Coverage-sensitive mechanism of electrochemical NO reduction on the SrTiO₃(001) surface: a DFT investigation

Due to its adverse environmental and human health hazards, addressing the elimination of nitric oxide (NO) has become a pressing concern for modern society. Currently, electrochemical NO reduction provides a new alternative to traditional selective catalytic reduction technology under mild reaction conditions. However, the complexity and variability of products make the coverage of NO an influencing factor that needs to be investigated. Hence, this study delves into the coverage-sensitive mechanism of electrochemical NO reduction on cost-effective perovskite catalysts, using SrTiO₃ as an example, through density functional theory calculations. Phase diagrams analysis reveals that the coverage range from 0.25 to 1.00 monolayer (ML) coverage is favorable for NO adsorption. Gibbs free energy results indicate that the selectivity is significantly influenced by NO coverage. NH₃ is likely to be generated at low coverage, while N₂O and N₂ are more likely to be produced at high coverage through a dimer mechanism. Charge analysis suggests that the charge transfer and Ti-O bond strength between reactants and catalysts are crucial factors. This work not only provides deep insights into coverage-sensitive reaction mechanisms but also is a guideline towards further rational design of high-performance perovskite catalysts.