Carbon dioxide (CO2) electroreduction by metal–nitrogen-doped carbon (MNC) catalysts is a promising and efficient method to mitigate global warming by converting CO2 molecules to value-added chemicals. In this research, we systematically studied the behaviours of single and dual-atom Cu catalysts during the CO2 electroreduction process using density functional theory (DFT) calculations. Two structures, i.e., CuNC-4-pyridine and CuCuNC-4a, were found to be beneficial for C2 chemical generation with relatively high stabilities. Subsequently, we explored the detailed pathways of key products (CO, HCOOH, CH3OH, CH4, C2H6O, C2H4 and C2H6) during CO2 electroreduction on CuNC-4-pyridine and CuCuNC-4a. This research reveals the mechanisms of key product formation during CO2 electroreduction on CuNC-4-pyridine and CuCuNC-4a, which would provide important insights to guide the design of MNC catalysts with low limiting potentials and high product selectivity
