Construction of Ru Single-Atoms on Ceria to Reform the Products of CO₂ Photoreduction.

Abstract

Highly selective production of CH₄ from photocatalytic CO₂ reduction is still a great challenge which involves the kinetically unfavorable transfers of 8 protons and 8 electrons. Herein, CeO₂ photocatalysts incorporated with isolated Ru single-atoms have been fabricated, which demonstrate dramatically elevated selectivity of CH₄ from CO₂ reduction. The introduced Ru single-atoms promote carrier separation and accelerate electron transfer, which efficiently enhances the photocatalytic activity. Density functional theory (DFT) calculations and <i>in situ</i> FT-IR analysis manifest that the Ru single-atom active sites play an indispensable role in strengthening the adsorption of *CO intermediate on the catalyst surface and promoting H₂O oxidation to generate abundant protons, thus favoring *CO protonation into *CH_<i>x</i>O (<i>x</i> = 1, 2, 3) species and final deoxygenation into CH₄. This work provides an effective strategy by constructing single-atom active sites to modulate and stabilize the key intermediates of CO₂ photoreduction to improve the selectivity of the target products.