Targeted C-O Bond Cleavage of *Ch2cho at Copper Active Sites for Efficient Electrosynthesis of Ethylene from Co2 Reduction

*CH2CHO, a pivotal intermediate in CO2 reduction reaction (CO2RR) on copper-based catalysts, hinges on the strength of Cu-C and C-O bonds for the selective production of ethanol and ethylene. However, the targeted cleavage of these bonds at Cu active sites presents a formidable challenge. In this study, we manipulated the selective C-O bond breaking at Cu through an electron enrichment strategy, steering the reaction towards ethylene synthesis. Both experimental and theoretical investigations reveal that Gd incorporation elevates electron density at Cu sites, thereby enhancing Cu-O interaction and concurrently weakening the C-O bond at the critical Cu-*O-CHCH2 bifurcation point. Notably, Gd-doped Cu2O (Gd-Cu2O) demonstrated a 1.43-fold increase in the ethylene/CO ratio relative to undoped Cu2O. This alteration steers the reaction mechanism towards ethylene generation. Our study highlights the pivotal role of regulating reaction intermediates in optimizing activity and selectivity of CO2RR in copper-based catalysts, providing valuable insights for future catalyst development.