the growth of COF nanosheets. Chemically asymmetric polyvinylpyrrolidone (PVP) is developed as the manipulator that selectively interacts with the aldehydes and (100) facet to induce anisotropic growth of COFs. The number of PVP constitutional units determines this specific interaction, leading to molecularly thin but thickness-controllable nanosheets with excellent dispersity. We process these nanosheets into robust A4-sized membranes for ultraselective molecular separation. The membrane intercalated with long-chain PVP demonstrates largely improved performance, surpassing the reported COF membranes. This work reports a strategy for anisotropically crystallizing 2D COFs to yield processable nanosheets toward practical applications.
RESUMEN
A heterostructured covalent organic framework (COF) membrane is synthesized via in situ linker exchange. Narrowed pores can be formed at the interface between two types of COFs by adjusting the linker exchange duration. The resultant COF membrane demonstrates a high rejection rate toward Na2SO4 of up to 97%.
RESUMEN
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.
RESUMEN
Covalent organic frameworks (COFs) with ordered arrays of sub-2 nm regular pores are drawing increasing attention in membrane separation, and it remains highly desirable for effective and controllable strategies to fabricate COF-based membranes. Herein, we demonstrate a perforated polymer-assisted transfer strategy enabling COF nanofilms for molecular separation. Solvothermal synthesis is used for the confined growth of TpPa, a stable, imine-linked COF, on the smooth surfaces of silicon substrates. Continuous, crystalline COF nanofilms are obtained, and their thicknesses are tunable in the range from a few tens to several hundred nanometers depending on monomer concentrations and reaction time. A block copolymer layer is coated on the COF nanofilms, which is then perforated to produce interconnected mesopores by the mechanism of selective swelling-induced pore generation. The perforated polymer coating functions as a protective but permeable layer enabling the easy transfer of the COF nanofilm onto porous substrates. Thus, we obtain a new type of composite membranes with the microporous COF nanofilm as the selective layer, sandwiched between the macroporous substrate and the mesoporous protective layer. The composite membranes exhibit good separation performances with water permeance up to â¼51 L m-2 h-1 bar-1 and high rejection rates to various dyes. This work demonstrates a new method to prepare COF-based membranes for molecular separation, and the invented perforated polymer-assisted transfer technology is expected to find applications in transferring other ultrathin materials to demanded substrates.
