Density functional theory study of carbon dioxide electrochemical reduction on the Fe(100) surface

Carbon dioxide electroreduction offers the possibility of producing hydrocarbon fuels using energy from renewable sources. Herein, we use density functional theory to analyze the feasibility of CO₂ electroreduction on a Fe(100) surface. Experimentally, iron is nonselective for hydrocarbon formation. A simplistic analysis of low-coverage reaction intermediate energies for the paths to produce CH₄ and CH₃OH from CO₂ suggests Fe(100) could be more active than Cu(111), currently the only metallic catalyst to show selectivity towards hydrocarbon formation. We consider a series of impediments to CO₂ electroreduction on Fe(100) including O*/OH* (* denotes surface bound species) blockage of active surface sites; competitive adsorption effects of H*, CO* and C*; and iron carbide formation. Our results indicate that under CO ₂ electroreduction conditions, Fe(100) is predicted to be covered in C* or CO* species, blocking any C-H bond formation. Further, bulk Fe is predicted to be unstable relative to FeC_x formation at potentials relevant to CO₂ electroreduction conditions. This journal is