Hydrogen binding of molecules on solid surfaces is an attractive interaction that can be used as the driving force for bond activation, material-directed assembly, protein protection, etc. However, the lack of a quantitative characterization method for hydrogen bonds (HBs) on surfaces seriously limits its application. We measured the standard Gibbs free energy change (ΔG0 ) of on-surface HBs using NMR. The HB-accepting ability of the surface was investigated by comparing ΔG0 values employing the model biomass platform 5-hydroxymethylfurfural on a series of Co-N-C-n catalysts with adjustable electron-rich nitrogen-doped contents. Decreasing ΔG0 improves the HB-accepting ability of the nitrogen-doped surface and promotes the selectively initiated activation of O-H bonds in the oxidation of 5-hydroxymethylfurfural. As a result, the reaction kinetics is accelerated. In addition to the excellent catalytic performance, the turnover frequency (TOF) for this oxidation is much higher than for reported non-noble-metal catalysts.