Regulation of Electronic Structures of the Urchin-Like NiCoP/CoP Nanocatalysts for Fast Hydrogen Evolution

Graphical Urchin-like NiCoP/CoP heterostructures have been developed through a three-step hydrothermal-oxidation-phosphorization synthesis process. The nano-architecture and electronic configuration can be regulated by adjusting the original Ni/Co molar ratio and the amount of phosphorus. Consequently, the optimal Ni 1 Co 2 P shows excellent performance in the hydrolytic dehydrogenation of ammonia borane. Furthermore, by combining infrared spectroscopy and isotope kinetics experiments, a possible reaction mechanism has been proposed. The exploration of stable, efficient, and low-cost catalysts toward ammonia borane hydrolysis is of vital significance for the practical implementation of this hydrogen production technology. Integrating interface engineering and nano-architecture engineering is a favorable strategy to elevate catalytic performance, as it can modify the electronic structure and provide sufficient active sites simultaneously. In this work, urchin-like NiCoP/CoP heterostructures are prepared via a three-step hydrothermal-oxidation-phosphorization synthesis route. It is demonstrated that the original Ni/Co molar ratio and the amount of phosphorus are crucial for adjusting the morphology, enhancing the exposed surface area, facilitating charge transfer, and modulating the adsorption and activation of H 2 O molecules. Consequently, the optimal Ni 1 Co 2 P heterostructure displays remarkable catalytic properties in the hydrolysis of ammonia borane with a turnover frequency (TOF) value of 30.3 mol H2 ⋅ min −1 ⋅ mol metal −1 , a low apparent activation energy of 25.89 kJ ⋅ mol −1 , and good stability. Furthermore, by combining infrared spectroscopy and isotope kinetics experiments, a possible mechanism for the hydrolysis of ammonia borane was proposed.