Metal‐Triflate‐Programmed Ultramicropore Networks in Hybrid Carbon Molecular Sieve Membranes Enable Efficient Gas Separations

Carbon molecular sieve (CMS) membranes are promising for energy‐efficient gas separation, but remain limited by the difficulty of simultaneously controlling pore connectivity, molecular sieving precision and long‐term structural stability. Here we develop a metal‐triflate thermochemical programming strategy that converts polyimide precursors into hybrid CMS membranes with tunable ultramicropore networks. During carbonization, thermally labile triflate anions release volatile fragments to generate interconnected transport pathways, while metal centers regulate carbon ordering, interlayer spacing, and pore‐neck distributions. Al(OTf) 3 ‐programmed membranes achieve a CO 2 permeability of 5058.6 Barrer and a CO 2 /CH 4 selectivity of 54.6, whereas AgOTf‐programmed membranes deliver an H 2 permeability of 9106.5 Barrer and an H 2 /CH 4 selectivity of 165.9 while retaining over 95% of their initial permeability after 28 days. Molecular simulations reveal enhanced ultramicropore connectivity, optimized pore‐neck distributions, and suppressed nonselective transport. This work establishes metal‐triflate programming as a versatile strategy for high‐performance CMS membranes for efficient molecular gas separations.