Heterostructured nickel/vanadium nitrides composites for efficient electrocatalytic hydrogen evolution in neutral medium.

Water electrolysis capable of working in a neutral medium is compatible with direct seawater splitting, solar-driven water splitting cells, and hybrid inorganic–biological systems for renewable energy conversion and storage. Non-precious electrocatalysts for efficient and durable hydrogen evolution reactions (HER) are of paramount significance. Herein, we report that the heterostructured nitrides composites that are made of poor HER electrocatalysts of Ni 3 N and VN show remarkable activity and durability for HER in a neutral medium. Ni 3 N-VN composite rivals the state-of-the-art Pt/C electrocatalyst, requiring an overpotential of only 85 mV to deliver a benchmark current density of 10 mA cm−2 in 1.0 M phosphate-buffered saline. The HER kinetics are significantly promoted in comparison with Ni 3 N and VN, showing 6–17 times higher current densities and lowered Tafel slopes (73 mV decade for Ni 3 N-VN and >120 mV decade−1 for Ni 3 N and VN). The promoted kinetics is ascribed to the interfacial heterostructures, where the electronic structures are tailored for optimal hydrogen absorption and promoted water adsorption and dissociation. This research demonstrates a powerful interfacial engineering strategy in promoting the sluggish kinetics of nitrides for HER in a neutral medium, which deserves further attention to electrocatalysts in other reactions. [Display omitted] • A simple method for synthesizing heterojunction electrocatalysts is introduced. • Ni 3 N-VN heterojunction enhances the adsorption and dissociation of water molecules. • Ni 3 N-VN heterojunction shows the extended energy states in the near Fermi level. • 3D hierarchical structure catalyst has excellent alkaline/neutral HER performance. [ABSTRACT FROM AUTHOR]