Abstract

AbstractMetal–organic framework membranes are frequently used in gas separations, but rare in pervaporation for liquid chemical upgrading, especially for separating water from polyols, due to lack of highly compact and robust micro‐architecture. Here, we report hetero‐lattice intergrown membranes in which amino‐MIL‐101 (Cr) particles embedded into the micro‐gaps of MIL‐53 (Al) rod arrays after secondary growth. By means of high‐resolution TEM and two‐dimensional topologic simulation, the connection between these two distinct MOF lattices at the molecular‐level and their crystallographic geometry harmony is identified, which leads to a close‐knit structure at the crystal boundaries of membranes. Typically, the membrane shows a separation factor as high as 13 000 for a 90/10 ethanediol/water solution in pervaporation, yields polymer‐grade ethanediol, and saves ca. 32 % of energy consumption vs. vacuum distillation. It has a highly robust micro‐architecture, with great tolerance to high pressure, durability against ultrasonic therapy and long‐term separation stability over 600 h.

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