Strain regulation of bond length in single Ru sites via curving support surface for enhanced hydrogen evolution reaction

The intrinsic activity of single-atom catalysts is influenced by the local electronic structures of metal centers, with existing modulation strategies limited to adjacent atomic coordination. However, the impacts of support surface geometry on local bonding environment, and thus electronic structures of single-atom centers have rarely been known. Here, we prepared highly curved B,N co-doped carbon-supported ruthenium catalyst with an ultra-low Ru loading of 0.4 wt%, which exhibited an ultrahigh turnover frequency (TOF) of 10 H2 s−1 (38 times that of Pt/C) and superior stability in alkaline hydrogen evolution reaction (HER). We found that curving support surface induced the strain, resulting in 1.5% compressed Ru-N and 4% stretched Ru-B bonds, leading to the accumulation of positive charge and quenching of spin polarization at Ru sites, thereby achieving the optimal binding of H* and enhanced performance for HER. This work highlights the significant support effects upon the structural design of active sites. [Display omitted] •Two types of B, N co-doped carbon-supported Ru site catalysts with and without support surface curvature were synthesized.•Curving the support surface induces strain and thereby changes the local bond length at the Ru sites.•Regulating bond length increases the aggregation of positive charges and suppresses spin polarization at the Ru sites.•The B, N co-doped carbon-supported Ru site catalyst with curvature achieves optimal H* binding strength for HER.•The turnover frequency of Ru sites with curvature is significantly higher than those without surface curvature.