Modulation of *CH_xO Adsorption to Facilitate Electrocatalytic Reduction of CO₂ to CH₄ over Cu-Based Catalysts

Copper (Cu) can efficiently catalyze the electrochemical CO₂ reduction reaction (CO₂RR) to produce value-added fuels and chemicals, among which methane (CH₄) has drawn attention due to its high mass energy density. However, the linear scaling relationship between the adsorption energies of *CO and *CH_xO on Cu restricts the selectivity toward CH₄. Alloying a secondary metal in Cu provides a new freedom to break the linear scaling relationship, thus regulating the product distribution. This paper describes a controllable electrodeposition approach to alloying Cu with oxophilic metal (M) to steer the reaction pathway toward CH₄. The optimized La₅Cu₉₅ electrocatalyst exhibits a CH₄ Faradaic efficiency of 64.5%, with the partial current density of 193.5 mA cm^-2. The introduction of oxophilic La could lower the energy barrier for *CO hydrogenation to *CH_xO by strengthening the M-O bond, which would also promote the breakage of the C-O bond in *CH₃O for the formation of CH₄. This work provides a new avenue for the design of Cu-based electrocatalysts to achieve high selectivity in CO₂RR through the modulation of the adsorption behaviors of key intermediates.