Condensability sieving porous coordination polymer membranes for preferential permeation of C1–C4 alkanes over H2

Refinery gas contains abundant H 2 and a small amount of C 1 –C 4 hydrocarbons. Here, we propose a condensability sieving strategy to realize preferential permeation of hydrocarbons over H 2 by developing halogen-induced porous coordination polymer (PCP) mixed matrix membranes (MMMs) that display condensability sieving gas transport. The 4-Cl-PCP, 5-Cl-PCP and 5-Br-PCP are synthesized by using Zr 4+ and X-isophthalic acid (where X ​= ​4-Cl or 5-Cl or 5-Br) exhibit increased gas adsorption capacity with the increase in carbon number of the feed gas, but with almost no H 2 adsorption. MMMs containing the PCPs with different charge distributions enhance condensability sieving selectivity and inhibit diffusion selectivity. The permeances of the MMMs originated from condensability sieving are consistent with the polarizability-dependent adsorption of the PCP. The selectivity of the obtained MMMs for n-C 4 H 10 /H 2 , C 3 H 8 /H 2 , C 2 H 6 /H 2 , and CH 4 /H 2 achieve ∼40, ∼15, ∼5, and ∼2, respectively, exhibiting promising applications in refinery gas purification owing to their lower energy consumption compared with H 2 -preferential permeation membranes.