Vanadium-Doping and Interface Engineering for Synergistically Enhanced Electrochemical Overall Water Splitting and...

Fabricating effective non-precious metal-based catalysts for hydrogen production via electrochemical water splitting is of considerable importance but remains challenging. Transition metal nitrides possessing metallic character and corrosion resistance have been considered as potential replacements for precious metals. However, their activities for water electrolysis are impeded by the strong hydrogen adsorption and low water adsorption energies. Herein, V-doped bimetallic nitrides, V-FeNi₃N/Ni₃N heterostructure, are synthesized via a hydrothermal-nitridation protocol and used as electrocatalysts for water splitting and urea electrolysis. The V-FeNi₃N/Ni₃N electrode exhibits superior HER and OER activities, and the overpotentials are 62 and 230 mV to acquire a current density of 10 mA cm^-2, respectively. Moreover, as a bifunctional electrocatalyst for overall water splitting, a two-electrode device needs a voltage of 1.54 V to reach a current density of 10 mA cm^-2. The continuous electrolysis can be run for more than 120 h, surpassing most previously reported electrocatalysts. The excellent performance for water electrolysis is dominantly due to V-doping and interface engineering, which could enhance water adsorption and regulate the adsorption/desorption of intermediates species, thereby accelerating HER and OER kinetic processes. Besides, a urea-assisted two-electrode electrolyzer for electrolytic hydrogen production requires a cell voltage of 1.46 V at 10 mA cm^-2, which is 80 mV lower than that of traditional water electrolysis.