Hierarchically Porous Poly(aryl thioether)s Through Dynamic Linker Engineering for Thiyl Radical Photocatalysis

Abstract 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 N₂. 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.