Highly Phosphatized Magnetic Catalyst with Electron Transfer Induced by Quaternary Synergy for Efficient Dehydrogenation of Ammonia Borane

Exploitation of high-efficiency and low-cost catalysts for dehydrogenation of the ideal hydrogen storage material (ammonia borane) can effectively promote the development of hydrogen economy. Here, we report an efficient and economical non-noble-metal magnetic catalyst (Ni_0.23Co_0.19P_0.58@NHPC900) with nanoparticles uniformly distributed on MOF-derived (metal-organic framework) nitrogen-doped hierarchical porous carbon (NHPC900) by a one-step in situ synthesis method. The catalyst has achieved a superior initial total turnover frequency (TOF) of 125.2 mol_H2·mol_cat^-1·min^-1. Based on isotopic analyses and ion effects, we further obtain an unprecedentedly higher TOF of 282.4 mol_H2·mol_cat^-1·min^-1, the highest among non-noble-metal heterogeneous systems. Through experiments and theoretical studies, we confirm that the highly doped phosphorus component leads to a C-P-Ni-Co quaternary synergy in the catalyst. Then, the induced strong electron transfer and increased partial charge can reduce the reaction energy barrier, strengthen the adsorption of ammonia borane, and ultimately result in superior catalytic performance. The proposed mechanisms and strategies are helpful to develop non-noble-metal catalysts for practical applications of hydrogen energy systems in the future.