Selective CO<sub>2</sub> Photoreduction to Acetate at Asymmetric Ternary Bridging Sites.

Gong, Shuaiqi; Niu, Yanli; Liu, Xuan; Xu, Chen; Chen, Chuncheng; Meyer, Thomas J; Chen, Zuofeng · ACS Nano · 2023

basic_science · Level V

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Abstract

Photoreduction of CO<sub>2</sub> is a promising strategy to synthesize value-added fuels or chemicals and realize carbon neutralization. Noncopper catalysts are seldom reported to generate C<sub>2</sub> products, and the selectivity over these catalysts is low. Here, we design rich-interface, heterostructured In<sub>2</sub>O<sub>3</sub>/InP (r-In<sub>2</sub>O<sub>3</sub>/InP) for highly competitive photocatalytic CO<sub>2</sub>-to-CH<sub>3</sub>COOH conversion with a productivity of 96.7 μmol g<sup>-1</sup> and selectivity > 96% along with water oxidation to O<sub>2</sub> 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-In<sub>2</sub>O<sub>3</sub>/InP with the isogenesis cation adjusts the coordination environment via interface engineering and forms O-In-P polarized sites at the interface. <i>In situ</i> 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-In<sub>2</sub>O<sub>3</sub>/InP with rich O-In-P polarized sites promotes C-C coupling to form C<sub>2</sub> products because of the imbalanced adsorption energies of two carbon atoms. This work reports an interesting indium-based photocatalyst for selective CO<sub>2</sub> photoreduction to acetate under strict solution and irradiation conditions and provides significant insights into fabricating interfacial polarization sites to promote the process.