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

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.