Superwetting Porous Polydivinylbenzene: A Transformative Platform for Advanced Catalysis

ABSTRACT Porous functional materials have great potential in adsorption, separation, heterogeneous catalysis, and energy storage/conversion. Nanoporous poly(divinylbenzene) (PDVB), prepared via unique solvothermal and template‐free methods, is distinct in this field. Its highly crosslinked aromatic framework and hierarchical porosity provide excellent chemical/thermal stability, intrinsic superwettability (superhydrophobicity and superoleophilicity), and tunable catalytically active sites, making PDVB a versatile platform for regulating surface/interface wettability and reaction microenvironments, especially in heterogeneous catalysis. This review summarizes recent advances in designing and synthesizing PDVB‐based catalysts. Key strategies for tailoring pore structure, surface/interface chemistry, and wettability are highlighted, as well as in situ and post‐functionalization methods for integrating diverse catalytic functionalities. Representative catalytic systems (acid/base, metal‐supported, chiral, hybrid, and photocatalytic catalysts) are elaborated to illustrate rational PDVB engineering for versatile catalysis. Special emphasis is on the synergistic effects of superwettability, network swelling and hierarchical porosity in modulating reactant enrichment, mass transport, and active‐site accessibility – enhancing catalytic activity, selectivity, and recyclability. Typical applications in biomass conversion, fine chemical synthesis, and environmental remediation are systematically discussed, focusing on structure–performance relationships. Finally, current challenges and future outlooks (scalable synthesis, catalyst shaping, long‐term stability, and process‐oriented engineering) are outlined to guide the rational development of PDVB‐based catalysts toward practical and sustainable applications.