Shape‐Matched Nonpolar Pore Surfaces Enhance Alkane Recognition Toward Natural Gas Upgrading

Abstract Efficiently removing C 3 H 8 and C 2 H 6 from natural gas remains a formidable challenge in meeting industrial purification demands. Traditional strategies have primarily focused on subtle polarizability differences among alkane molecules, there have been no reported efforts that exploit their substantial shape disparities for separation purposes. Hence, we customized a two‐dimensional (2D) metal‐organic framework (MOF), Zn‐BPDP, featuring zigzag aromatic pore channels. Zn‐BPDP achieves specific capture of V‐shaped C 3 H 8 and linear C 2 H 6 through the synergistic effect of shape‐matched and nonpolar pore surfaces. Ultimately, Zn‐BPDP exhibits considerable C 3 /C 2 adsorption capacities, along with outstanding C 3 H 8 /CH 4 and C 2 H 6 /CH 4 ideal adsorbed solution theory (IAST) selectivities. Under harsh simulated industrial conditions, including high flow rate (4 mL min −1 ), elevated temperature (318 K), and saturated humidity (RH = 100%), Zn‐BPDP demonstrates superior separation performance for C 3 H 8 /C 2 H 6 /CH 4 mixtures. Theoretical calculations further indicate that shape‐matched aromatic surfaces provide enlarged contact interfaces with both C 3 H 8 and C 2 H 6 through multiple C─H ··· π interactions, thereby presenting an innovative approach for natural gas upgrading.