Tuning the reaction path of CO2 electroreduction reaction on indium single-atom catalyst: Insights into the active sites

Modulating the local coordination structure of metal single-atom catalysts (SACs) is extensively employed to tune the catalytic activity, but rarely involved in regulating the reaction pathway which fundamentally determines the product selectivity. Herein, we report that the product selectivity of electrochemical CO2 reduction (CO2RR) on the single-atom indium-NxC4-x (1 <= x <= 4) catalysts could be tuned from formate to CO by varying the carbon and nitrogen occupations in the first coordination sphere. Surprisingly, the optimal In SAC showed great promise for CO production with the maximum Faradic efficiency of 97%, greatly different from the reported In-based catalysts where the formate is the dominant product. Combined experimental verifications and theoretical simulations reveal that the selectivity switch from formate to CO on In SACs originates from active sites shift from indium center to the indium-adjacent carbon atom, where the indium site favors formate formation and the indium-adjacent carbon site prefers the CO pathway. The present work suggests the active sites in metal SACs may shift from the widely accepted metal center to surrounding carbon atoms, thereby offering a new implication to revisit the active sites for metal SACs.

Automated summary

Modulating the local coordination structure of metal single-atom catalysts can effectively tune the catalytic activity and reaction pathway, leading to controllable product selectivity. In this study, the product selectivity of electrochemical CO2 reduction on single-atom indium catalysts was successfully switched from formate to CO by varying the carbon and nitrogen occupations in the first coordination sphere. The shift in active sites from the indium center to adjacent carbon atoms was identified as the mechanism behind the selectivity switch. These findings suggest a new implication for the active sites in metal single-atom catalysts.