Sequential Phase Conversion‐Induced Phosphides Heteronanorod Arrays for Superior Hydrogen Evolution Performance to Pt in Wide pH Media

Developing an efficient and non-precious pH-universal hydrogen evolution reaction electrocatalyst is highly desirable for hydrogen production by electrochemical water splitting but remains a significant challenge. Herein, a hierarchical structure composed of heterostructured Ni2 P-Ni12 P5 nanorod arrays rooted on Ni3 S2 film (Ni2 P-Ni12 P5 @Ni3 S2 ) via a simultaneous corrosion and sulfidation is built followed by a phosphidation treatment toward the metallic nickel foam. The combination of theoretical calculations with in/ex situ characterizations unveils that such a unique sequential phase conversion strategy ensures the strong interfacial coupling between Ni2 P and Ni12 P5 as well as the robust stabilization of 1D heteronanorod arrays by Ni3 S2 film, resulting in the promoted water adsorption/dissociation energy, the optimized hydrogen adsorption energy, and the enhanced electron/proton transfer ability accompanied with an excellent stability. Consequently, Ni2 P-Ni12 P5 @Ni3 S2 /NF requires only 32, 46, and 34 mV overpotentials to drive 10 mA cm-2 in 1.0 m KOH, 0.5 m H2 SO4 , and 1.0 m phosphate-buffered saline electrolytes, respectively, exceeding almost all the previously reported non-noble metal-based electrocatalysts. This work may pave a new avenue for the rational design of non-precious electrocatalysts toward pH-universal hydrogen evolution catalysis.