Hydrogen‐Binding‐Initiated Activation of O−H Bonds on a Nitrogen‐Doped Surface for the Catalytic Oxidation of Biomass Hydroxyl Compounds

Abstract 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 (Δ G 0 ) of on‐surface HBs using NMR. The HB‐accepting ability of the surface was investigated by comparing Δ G 0 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 Δ G 0 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.