LAUSR

In the electrochemical reduction of CO2 to CO, controlling the binding of the *COOH intermediate is key to adjusting the selectivity and catalytic activity of the CO product. Herein, we report that CN vacancies were used to control the binding of the *COOH intermediate on a Co PBA-VCN catalyst treated by H2 cold plasma bombardment to improve the CO2RR into CO. The CN vacancies can tune the local electronic structure and coordination environment of CoIII-CN-CoII (Co-PBA-VCN) with a high CO faradaic efficiency close to 100% with remarkable durability (>87 h), and a low onset overpotential of 0.17 V in CO2RR. The steric effects of the VCN can decrease the free energy barrier of the rate limiting step for the formation of *COOH which can further crack into *CO on the active site of the Co near the VCN. This work provides a new strategy to tune the binding of the *COOH intermediate on the catalyst surface by new vacancies of VCN to enhance the CO2RR into a single product.