Selective CO₂ Photoreduction to Acetate at Asymmetric Ternary Bridging Sites

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Photoreduction of CO₂ is a promising strategy to synthesize value-added fuels or chemicals and realize carbon neutralization. Noncopper catalysts are seldom reported to generate C₂ products, and the selectivity over these catalysts is low. Here, we design rich-interface, heterostructured In₂O₃/InP (r-In₂O₃/InP) for highly competitive photocatalytic CO₂-to-CH₃COOH conversion with a productivity of 96.7 μmol g⁻¹ and selectivity > 96% along with water oxidation to O₂ in pure water (no sacrificial agent) under visible light irradiation. The hard X-ray absorption near-edge structure (XANES) shows that the formation of r-In₂O₃/InP with the isogenesis cation adjusts the coordination environment via interface engineering and forms O-In-P polarized sites at the interface. In situ FT-IR and Raman spectra identify the key intermediates of OCCO* for acetate production with high selectivity. Density functional theory (DFT) calculations reveal that r-In₂O₃/InP with rich O-In-P polarized sites promotes C-C coupling to form C₂ products because of the imbalanced adsorption energies of two carbon atoms. This work reports an interesting indium-based photocatalyst for selective CO₂ photoreduction to acetate under strict solution and irradiation conditions and provides significant insights into fabricating interfacial polarization sites to promote the process.