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

Abstract

Copper (Cu) emerges as a highly efficient and cheap catalytic agent for the electrochemical reduction of carbon dioxide (CO 2 RR), 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 (CO 2 RR). 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 CO 2 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 CH 4 . Conversely, the Cu−Ni catalyst preferentially produces *CHO, thereby favoring the production of CH 3 OH. 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 CO 2 RR process.