Advances in the understanding of selective CO₂ reduction catalysis

Abstract The electrochemical synthesis for value‐added chemicals and fuels via carbon dioxide reduction reaction (CO 2 RR) offers an effective route to close the anthropogenic carbon cycle and store renewable energy. Currently, the copper‐based catalyst is still the only choice for generating various CO 2 RR species beyond two electron products. However, the wide range of CO 2 RR products generated on copper leads to low selectivity, and their low concentrations in electrolytes pose great costs in the downstream purification process and significantly challenge the scalability of this technology. To make this technology economically viable, enhancing product selectivity is crucial. In this review, we identify the primary CO 2 RR species and discuss the latest insights into the reaction mechanisms controlling CO 2 RR selectivity. Then, we examined factors that affect CO 2 RR selectivity. Emphasizing these factors in catalyst design, we highlight the importance of advanced technologies to expand our knowledge and prospects for the future of the CO 2 RR.