Photocatalytic asymmetric C-C coupling for CO2 reduction on dynamically reconstructed Ruδ+-O/Ru0-O sites

Hongguang Zhang; Asfaw Yohannes; Heng Zhao; Zheng Li; Yejun Xiao; Xi Cheng; Hui Wang; Zhangkang Li; Samira Siahrostami; Md Golam Kibria; Jinguang Hu

doi:10.1038/s41467-025-55885-z

Photocatalytic asymmetric C-C coupling for CO₂ reduction on dynamically reconstructed Ru^δ+-O/Ru⁰-O sites

Nat Commun. 2025 Jan 9;16(1):534. doi: 10.1038/s41467-025-55885-z.

Authors

Affiliations

¹ Department of Chemical and Petroleum Engineering, University of Calgary, 2500 University Drive, NW, Calgary, AB, Canada.
² Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, AB, Canada.
³ State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China.
⁴ Department of Chemistry, Simon Fraser University, 8888 Burnaby, 8888 University Drive, Burnaby, BC, Canada. [email protected].
⁵ Department of Chemical and Petroleum Engineering, University of Calgary, 2500 University Drive, NW, Calgary, AB, Canada. [email protected].
⁶ Department of Chemical and Petroleum Engineering, University of Calgary, 2500 University Drive, NW, Calgary, AB, Canada. [email protected].

Abstract

Solar-driven CO₂ reduction to value-added C₂ chemicals is thermodynamically challenging due to multiple complicated steps. The design of active sites and structures for photocatalysts is necessary to improve solar energy efficiency. In this work, atomically dispersed Ru-O sites in Ru_xIn_2-xO₃ are constructed by interior lattice anchoring of Ru. This results in the dynamic reconstruction of Ru^δ+-O/Ru⁰-O sites upon photoexcitation, which facilitates the CO₂ activation, *CO intermediates adsorption, and C-C coupling as demonstrated by varied in situ techniques. A SiO₂ core in Ru_xIn_2-xO₃/SiO₂ construction further enhances the solar energy utilization and individual Ru_xIn_2-xO₃ nanocrystals dispersion for photocatalytic CO₂ reduction reaction. It results in the maximum ethanol production rate up to 31.6 μmol/g/h with over 90% selectivity. DFT simulation reveals that the C₂ dimer formation primarily underwent an asymmetric *CO-*CHO coupling route via a low-energy precedence ladder of *CHO. This work provides an insightful understanding of active sites with dynamic reconstruction towards asymmetric C-C coupling for CO₂RR at the atomic scale.