Activities per year
The electrochemical reduction (electroreduction) of CO2 toformic acid (HCOOH) and its competing reactions, that is, theelectroreduction of CO2 to CO and the hydrogen evolution reaction(HER), on twenty-seven different metal surfaces havebeen investigated using density functional theory (DFT) calculations.Owing to a strong linear correlation between the freeenergies of COOH* and H*, it seems highly unlikely that theelectroreduction of CO2 to HCOOH via the COOH* intermediateoccurs without a large fraction of the current going to HER. On the other hand, the selective electroreduction of CO2 to HCOOH seems plausible if the reaction occurs via the HCOO*intermediate, as there is little correlation between the free energies of HCOO* and H*. Lead and silver surfaces are found to be the most promising monometallic catalysts showing high faradaic efficiencies for the electroreduction of CO2 to HCOOH with small overpotentials. Our methodology is widely applicable,not only to metal surfaces, but also to other classes of materialsenabling the computational search for electrocatalysts for CO2 reduction to HCOOH.