The Crystal Plane is not the Key Factor for CO₂ -to-Methane Electrosynthesis on Reconstructed Cu₂ O Microparticles

Cu₂ O microparticles with controllable crystal planes and relatively high stability have been recognized as a good platform to understand the mechanism of the electrocatalytic CO₂ reduction reaction (CO₂ RR). Herein, we demonstrate that the in situ generated Cu₂ O/Cu interface plays a key role in determining the selectivity of methane formation, rather than the initial crystal plane of the reconstructed Cu₂ O microparticles. Experimental results indicate that the methane evolution is dominated on all three different crystal planes with similar Tafel slopes and long-term stabilities. Density functional theory (DFT) calculations further reveal that *CO is protonated via a similar bridge configuration at the Cu₂ O/Cu interface, regardless of the initial crystal planes of Cu₂ O. The Gibbs free energy changes (ΔG) of *CHO on different reconstructed Cu₂ O planes are close and more negative than that of *OCCOH, indicating the methane formation is more favorable than ethylene on all Cu₂ O crystal planes.