Three-Dimensional Pillared [W₁₀O₃₂]-Based Metal–Organic Frameworks for Enhanced Photocatalytic CO₂ Reduction

Photocatalytic reduction technology offers a promising pathway for the sustainable transformation of carbon dioxide into value-added chemicals. In this study, two isostructural three-dimensional pillared [W10O32]4–-based metal–organic frameworks (POMOFs), [M2(4,4′-bipy)6(DMA)2W10O32] (M = Co 1, Ni 2), have been synthesized under solvothermal conditions. Structural characterization verifies their effective light absorption and photogenerated charge separation capability. As photocatalysts for CO2 reduction, compound 1 achieves an effective gaseous product (CO + H2) yield of 3149.4 μmol g–1 h–1, while compound 2 exhibits moderate yields of 1171.1 μmol g–1 h–1 with a CO selectivity of 79%. Mechanistic investigations suggest that the electronic band structures of 1 and 2 facilitate the catalytic reduction of CO2 to CO. This research advances the development of tailored [W10O32]4–-based POMOFs for enhanced photocatalytic CO2 conversion.