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

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.