Membrane-based approaches can offer energy-efficient and cost-effective methods for various separation processes. Practical membranes must have high permselectivity at industrially relevant high pressures and under aggressive conditions, and be manufacturable in a scalable and robust fashion. We report a versatile electrochemical directed-assembly strategy to fabricate polycrystalline metal–organic framework membranes for separation of hydrocarbons. We fabricate a series of face-centred cubic metal–organic framework membranes based on 12-connected rare-earth or zirconium hexanuclear clusters with distinct ligands. In particular, the resultant fumarate-based membranes containing contracted triangular apertures as sole entrances to the pore system enable molecular-sieving separation of propylene/propane and butane/isobutane mixtures. Prominently, increasing the feed pressure to the industrially practical value of 7 atm promoted a desired enhancement in both the total flux and separation selectivity. Process design analysis demonstrates that, for propylene/propane separation, the deployment of such face-centred cubic Zr-fumarate-based metal–organic framework membranes in a hybrid membrane–distillation system offers the potential to decrease the energy input by nearly 90% relative to a conventional single distillation process.

基于膜的方法可以为各种分离过程提供节能和经济有效的方法。实用的膜必须在工业相关高压和侵蚀性条件下具有高选择性渗透性，并且可以以可扩展和稳健的方式制造。我们报告了一种通用的电化学定向组装策略来制造用于分离碳氢化合物的多晶金属有机框架膜。我们基于具有不同配体的 12 连接稀土或锆六核簇制造了一系列面心立方金属有机框架膜。特别地，所得到的基于富马酸盐的膜包含收缩的三角形孔作为孔系统的唯一入口，能够实现丙烯/丙烷和丁烷/异丁烷混合物的分子筛分离。突出的是，将进料压力提高到 7 个大气压的工业实用值促进了总通量和分离选择性的预期提高。工艺设计分析表明，对于丙烯/丙烷分离，在混合膜蒸馏系统中部署这种面心立方富马酸锆基金属有机骨架膜提供了将能量输入相对减少近 90% 的潜力。与传统的单一蒸馏工艺相比。