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Platinum-group metals have an irreplaceable role in electrocatalyzing oxygen reduction reaction (ORR) process due to their affinity for oxygen and oxygenated intermediates. However, large overpotential and poor long-term durability prohibit their utilization in scalable industrial applications. Owing to their inherent scarcity, substantial improvements in the electrocatalytic performance (both selectivity and stability) of the catalysts are urgently necessary. Herein, a synergistic hybrid PtPd-Al2O3 catalyst is developed for highly selective and long-term stable hydrogen peroxide (H2O2) electroproduction. Synchrotron radiation characterizations are carried out to clarify the synergistic effect in the catalyst. The incorporation of Pd with Pt induces a valence band restructuring and reconstructs the coordination environment of the nanoparticles. For H2O2 electrosynthesis through the 2e− ORR, these electronic and structural modifications resulted in optimal adsorption energies of reaction intermediates. Therefore, the synergy hybrid of Pt and Pd not only enhances electrocatalytic activity and selectivity (96%) but also creates a new coordination structure in the catalyst, increasing its long-term durability. This study introduces a new paradigm for the development of high-performance H2O2 electrocatalyst by demonstrating the synergistic dual function of Pd as electron promoter and structure stabilizer.

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