Role of atomicity in the oxygen reduction reaction activity of platinum sub nanometer clusters: A global optimization study

Metal nanoclusters are an important class of materials for catalytic applications. Sub nanometer clusters are relatively less explored for their catalytic activity on account of undercoordinated surface structure. Taking this into account, we studied platinum‐based sub nanometer clusters for their catalytic activity for oxygen reduction reaction (ORR). A comprehensive analysis with global optimization is carried out for structural prediction of the platinum clusters. The energetic and electronic properties of interactions of clusters with reaction intermediates are investigated. The role of structural sensitivity in the dynamics of clusters is unraveled, and unique intermediate specific interactions are identified. ORR energetics is examined, and exceptional activity for sub nanometer clusters are observed. An inverse size versus activity relationship is identified, challenging the conventional trends followed by larger nanoclusters. The principal role of atomicity in governing the catalytic activity of nanoclusters is illustrated. The structural norms governing the sub nanometer cluster activity are shown to be markedly different from larger nanoclusters. Platinum‐based sub nanoclusters show a strong dependence on their atomicity to catalyze oxygen reduction reaction (ORR). Contrary to the widespread conviction, the precise atomic structure of these clusters is identified with an ORR activity equivalent to larger nanoclusters with a drastic reduction in platinum utilization. There exist considerable activity differences between clusters which differ by only a single atom. Hence accurate structure determination and atomicity specific catalytic study can provide significant insights in this direction.