MoS₂/Ni₃S₂ Schottky heterojunction regulating local charge distribution for efficient urea oxidation and hydrogen...

Electrocatalytic urea oxidation reaction (UOR) is a prospective method to substitute the slow oxygen evolution reaction (OER) and solve the problem of urea-rich water pollution due to the low thermodynamic voltage, but its complex six-electron oxidation process greatly impedes the overall efficiency of electrolysis. Here, density functional theory (DFT) calculations imply that the metallic Ni₃S₂ and semiconductive MoS₂ could form Mott-Schottky catalyst because of the suitable band structure. Therefore, we synthesized MoS₂/Ni₃S₂ electrocatalyst by a simple hydrothermal method, and studied its UOR and hydrogen evolution reaction (HER) performance. The formed MoS₂/Ni₃S₂ Schottky heterojunction is only required 109  and 166 mV to obtain ±10 mA cm^-2 for UOR and HER, respectively, showing great bifunctional catalytic activity. Moreover, the full urea electrolysis driven by MoS₂/Ni₃S₂ delivers 10 and 100 mA cm^-2 at a relatively low potential of 1.44 and 1.59 V. Comprehensive experiments and DFT calculations demonstrate that the MoS₂/Ni₃S₂ Schottky heterojunction causes self-driven charge transfer at the interface and forms built-in electric field, which is not only benefit to reduce H* adsorption energy, but also helps to adjust the absorption and directional distribution of urea molecules, thereby promoting the activity of decomposition of water and urea. This research furnishes a tactic to devise more efficient catalysts for H₂ generation and the treatment of urea-rich water pollution.