Operando Investigation of the Origin of C─C Coupling in Electrochemical CO2 Reduction Upon Releasing Bonding Strength, Structural Ordering in Pd─Cu Catalyst

Abstract It is widely established that the electroreduction of carbon dioxide on a copper surface yields a spectrum of alcohols and hydrocarbons. But the selectivity of Cu toward a certain product is extremely poor as it forms a variety of reduced products concurrently. Controlling selectivity and overall performance depends on the modification of the Cu site and local environment. This study depicts how the product selectivity can be switched from C1 to C2 and multicarbon products by systematic incorporation of secondary metal (Pd) into the Cu lattice. Upon releasing the structural ordering from intermetallic to alloy and then to bimetallic, a systematic enhancement on the formation of C2 products from CO 2 has been observed. Real‐time in situ X‐ray absorption spectroscopy (XAS) study showed the potential dependent evolution of Pd─Cu and Cu─Cu bonds in different Pd‐Cu‐based catalysts. The detailed analysis of in situ IR and Raman also determined the adsorbed intermediate species and helped to identify the mechanism. Computational studies show the feasibility of multicarbon product formation on bimetallic catalysts compared to alloy and intermetallic catalysts. The current density and the activity of the CO 2 electroreduction have been enhanced by the utilization of the flow cell in the gas diffusion electrode configuration.