We report SiO2-supported monometallic Pt, Pd, Au, Ni, Cu and Co catalysts for protondriven NAD+ regeneration, co-producing H2. All metals are fully selective to NAD+ where the order of turnover frequencies (Pt >> Pd > Cu > Au, Ni and Co) coincides with those otherwise observed in electrochemical hydrogen evolution reactions. This has revealed that NADH is capable of converting the metal sites into a “cathode” without an external potential and the NADH to NAD+ reaction involves transferring electron and hydrogen atom separately. Electron-deficient Ptδ+ (on CeO2) enhances TOF and the heterogeneous Pt/CeO2 catalyst is recyclable without losing any activity/selectivity.