Au Single Metal Atom for Carbon Dioxide Reduction Reaction

Abstract

CO2 is the gas that contributes the most to the greenhouse effect and, therefore, to global warming. One of the greatest challenges facing humanity is the reduction of the concentration of CO2 in the air. Here, we analyze the possible use of Au1@g-C3N4 electrocatalyst to transform CO2 into add-ed-value products. We use density functional theory (DFT) to determine the reaction Gibbs ener-gies for eight electron-proton transfer reaction paths of the electrochemical carbon dioxide reduc-tion reaction (CO2RR) using a single Au atom supported on 2D carbon nitride support. Our sim-ulations classify the Au1@g-C3N4 electrocatalysts as 'beyond CO' since their formation is energet-ically favored, although their strong binding with a Au single atom does not allow the desorption process. DFT calculations revealed that the lowest energy pathway is CO2(g)→ COOH*→ CO*→ HCO*→ HCOH* → CH2OH* → CH2* →CH3* → CH4(g), where the first hydrogenation of CO to HCO is predicted as the rate-limiting step of the reaction with slightly lower potential than pre-dicted for Cu electrodes, the most effective catalysts for CO2RR. Methane is predicted to be the main reaction product after eight proton-electron transfers (CO2 + 8 H+ + 8e− → CH4 + 2H2O). The generation of formaldehyde is discarded due to the large formation energy of the adsorbed moiety and the production of methanol is slightly less favorable than methane formation. Our computa-tional study helps to identify suitable electrocatalysts for CO2RR by reducing the amount of metal and using stable and low-cost supports