Switching CO2 Electroreduction Selectivity Between C1 and C2 Hydrocarbons on Cu Gas‐Diffusion Electrodes.

Regulating the selectivity toward a target hydrocarbon product is still the focus of CO2 electroreduction. Here, we discover that the original surface Cu species in Cu gas‐diffusion electrodes plays a more important role than the surface roughness, local pH, and facet in governing the selectivity toward C1 or C2 hydrocarbons. The selectivity toward C2H4 progressively increases, while CH4 decreases steadily upon lowering the Cu oxidation species fraction. At a relatively low electrodeposition voltage of 1.5 V, the Cu gas‐diffusion electrode with the highest Cuδ+/Cu0 ratio favors the pathways of ∗CO hydrogenation to form CH4 with maximum Faradaic efficiency of 65.4% and partial current density of 228 mA cm−2 at −0.83 V vs RHE. At 2.0 V, the Cu gas‐diffusion electrode with the lowest Cuδ+/Cu0 ratio prefers C–C coupling to form C2+ products with Faradaic efficiency topping 80.1% at −0.75 V vs RHE, where the Faradaic efficiency of C2H4 accounts for 46.4% and the partial current density of C2H4 achieves 279 mA cm−2. This work demonstrates that the selectivity from CH4 to C2H4 is switchable by tuning surface Cu species composition of Cu gas‐diffusion electrodes. [ABSTRACT FROM AUTHOR]