Tuning the Phase Composition of Metal-Organic Framework Membranes for Helium Separation through Incorporation of Fullerenes.

Metal-organic framework (MOF) membranes have attracted significant research interest in gas separation, but efficient helium (He) separation remains a challenge due to the weak polarizability of He and the intrinsic pore size flexibility of MOFs. Herein, incorporated fullerenes (C and C) were used to tune the crystallographic phase composition of ZIF-8 membranes, thus creating small and fixed apertures for selective He permeation. The fullerene-modified ZIF-8 (C@ZIF-8 and C@ZIF-8) membranes contain about 20% of the rigid-lattice ZIF-8_I-43m phase and have been prepared as 200-350 nm thick supported layers through electrochemical synthesis. They show a significantly enhanced molecular sieving for He/N,CH together with a satisfactory He permeance of >200 GPU. Specifically, the He/N selectivity of the C@ZIF-8 membrane is up to 30.4, which is much higher than that of the fullerene-free ZIF-8 membrane (5.1) and nearly an order of magnitude higher than those of other reported He-selective MOF membranes. A continuous long-term gas permeation test over 780 h under dry and humid conditions proved the excellent stability of the fullerene-modified ZIF-8 membranes. The general validity and versatility of the proposed strategy for MOF membrane preparation are also demonstrated by the enhancement of the separation performance of a fullerene-modified ZIF-76 membrane.