Kumar, Sunil Kim, Doyun Song, Youngdong Bayarkhuu, Bolormaa Park, Jueun Hoh, Donghee Yavuz, Cafer T. Byun, Jeehye 2025-03-23T12:30:33Z 2025-03-23T12:30:33Z 2025-03-19 2025-07 1613-6810 https://pubs.kist.re.kr/handle/201004/152096 Hierarchically porous polymers offer large surface areas for enhanced catalytic activity, but incorporating photocatalytic sites into these pore channels remains challenging. Inspired by nature's disulfide bonds, which stabilize proteins and enable redox activity, this study introduces a hierarchically porous poly(aryl thioether) photocatalyst via dual disulfide and thioether linkages formed by polycondensation. Thiolate intermediates undergo partial oxidation in air, yielding a micro/mesoporous polymer with a 757 m(2) g(-)(1) surface area, comparable to its microporous counterpart synthesized in N-2. This structure exhibits enhanced adsorption capacity, as demonstrated by tests with volatile organic compounds and mercury ions. The disulfide-functionalized pore walls enable thiyl radical formation under visible light, achieving outstanding diphenylacetylene oxidation performance. This heterogeneous photocatalyst surpasses homogeneous systems, showing >99% conversion efficiency with 3.5% apparent quantum yield at 440 nm. This study pioneers a linker engineering strategy to integrate hierarchical porous structure and photoactive radical generation in a single porous polymer photocatalyst. English Wiley - V C H Verlag GmbbH & Co. Hierarchically Porous Poly(aryl thioether)s Through Dynamic Linker Engineering for Thiyl Radical Photocatalysis Article 10.1002/smll.202501398 1 Small, v.21, no.27 Small 21 27 N scie scopus 001435653100001 2-s2.0-86000270461 Chemistry, Multidisciplinary Chemistry, Physical Nanoscience & Nanotechnology Materials Science, Multidisciplinary Physics, Applied Physics, Condensed Matter Chemistry Science & Technology - Other Topics Materials Science Physics Article; Early Access COVALENT ORGANIC FRAMEWORKS AEROBIC OXIDATION MOLECULAR-OXYGEN ALPHA-DIKETONES REMOVAL ADSORPTION PHOTOOXIDATION DIARYLALKYNES 1,2-DIKETONES THIOL-DISULFIDE EXCHANGE porous organic polymer photocatalyst thiyl radicals disulfide linkages hierarchical porous structure photocatalyzed organic transformations