Isoporous nanomaterials, with their proven potential for accurate molecular sieving, are of substantial interest in propelling sustainable membrane techniques. Covalent organic frameworks (COFs) are prominent due to their customizable isopores and chemistry. Still, the discrepancy in experimental and theoretical structures poses a challenge to developing COF membranes for molecular separations. Here, we report high-selectivity sieving of complex ultrafine molecules through solvating pore-to-pore-aligned two-dimensional COF membranes. Our structurally oriented membrane shows reversible interlayer expansion with intralayer shift in response to solvent exposure. This dynamic deformation induced by solvents leads to a reduction in the aperture of the membrane’s sieving pores, which correlates with the number of COF layers. The resultant membranes yield largely improved molecular selectivity to discriminate binary and trinary complex mixtures, exceeding the conventional COF membranes. The membrane’s robustness against solvents and physical aging permits extremely stable microporosity and reliable operation for over 3000 h. This exceptional performance positions our membrane as an alternative to enriching and purifying value-added chemicals, such as active pharmaceutical ingredients.

中文翻译：

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通过溶剂化二维共价有机框架膜精确分离复杂的超细分子


等孔纳米材料具有被证明具有精确分子筛分的潜力，在推动可持续膜技术方面具有重大意义。共价有机框架 （COF） 因其可定制的等孔和化学性质而备受瞩目。尽管如此，实验和理论结构的差异对开发用于分子分离的 COF 膜构成了挑战。在这里，我们报道了通过溶剂化孔对孔对齐的二维 COF 膜对复杂的超细分子进行高选择性筛选。我们的结构定向膜显示出可逆的层间膨胀，响应溶剂暴露而出现层内偏移。溶剂引起的这种动态变形导致膜筛孔孔径减小，这与 COF 层数相关。所得膜在区分二元和三元复合物混合物方面产生了很大的分子选择性，超过了传统的 COF 膜。该膜对溶剂和物理老化的稳健性使其具有极其稳定的微孔性和超过 3000 小时的可靠运行。这种卓越的性能使我们的膜成为富集和净化增值化学品（如活性药物成分）的替代品。