Facile Synthesis of Sub‐Nanometric Copper Clusters by Double Confinement Enables Selective Reduction of Carbon Dioxide to Methane

Abstract

Previous density-functional theory (DFT) calculations show that sub-nanometric Cu clusters (i.e., 13 atoms) favorably generate CH₄ from the CO₂ reduction reaction (CO₂ RR), but experimental evidence is lacking. Herein, a facile impregnation-calcination route towards Cu clusters, having a diameter of about 1.0 nm with about 10 atoms, was developed by double confinement of carbon defects and micropores. These Cu clusters enable high selectivity for the CO₂ RR with a maximum Faraday efficiency of 81.7 % for CH₄ . Calculations and experimental results show that the Cu clusters enhance the adsorption of *H and *CO intermediates, thus promoting generation of CH₄ rather than H₂ and CO. The strong interactions between the Cu clusters and defective carbon optimize the electronic structure of the Cu clusters for selectivity and stability towards generation of CH₄ . Provided here is the first experimental evidence that sub-nanometric Cu clusters facilitate the production of CH₄ from the CO₂ RR.