Unraveling and tuning the linear correlation between CH4 and C2 production rates in CO2 electroreduction

Although many catalysts have been reported for the CO2 electroreduction to C1 or C2 chemicals, the insufficient understanding of fundamental correlations among different products still hinders the development of universal catalyst design strategies. Herein, we first discover that the surface *CO coverage is stable over a wide potential range and reveal a linear correlation between the partial current densities of CH4 and C2 products in this potential range, also supported by the theoretical kinetic analysis. Based on the mechanism that *CHO is the common intermediate in the formation of both CH4 (*CHO → CH4) and C2 (*CHO + *CO → C2), we then unravel that this linear correlation is universal and the slope can be varied by tuning the surface *H or *CO coverage to promote the selectivity of CH4 or C2 products, respectively. As proofs-of-concept, using carbon-coated Cu particles, the surface *H coverage can be increased to enhance CH4 production, presenting a high CO2-to-CH4 Faradaic efficiency ( [Formula: see text] ∼52%) and an outstanding CH4 partial current density of -337 mA cm-2. On the other hand, using an Ag-doped Cu catalyst, the CO2RR selectivity is switched to the C2 pathway, with a substantially promoted [Formula: see text] of 79% and a high partial current density of -421 mA cm-2. Our discovery of tuning intermediate coverages suggests a powerful catalyst design strategy for different CO2 electroreduction pathways.