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Developing acid-stable manganese-based catalysts for the oxygen evolution reaction (OER) is pivotal for advancing proton exchange membrane water electrolysis (PEMWE). Here, we present a selenium-doped MnO2 catalyst, where the synergistic effects of Se and oxygen defects stabilize Mn3+ species and regulate *OH adsorption dynamics. In situ spectroscopic studies and density functional theory (DFT) calculations confirm that Se doping modulates the electronic structure of Mn centers, lowering the energy barrier for *OH deprotonation and accelerating OER kinetics. In 0.5 M H2SO4, Se-MnO2 achieves current densities of 10 and 100 mA·cm−2 with overpotentials of 345 ± 5 and 398 ± 5 mV, respectively, outperforming commercial RuO2. Integrated into PEM electrolyzers, the catalyst demonstrates exceptional stability over 400 h under dynamic current densities (100–500 mA·cm−2), showcasing structural integrity and negligible activity decay. The strategic doping of selenium significantly enhances catalytic performance, thereby offering a promising pathway toward the development of cost-effective electrocatalysts for applications under acidic conditions.

This is an open access article under the terms of the Creative Commons Attribution 4.0 International License (CC BY 4.0, https://creativecommons.org/licenses/by/4.0/).
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