Global Activity Search Uncovers Reaction Induced Concomitant Catalyst Restructuring For Alkane Dissociation On Model Pt Catalysts

Although there is evidence that catalytic active sites can restructure under reaction conditions, their optimal reconstruction to provide the lowest activation barrier is still unclear. Here, we show with methane activation on supported Pt clusters and by an explicit sampling of cluster configurations at the transition state that important restructuring is required to reach the most active transition state. The capability of the cluster to reconstruct, simultaneously with the C-H dissociation, is a key aspect for catalytic activity. We underline two types of reconstructions, concomitant or independent, depending on whether they emerge in or off the course of reactive trajectories. The concomitant reconstructions depict the significant rearrangement of the catalyst itself as part of the reaction coordinate and play critical roles in the most competitive pathways. The best active sites can only be found in the course of the reactive trajectories and not from the equilibrium geometry prior to the reaction.