Graphite-Supported Ptn 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 the active sites on these catalysts under electrocatalytic conditions presents a formidable challenge for both experiment and theory, due to their dynamic fluxional character. Here, we combine global optimization with the electronic Grand Canonical DFT to elucidate the structure and dynamics of subnano Ptn clusters deposited on electrified graphite. We show that, under electrochemical conditions, these clusters exist as statistical ensembles of multiple states, whose fluxionality is greatly affected by the applied potential, electrolyte, and adsorbate coverage. The results reveal the presence of potential-dependent active sites and, hence, reaction energetics.

Automated summary

In this study, the structure and dynamics of subnano Ptn clusters deposited on electrified graphite under electrochemical conditions were elucidated using a combination of global optimization and electronic Grand Canonical DFT. The results showed that these clusters exist as statistical ensembles of multiple states with fluctuating characteristics, which are greatly influenced by the applied potential, electrolyte, and adsorbate coverage.