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.