Identifying Pd9OX as the optimum catalyst for the direct synthesis of H2O2 through microkinetic modeling with coverage effects

Identifying efficient active sites for the direct synthesis of hydrogen peroxide over Pd-based catalysts has been a subject of considerable debate. In this study, we employ particle swarm optimization method and density functional theory to explore the H2O2 synthesis mechanism on Pd, PdO, and the partially oxidized surface (Pd9OX). A comprehensive mechanism for Pd9OX is elucidated, and subsequent coverage-dependent kinetic analysis allows for a quantitative assessment of catalytic performance at the interphase. Our findings conclusively establish that the interphase between Pd and PdO represents the optimal active site. Phase diagram analysis further aids in determining stable structures under reaction conditions. At 298.15 K and under oxygen balance, the Pd9O6 surface remains stable throughout the reaction, demonstrating high activity and selectivity. This work underscores the significance of the interphase in comprehending catalytic performance and unveils promising avenues for optimizing catalyst performance by controlling reaction conditions and surface composition.