Highly Efficient and Selective Co@ZIF‐8 Nanocatalyst for Hydrogen Release from Sodium Borohydride Hydrolysis

Abstract Sodium borohydride hydrolysis catalyzed by composite nanomaterials has long been proposed as a viable possibility for hydrogen generation, but it required either expensive noble metals or sophisticated composites. Herein, the catalysis of NaBH 4 hydrolysis is studied with single earth‐abundant Fe, Co, Ni, and Cu nanoparticles supported by a metal organic framework (MOF), ZIF‐8. It appears that CoNPs@ZIF‐8 is the most efficient and selective catalyst in this series. The turnover frequency (TOF) related to the total atoms number within the cobalt nanoparticles reaches 14000 mL H2 min −1 g Co −1 at 30 °C, and the TOF(s) related to the number of surface atoms of the cobalt nanoparticles 19400 mL H2 min −1 g Co −1 at 30 °C. Kinetic studies including a high kinetic isotope effect disclosed using D 2 O (k H /k D =6.85) and the favorable effect of NaOH lead to the suggestion of an oxidative addition of a O−H bond of water in the rate‐determining step.