Promoting the conversion of CO2 to CH4via synergistic dual active sites.

Carbon-based single-atom catalysts (SACs) have shown promising applications in the conversion of CO2 into CO. However, the deep reduction process for the production of high-value hydrocarbons is largely limited due to the weak activation of CO. Herein, on the basis of first-principles calculations, a simple coordination regulation method of the active site is proposed to improve the conversion of CO2. Taking NiN4 as an example, by introducing heteroatoms (B, C, O, P, and S atoms), we reveal that NiN3B can effectively capture *CO and further convert to CH4 with an ultralow limiting potential of −0.42 V. The excellent catalytic performance is probably attributed to the formed synergistic dual active sites between non-metal B and metal Ni atoms. Moreover, NiN3B can maintain good stability and the catalytic performance can be further enhanced by increasing the B-doping concentration. This work demonstrates that coordination regulation is an effective strategy to improve the performance of single-atom catalysts and paves a possible way to advance the development of non-Cu-based CO2RR electrocatalysts for high-value hydrocarbon products.