Two-dimensional covalent organic frameworks (2D-COFs) have well-defined porosity and stability. Herein, we demonstrate that 2D-COFs can have three roles in nanolaminated graphene membranes for organic solvent nanofiltration (OSN). The optimized hybrid nanolaminate, assembled from 2D-COFs and reduced graphene oxide (rGO), shows a 162% enhancement in methanol permeance without sacrificing selectivity. When dry, intercalated 2D-COFs serve as a nanospacer to prevent the restacking of rGO. However, when wetted, 2D-COFs assume the additional roles of a stabilizer and a porous filler material. 2D-COFs alleviate rGO swelling in solvents because of a solvation-driven charge redistribution at the COF/rGO interface, which induces an attractive stabilizing force between COF and rGO nanosheets. Further, 2D-COFs can reduce transport pathway length by 15.5% and deliver “shortcuts” for solvent permeance. This work unravels the tripartite role of 2D-COFs as nanospacers/stabilizers/porous fillers, offering new insights into shaping the development of hybrid nanolaminated membranes for OSN.

二维共价有机框架 (2D-COFs) 具有明确的孔隙率和稳定性。在此，我们证明了 2D-COF 在用于有机溶剂纳滤 (OSN) 的纳米层压石墨烯膜中可以发挥三种作用。优化的混合纳米层压板由 2D-COF 和还原氧化石墨烯 (rGO) 组装而成，在不牺牲选择性的情况下，甲醇渗透率提高了 162%。干燥时，插入的 2D-COF 可作为纳米间隔层，防止 rGO 重新堆积。然而，当润湿时，2D-COF 承担了稳定剂和多孔填充材料的额外作用。由于在 COF/rGO 界面处溶剂化驱动的电荷重新分布，2D-COFs 减轻了 rGO 在溶剂中的膨胀，这在 COF 和 rGO 纳米片之间产生了有吸引力的稳定力。此外，2D-COFs 可以将运输路径长度减少 15。5% 并为溶剂渗透提供“捷径”。这项工作揭示了 2D-COF 作为纳米间隔物/稳定剂/多孔填料的三方作用，为塑造用于 OSN 的混合纳米层压膜的发展提供了新的见解。