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

Covalent organic frameworks (COFs) represent a new family of porous polymers with highly ordered two or three-dimensional channels. Although numerous studies have been focused on the design and synthesis of COF in the form of powders, the development of COF-based separation membranes is still hampered by the challenges of COF particles agglomeration and harsh synthetic conditions. In this work, interfacial polymerization (IP) directly performed on polymeric substrates as employed in the traditional IP process of polyamide (PA) membranes is developed for the synthesis of COF-based membranes. With the moderate reaction rate between monomer pairs in corresponding aqueous and organic solutions, a conformal growth of COF crystallites directly composited with the polysulfone (PSF) ultrafiltration substrates can be realized within 1 min. The synthesis parameters including reaction time and precursor concentrations are optimized, and thus-synthesized COF/PSF membrane presents a stable rejection to dye (Congo red) of 99.5% with a high water permeance of up to 50 L m h bar, which is 2–10 times higher than that of many other membranes with similar rejection. This convenient IP process is expected to facilitate the up-scaling and real-world applications of COF-based membranes

Selective Swelling of Electrospun Block Copolymers: From Perforated Nanofibers to High Flux and Responsive Ultrafiltration Membranes

This work is devoted to the development of high-flux ultrafiltration membranes using electrospun nanofibers of amphiphilic block copolymers (BCPs) of polystyrene-<i>block</i>-poly­(2-vinylpyridine) (PS-<i>b</i>-P2VP) as building blocks. When soaked in hot ethanol, the solid as-spun BCP fibers are progressively transformed into three-dimensionally perforated fibers with increasing porosities with rising degrees of swelling, which ended up with the equilibrated morphology of spherical micelles. The BCP nanofibers are collected on macroporous substrates and subjected to heating to convert loosely stacked fibers to dense and continuous films. Subsequent swelling in hot ethanol leads to robust composite membranes with nanoporous BCP selective layers tightly adhered to the substrates. Filtration performances of the composite membranes can be conveniently modulated by electrospinning durations. The water permeabilities are as high as 6100 L m^–2 h^–1 bar^–1, which is ∼10–35 times higher than that of commercial membranes with similar rejections. Moreover, with the surface enrichment of P2VP chains the membranes exhibit a strikingly sharp pH-dependent water permeability switchable in the largest amplitude ever reported for multiple cycles. Electrospun fibers can be promising building materials to produce a wide range of membranes with 3D interconnected nanoporosities which also show great potential in separation and biomedical applications

Homoporous Membranes with Tailored Pores by Soaking Block Copolymer/Homopolymer Blends in Selective Solvents: Dissolution versus Swelling

Extraction homopolymers premixed in aligned films of block copolymers by rinsing with selective solvents has long been used for the preparation of membranes with uniform straight pores (homoporous membranes). It is frequently assumed that only the dissolution of homopolymers contributes to the pore formation. However, in this work, we demonstrate that the effect of swelling plays a significant role in determining the pore sizes. We prepare blended films of block copolymers of polystyrene-<i>block</i>-poly­(2-vinyl­pyridine) (PS-<i>b</i>-P2VP) and P2VP homopolymers with low molecular weight and anneal the films to perpendicularly align the P2VP microdomains. Rinsing the aligned films in ethanol results in homoporous membranes, and the pore sizes can be tuned by the dosages of P2VP homopolymers. Interestingly, the pore sizes can also be effectively tailored by changing the rinsing temperatures and/or durations because of the significant contribution of the selective swelling of P2VP blocks under strong rinsing conditions in addition to the contribution of the dissolution of P2VP homopolymers. We identify the portion of the contribution from dissolution and from swelling and demonstrate that the pore sizes can be flexibly tuned within a wider range at no expense of pore ordering and uniformity by balancing the effect of dissolution and swelling

Temperature-dependent rearrangement of gas molecules in ultramicroporous materials for tunable adsorption of CO2 and C2H2

Abstract The interactions between adsorbed gas molecules within porous metal-organic frameworks are crucial to gas selectivity but remain poorly explored. Here, we report the modulation of packing geometries of CO2 and C2H2 clusters within the ultramicroporous CUK-1 material as a function of temperature. In-situ synchrotron X-ray diffraction reveals a unique temperature-dependent reversal of CO2 and C2H2 adsorption affinities on CUK-1, which is validated by gas sorption and dynamic breakthrough experiments, affording high-purity C2H2 (99.95%) from the equimolar mixture of C2H2/CO2 via a one-step purification process. At low temperatures (10) and capacity (170 cm3 g−1) owing to the formation of CO2 tetramers that simultaneously maximize the guest-guest and host-guest interactions. At room temperature, conventionally selective adsorption of C2H2 is observed. The selectivity reversal, structural robustness, and facile regeneration of CUK-1 suggest its potential for producing high-purity C2H2 by temperature-swing sorption