Subnanometric Ru clusters with upshifted D band center improve performance for alkaline hydrogen evolution reaction

Subnanometric metal clusters usually have unique electronic structures and may display electrocatalytic performance distinctive from single atoms (SAs) and larger nanoparticles (NPs). However, the electrocatalytic performance of clusters, especially the size-activity relationship at the sub-nanoscale, is largely unexplored. Here, we synthesize a series of Ru nanocrystals from single atoms, subnanometric clusters to larger nanoparticles, aiming at investigating the size-dependent activity of hydrogen evolution in alkaline media. It is found that the d band center of Ru downshifts in a nearly linear relationship with the increase of diameter, and the subnanometric Ru clusters with d band center closer to Femi level display a stronger water dissociation ability and thus superior hydrogen evolution activity than SAs and larger nanoparticles. Benefiting from the high metal utilization and strong water dissociation ability, the Ru clusters manifest an ultrahigh turnover frequency of 43.3 s(-1) at the overpotential of 100 mV, 36.1-fold larger than the commercial Pt/C. Metal nanocluster properties undergo drastic activity alterations with slight size variations, although in-depth examinations of such changes are challenging to perform. Here, authors demonstrate Ru cluster size governs the d-band center position and electrocatalytic activity for H-2 evolution.