Highly Selective and Sharp Volcano-type Synergistic Ni2Pt@ZIF-8-Catalyzed Hydrogen Evolution from Ammonia Borane Hydrolysis.

Ammonia borane hydrolysis is considered as a potential means of safe and fast method of H2 production if it is efficiently catalyzed. Here a series of nearly monodispersed alloyed bimetallic nanoparticle catalysts are introduced, optimized among transition metals, and found to be extremely efficient and highly selective with sharp positive synergy between 2/3 Ni and 1/3 Pt embedded inside a zeolitic imidazolate framework (ZIF-8) support. These catalysts are much more efficient for H2 release than either Ni or Pt analogues alone on this support, and for instance the best catalyst Ni2Pt@ZiF-8 achieves a TOF of 600 molH2·molcatal-1·min-1 and 2222 molH2·molPt-1·min-1 under ambient conditions, which overtakes performances of previous Pt-base catalysts. The presence of NaOH boosts H2 evolution that becomes 87 times faster than in its absence with Ni2Pt@ZiF-8, whereas NaOH decreases H2 evolution on the related Pt@ZiF-8 catalyst. The ZIF-8 support appears outstanding and much more efficient than other supports including graphene oxide, active carbon and SBA-15 with these nanoparticles. Mechanistic studies especially involving kinetic isotope effects using D2O show that cleavage by oxidative addition of an O-H bond of water onto the catalyst surface is the rate-determining step of this reaction. The remarkable catalyst activity of Ni2Pt@ZiF-8 has been exploited for successful tandem catalytic hydrogenation reactions using ammonia borane as H2 source. In conclusion the selective and remarkable synergy disclosed here together with the mechanistic results should allow significant progress in catalyst design toward convenient H2 generation from hydrogen-rich substrates in the close future.