Electrocatalysis for CO2 Reduction to Hydrocarbons: Theory-Driven Design Principles Developed From Transition Metals

The efficient reduction of CO₂ can enable the production of hydrocarbons from renewable and low-carbon sources of energy. We have used density functional theory and a computational hydrogen electrode model in order to understand the reactivity of transition metals in reducing CO₂ to hydrocarbons, carbon monoxide, and hydrogen gas. Using scaling relations to generalize binding energies of the important intermediates of CO₂ reduction, we show how the descriptors of CO₂ reduction can be reduced to key parameters. Our analysis indicates that the key descriptor is the free energy change in the first protonation of adsorbed carbon monoxide. We outline this and other key descriptors to develop catalysts that are efficient and selective in CO₂ reduction to hydrocarbons and alcohols.