Engineering bimetallic interfaces and revealing the mechanism for carbon dioxide electroreduction to C3+liquid chemicals

The reduction reaction of carbon dioxide (CO2RR) to liquid C3+ chemicals is a potential net-zero carbon process that can increase local resiliency to power outages and fuel consumption. However, the mechanism and catalyst design rules to promote CO2RR-to-C3+ are unknown. Engineering bimetallic interfaces (e.g., palladium/ gold) to tune intermediate adsorption is promising for promoting C3+ formation. Our density functional theory calculations find that *CH2 could be the key intermediate, and C1-CH2 coupling could be the rate-limiting step to generate C3+. High CO surface coverages can promote the bimetallic interfacial sites, lower the energetics of the C1-CH2 coupling step, and enhance C3+ formation. We further construct a volcano plot of C1-CH2 kinetics as a function of the binding strength of key intermediate *CH2 via engineering the d-band center of the interfacial site. Our findings could guide the rational design of bimetallic interfaces and their near-surface microenvironment for enhancing CO2RR-to-C3+.