The proton-coupled electron transfer (PCET) mechanism of the oxygen reduction reaction (ORR) is a long-standing enigma in electrocatalysis. Despite decades of research, the factors determining the microscopic mechanism of ORR-PCET as a function of pH, electrolyte, and electrode potential remain unresolved, even on the prototypical Pt(111) surface. Herein, we integrate advanced experiments, simulations, and theory to uncover the mechanism of the cation effects on alkaline ORR on well-defined Pt(111). We unveil a dual-cation effect where cations simultaneously determine i) the active electrode surface by controlling the formation of Pt-O and Pt-OH overlayers and ii) the competition between inner- and outer-sphere PCET steps. The cation-dependent transition from Pt-O to Pt-OH determines the ORR mechanism, activity, and selectivity. These findings provide direct evidence that the electrolyte affects the ORR mechanism and performance, with important consequences for the practical design of electrochemical systems and computational catalyst screening studies. Our work highlights the importance of complementary insight from experiments and simulations to understand how different components of the electrochemical interface contribute to electrocatalytic processes.
Keywords: Constrained DFT; Electrocatalysis; Energy Conversion; Kinetic Isotope Effects; Marcus Theory.
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