Ru Modulation Effects in the Synthesis of Unique Rod-like Ni@NiP-Ru Heterostructures and Their Remarkable Electrocatalytic Hydrogen Evolution Performance.

The construction of highly efficient and stable Pt-free catalysts for electrochemical hydrogen generation is highly desirable. Herein, we demonstrate the first metal-phosphides-metal system consisting of Ru, NiP, and Ni, which forms unique multiheterogeneous Ni@NiP-Ru nanorods. Interestingly, a Ru modulation effects that promotes the desorption of H to achieve a moderate hydrogen adsorption energy (ΔG), and enables the formation of Ni@NiP nanorods via Ru-Ni coordination to enhance the conductivity was discovered. Due to its optimal ΔG, improved conductivity and rod-like morphology, this catalyst shows superior electrocatalytic HER performances in both acidic and alkaline conditions, which are superior to those of some recently reported phosphides and close to that of commercial 20% Pt/C. Such a design strategy is not limited to NiP and Ru but also may be extended to other similar phosphides and noble metals, providing a new promising approach and an alternative to Pt catalysts for electrocatalytic applications.