Spatially confined synthesis of bimetal phosphide nanoparticles encapsulated metal-organic framework architectures via localized phosphorization for efficient ammonia borane dehydrogenation

Robust multifunctional substrates in heterogeneous catalysts are highly demanded to effectively stabilize active -metal centers and synergistically improve the catalytic performances toward the hydrolysis of ammonia borane (AB). In this study, we introduce a porous quasi-metal-organic framework (quasi-NiCo-MOF) architectures as a novel and smart substrate to spatially confine the in-situ generated bimetallic NiCo-phosphide nanoparticles, and demonstrate a universal controllable thermal transformation strategy is effective for simultaneous partial deli-gandation and localized phosphorization of the parent NiCo-MOF. Benefiting from the compositional and structural merits, the resulting P-NiCo-MOF can efficiently activate and dissociate AB and H2O molecules, delivering a high hydrogen generation rate of 4333 mL min-1 gcat-1. Moreover, the optimal P-NiCo-MOF catalyst achieves a satisfactory turnover frequency (TOF) of 26.3 min-1 at reaction temperature of 298 K and a relatively low activation energy of 45.6 kJ mol-1. This study offers a new avenue for in-situ generation of functional inorganic compounds in quasi-MOF and enriches the structural and compostional design of heterogeneous catalysts.