Engineering advanced noble-metal-free electrocatalysts for energy-saving hydrogen production from alkaline water via urea electrolysis

When the anodic oxygen evolution reaction (OER) of water splitting is replaced by the urea oxidation reaction (UOR), the electrolyzer can fulfill hydrogen generation in an energy-economic manner for urea electrolysis as well as sewage purification. However, owing to the sluggish kinetics from a six-electron process for UOR, it is in great demand to design and fabricate high-performance and affordable electrocatalysts. Over the past years, numerous non-precious materials (especially nickel-involved samples) have offered huge potential as catalysts for urea electrolysis under alkaline conditions, even in comparison with frequently used noble-metal ones. In this review, recent efforts and progress in these high-efficiency noble-metal-free electrocatalysts are comprehensively summarized. The fundamentals and principles of UOR are first described, followed by highlighting UOR mechanism progress, and then some discussion about density functional theory (DFT) calculations and operando investigations is given to disclose the real reaction mechanism. Afterward, aiming to improve or optimize UOR electrocatalytic properties, various noble-metal-free catalytic materials are introduced in detail and classified into different classes, highlighting the underlying activity-structure relationships. Furthermore, new design trends are also discussed, including targetedly designing nanostructured materials, manipulating anodic products, combining theory and in situ experiments, and constructing bifunctional catalysts. Ultimately, we point out the outlook and explore the possible future opportunities by analyzing the remaining challenges in this booming field.