Single-cluster anchored on PC6 monolayer as high-performance electrocatalyst for carbon dioxide reduction reaction: First principles study

Abstract

Tremendous challenges remain to develop high-efficient catalysts for carbon dioxide reduction reaction (CO2RR) owing to the poor activity and low selectivity. However, the activity of catalyst with single active site is limited by the linear scaling relationship between the adsorption energy of intermediates. Motivated by the idea of multiple activity centers, triple metal clusters (M = Cr, Mn, Fe, Co, Ni, Cu, Pd, and Rh) doped PC6 monolayer (M3@PC6) were constructed in this study to investigate the CO2RR catalytic performance via density functional theory calculations. Results shows Mn3@PC6, Fe3@PC6, and Co3@PC6 exhibit high activity and selectivity for the reduction of CO2 to CH4 with limiting potentials of −0.32, −0.28, and −0.31 V, respectively. Analysis on the high-performance origin shows the more binding sites in M3@PC6 render the triple-atom anchored catalysts (TACs) high ability in regulating the binding strength with intermediates by self-adjusting the charges and conformation, leading to the improved performance of M3@PC6 than dual-atom doped PC6. This work manifests the huge application of PC6 based TACs in CO2RR, which hope to prove valuable guidance for the application of TACs in a broader range of electrochemical reactions.