Kim, Taehwan Kim, Jongbum Lee, Nahyeon Kim, Taewan Seo, Dongyi Yoo, Chun-Jae Lee, Ki Bong Ahn, Yun-Ho Eum, Kiwon 2026-02-19T04:30:34Z 2026-02-19T04:30:34Z 2026-02-19 2026-02 1385-8947 https://pubs.kist.re.kr/handle/201004/154275 Vapor-phase post-synthetic defect healing (VPDH) is shown to convert inherently defect-rich UiO-66 into a truly size-selective molecular sieve suitable for industrial hydrogen purification. Exposing polycrystalline UiO-66 to terephthalic-acid vapor at 260 degrees C lowers the missing-linker density from 1.24 to 0.09 per Zr6 node without the solvents that swell or degrade the framework. The resulting membranes display sharply narrowed pores and deliver single-gas H2/CH4 and H2/C3H8 selectivities of 61 and 99, respectively, while a mixed-gas H2/CH4 selectivity of 143 at 180 degrees C exceeds the Robeson upper bound by nearly a factor of two. Performance is retained up to 3 bar, after 60 days of ambient storage, and after mechanical sonication; exposure to humid 10 ppm SO2 at 180 degrees C causes less than 10% loss in hydrogen flux, whereas pristine UiO-66 and ZIF-8 fail catastrophically. The solvent-free, one-step VPDH route therefore offers a scalable, environmentally benign path to chemically and mechanically robust MOF membranes that meet the temperature, pressure and contaminant challenges of nextgeneration hydrogen purification. English Elsevier BV Solvent-free vapor-phase healing drives UiO-66 membranes beyond the H2/CH4 upper bound Article 10.1016/j.cej.2026.173104 1 Chemical Engineering Journal, v.530 Chemical Engineering Journal 530 N scie scopus 001681630000002 2-s2.0-105028361217 Engineering, Environmental Engineering, Chemical Engineering Article METAL-ORGANIC FRAMEWORKS PERFORMANCE DEFECTS Membrane Gas separation UiO-66 Defects healing Post-synthetic modification