Institute of Fundamental Technological Research

The urea oxidation reaction (UOR) is characterized by a lower overpotential compared to the oxygen evolution reaction (OER) during electrolysis, which facilitates the hydrogen evolution reaction (HER) at the cathode. Charge
distribution, which can be modulated by the introduction of a heterostructure, plays a key role in enhancing the adsorption and cleavage of chemical groups within urea molecules. Herein, a facile all-room temperature synthesis of functional heterojunction NiCo2 S4 /CoMo 2 S4 grown on carbon cloth (CC) is presented, and the as-prepared electrode served as a catalyst for simultaneous hydrogen evolution and urea oxidation reaction. The Density
Functional Theory (DFT) study reveals spontaneous transfer of charge at the heterointerface of NiCo 2 S4 /CoMo 2 S4 , which triggers the formation of localized electrophilic/nucleophilic regions and facilitates the adsorption of electron donating/electron withdrawing group in urea molecules during the UOR. The NiCo2 S4 /CoMo 2 S4 // NiCo 2 S4 /CoMo 2 S4 electrode pair required only a cell voltage of 1.17 and 1.18 V to deliver a current density of 10 and 100 mA cm−2 respectively in urea electrolysis cell and display very good stability. Tests performed in real urine samples show similar catalytic performance to urea electrolytes, making the work one of the best transition
metal-based catalysts for UOR applications, promising both efficient hydrogen production and urea decomposition.

The major hindrance to efficient electrocatalytic hydrogen generation from water electrolysis is the sluggish kinetics with corresponding large overvoltage of oxygen evolution reaction. Herein, we report a defective 2D NiCoMoS@Ni(CN)2 core-shell heterostructure derived from Hofmann-type MOF as an efficient and durable high-performance noble metal-free electrocatalyst for hydrazine oxidation reaction (HzOR) in alkaline media. The sluggish oxygen evolution reaction was replaced with a more thermodynamically favourable HzOR, enabling energy-saving electrochemical hydrogen production with 2D NiCoMoS@Ni(CN)2 acting as a bifunctional electrocatalyst for anodic HzOR and cathodic hydrogen generation. Operating at room temperature, the two-electrode electrolyzer delivers 100 mA cm−2 from a cell voltage of just 257 mV, with strong long-term electrochemical durability and nearly 100% Faradaic efficiency for hydrogen evolution in 1.0 M KOH aqueous solution with 0.5 M hydrazine. The density functional theory (DFT) was employed to investigate the origin of catalytic performance and showed that high vacancy creation within the heterointerface endowed NiCoMoS@Ni(CN)2 with favourable functionalities for excellent catalytic performance.

Defect engineering, Core-shell, Electrocatalyst, Hydrazine oxidation, Heterostructure