Photocatalytic asymmetric C-C coupling for CO(2) reduction on dynamically reconstructed Ru(δ+)-O/Ru(0)-O sites.

Solar-driven CO(2) reduction to value-added C(2) 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(x)In(2-x)O(3) are constructed by interior lattice anchoring of Ru. This results in the dynamic reconstruction of Ru(δ+)-O/Ru(0)-O sites upon photoexcitation, which facilitates the CO(2) activation, *CO intermediates adsorption, and C-C coupling as demonstrated by varied in situ techniques. A SiO(2) core in Ru(x)In(2-x)O(3)/SiO(2) construction further enhances the solar energy utilization and individual Ru(x)In(2-x)O(3) nanocrystals dispersion for photocatalytic CO(2) 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 C(2) 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 CO(2)RR at the atomic scale.