Unraveling the impact of the electronic structure of LaFeO₃(112) on oxygen evolution reaction

Self-consistent density functional theory calculations including a Hubbard U correction (DFT+U_Hub) were performed to investigate the oxygen evolution reaction (OER) on the LaFeO₃(112) surface, considering reaction mechanisms with and without lattice oxygen participation. First, the DFT+U_Hub approach was used to evaluate bulk properties of LaFeO₃, including the lattice parameters, magnetic moments, and band gap. Subsequently, the effect of the U_Hub parameter on the binding energies of key reaction intermediates and its influence on the catalytic activity were examined. The results highlight the critical role of electronic structure in governing OER activity and demonstrate that systematic variation of the U_Hub parameter provides a robust strategy for probing qualitative reaction trends in complex transition metal oxides, rather than relying on a single U_Hub value for quantitative predictions of activity. Based on the present level of theory and the adopted model system, the results also suggest that the most favorable OER pathway on surface Fe sites likely involves lattice oxygen participation.