Tailoring grain boundaries and doping on Cu-based electrocatalyst for efficient CO2 reduction reaction

Electrochemical conversion of CO2 on Cu-based catalysts offers an auspicious strategy for addressing the increasingly serious environmental issues. However, there is still a challenge in the regulation of selectivity for an efficient CO2 conversion process on Cu-based catalysts due to the complexity of the internal structure of catalysts. Herein, we step wisely control the intrinsic grain boundaries (GBs) and Sn doping in Cu substrate to optimize the CO2 reduction reaction (CO2RR) performance of catalyst, which also clearly clarify the contribution of above two factors towards CO2RR performance. As a result, the as-synthesized R-SnCu catalyst with both GBs and Sn doing exhibits the highest CO selectivity of 99 % at −0.8 V versus hydrogen electrode (vs. RHE). In-situ Raman spectroscopy was further used to provide critical evidence of the key intermediates during CO2RR. We find that compared to the catalysts containing only GBs or Sn doping, the R-SnCu catalyst controlled by both GBs and Sn doping exhibits a more pronounced adsorption preference for C-bound *COOH intermediate peaks related to CO generation. These findings provide new ideas for the effective design of high-performance Cu-based CO2RR catalysts.