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

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 NaBH4 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 mLH2 min−1 gCo−1 at 30 °C, and the TOF(s) related to the number of surface atoms of the cobalt nanoparticles 19400 mLH2 min−1 gCo−1 at 30 °C. Kinetic studies including a high kinetic isotope effect disclosed using D2O (kH/kD=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. Earth‐abundant nanocatalyst: CoNPs@ZIF‐8 showed excellent efficiency and selectivity in the hydrolysis of NaBH4 for the generation of H2. The performance of this nanocatalyst is better than those of most non‐noble metal catalysts, and even some noble metal catalysts.