Modulating the Electronic Structure of Ni/NiO Nanocomposite with High-Valence Mo Doping for Energy-Saving Hydrogen Production via Boosting Urea Oxidation Kinetics

Abstract

Electrocatalytic urea oxidation reaction (UOR) has emerged as a promising alternative to the anodic oxygen evolution reaction (OER) in water electrolysis. However, UOR faces challenges like slow kinetics, high energy barriers, and a complex mechanism, necessitating the development of efficient electrocatalysts. Herein, a rapid method is proposed for synthesizing Mo-doped Ni/NiO (Ni/MNO) nanocomposite as a highly effective UOR electrocatalyst. Mo doping oxidizes Ni2+ to Ni3+, creating abundant active sites for UOR. The Ni/MNO catalyst exhibits remarkable activity for both OER and UOR due to Mo doping, structural modulation, increased active sites, and the presence of Ni3+ ions. Optimized Ni/MNO-10 shows a low OER overpotential of 280 mV and a UOR working potential of 1.37 V versus reversible hydrogen electrode at 10 mA cm-2, with exceptional stability over 12 h of continuous electrolysis. Notably, urea-assisted water splitting requires only 1.45 V for 10 mA cm-2, significantly less than the overall water splitting voltage (1.65 V), indicating energy-efficient hydrogen production. Moreover, the Ni/MNO catalyst exhibits outstanding long-term stability. This work presents a rapid and effective approach to synthesizing cost-effective and efficient electrocatalysts for clean energy production and wastewater treatment. Mo-doped Ni/NiO nanocomposite by a pulsed laser technique is developed. The optimized nanocomposite exhibits excellent urea oxidation reaction performance with a working potential of 1.37 V versus reversible hydrogen electrode at 10 mA cm-2 and exceptional stability. Remarkably, using this nanocomposite for urea-assisted water splitting only needs 1.45 V at 10 mA cm-2, demonstrating its energy-efficient hydrogen production.image & COPY; 2023 WILEY-VCH GmbH