Selectivities of Stepped Cu–M (M = Pt, Ni, Pd, Zn, Ag, Au) Bimetallic Surface Environment for C1 and C2 Pathways

Copper (Cu) emerges as a highly efficient and cheap catalytic agent for the electrochemical reduction of carbon dioxide (CO2RR), promising a sustainable route toward carbon neutrality. Despite its utility, the Cu catalyst exhibits limitations in terms of product selectivity, highlighting the need for the development of a superior catalyst design. Herein, we present a density functional theory (DFT) investigation into the selectivities of Cu–M (M = Pt, Ni, Pd, Zn, Ag, Au) bimetallic catalysts (BMCs) for the carbon dioxide reduction reaction (CO2RR). The interaction between the metals of Cu–M makes the surface electrons reconstruct so that the d-band center shifts to the Fermi level. In terms of CO2 activation, the Cu–Ni catalyst exhibits superior performance. Additionally, the Cu–Pd catalyst favors the formation of *COH along the reaction pathway, favoring the generation of CH4. Conversely, the Cu–Ni catalyst preferentially produces *CHO, thereby favoring the production of CH3OH. For the Cu–Ag catalyst, the reaction intermediates along the C2 pathway are *CO–*CHO and *COH–*CHO. The Cu–Ni catalyst follows a reaction path that proceeds via *CO–*CO → *CO–*COH → *COH–CHO. On the other hand, the Cu–Pt catalyst exhibits a reaction sequence of *CO–*CO → *CO–*CHO → *OCH–*OCH. This study provides guiding significance for the design of Cu-based bimetallic catalysts aimed at improving the selectivities and efficiency of the CO2RR process.