Photodriven Catalytic Hydrogenation of CO₂ to CH₄ with Nearly 100% Selectivity over Ag₂₅ Clusters

This is the authors' abstract. We don't add key points for this paper.

The conversion of chemically inert carbon dioxide and its photoreduction to value-added products have attracted enormous attention as an intriguing prospect for utilizing the principal greenhouse gas CO 2 . Herein, we explore the use of Ag 25 clusters with well-defined atomic structures for high-selectivity photocatalytic hydrogenation of CO 2 to methane. Ag 25 clusters, with molecular-like properties and surface plasmon resonance, exhibit competitive catalytic activity for light-driven CO 2 reduction that yield an almost 100% product selectivity of methane at a relatively mild temperature (100 °C). DFT calculations reveal that the absorption of CO 2 on Ag 25 clusters is energetically favorable. The methanation of the Ag 25 cluster catalyst has been investigated by operando infrared spectroscopy, verifying that methane was produced through a −H-assisted multielectron reaction pathway via the transformation of formyl and formaldehyde species to form surface CH x . This work presents a highly efficient strategy for high-performance CO 2 methanation via well-defined metal cluster catalysts.