Synergistic Catalysis of Binary RuP Nanoclusters on Nitrogen-Functionalized Hollow Mesoporous Carbon in Hydrogen Production from the Hydrolysis of Ammonia Borane.

Exploring highly efficient nanocatalysts for hydrogen (H2) production from catalytic hydrolysis of ammonia borane (AB) under ambient conditions and further unveiling their catalytic mechanism are of critical importance for renewable energy conversion technologies but remain big challenges. Herein, ultrafine binary RuP alloy nanoclusters homogeneously encapsulated onto nitrogen-functionalized hollow mesoporous carbon supports (RuP@NHMCs) are reported as a high-performance platinum (Pt)-free nanocatalyst for catalytic hydrolysis of AB at room temperature. Remarkable catalytic activity with a very high turnover frequency of 1774 molH2 molRu-1 min-1 and a low activation energy of 36.3 kJ mol-1 is observed based on compositional and structural synergies of RuP@NHMCs. Results of control experiments and catalytic kinetics studies reveal that the rate-determining step of catalytic hydrolysis of AB is the oxidation cleavage of a covalently stable H-OH bond, while RuP@NHMCs result in multiple electronic, functional, size, and support effects that kinetically accelerate the cleavage of attacked H-OH. Furthermore, RuP@NHMCs exhibit a good catalytic activity with a high yield of >99% for tandem hydrogenation of nitroarenes coupled with the hydrolysis of AB. We strongly believe that the catalyst design principle reported here could provide a new opportunity for synthesizing other Pt-free high-performance nanocatalysts.