Dataset for "Polaronic Competition Triggers the H2O2 Evolution on Perovskite Oxides during Water Oxidation"

This dataset contains input files for density functional theory (DFT) simulations associated with the following publication: Polaronic Competition Triggers the H2O2 Evolution on Perovskite Oxides during Water Oxidation, Mohsen Sotoudeh, Axel Groß, ACS Catalysis, 2025, DOI: https://doi.org/10.1021/acscatal.5c02069 Abstract: Perovskite oxides, particularly calcium-based perovskites (CaMO3), are promising catalysts for the oxygen evolution reaction (OER) due to their high efficiency and economic feasibility. However, a comprehensive mechanistic understanding that elucidates the relationship between catalytic selectivity and mechanistic pathways has yet to be achieved. In this study, we employ density functional theory (DFT) to investigate the OER mechanism in a series of Ca-based perovskites. Our findings indicate that early transition metals in CaMO3 favor a conventional OER pathway, characterized by a four-step concerted proton-electron transfer process leading to O2 formation from H2O. In contrast, perovskites containing Mn, Fe, and Co exhibit two proton-electron transfer steps, favoring the selective formation of hydrogen peroxide (H2O2) over O2. This shift in selectivity is attributed to polaronic effects, which strengthen the metal-oxo bonding, enabling a transition from conventional OER to H2O2 evolution. Furthermore, we reveal that the thermodynamic stability of these perovskites in aqueous environments is significantly influenced by pH, where acidic conditions destabilize the perovskite structure. These insights suggest that modulating polaronic effects and maintaining high pH environments are key to optimizing both the stability and catalytic activity of perovskite oxides in OER applications.