Graphite-Supported Pt_<i>n</i> Cluster Electrocatalysts: Major Change of Active Sites as a Function of the Applied Potential

The oxygen reduction reaction (ORR) plays a key role in renewable energy transformation processes. Unfortunately, it is inherently sluggish, which greatly limits its industrial application. Sub-nano-cluster-decorated electrode interfaces are promising candidate ORR electrocatalysts. However, understanding the nature of active sites on these catalysts under electrocatalytic conditions presents formidable challenge for both experiment and theory, due to their dynamic fluxional character. Here, we combine global optimization with electronic Grand Canonical DFT elucidate structure dynamics subnano Ptn clusters deposited electrified graphite. We show that, electrochemical conditions, exist as statistical ensembles multiple states, whose fluxionality affected by applied potential, electrolyte, adsorbate coverage. results reveal presence potential-dependent and, hence, energetics.