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Urea is a common waste in agriculture runoff and has also been proposed as a promising oxidizable molecule in urea electrolysis for hydrogen production from wastewater. However, the overpotential of the electrochemical urea oxidation reaction (UOR) is high due to the complicated six-electron transfer process on most metal catalysts. The competition with oxygen evolution reaction (OER) further limits catalyst options for UOR. The most promising and studied catalysts for UOR are Ni-based catalysts. Here we study the reactivity of the basal β-NiOOH(001) surface for UOR and study the effects of metal doping (Mn, Fe, Co, and Cu) on the phase transformation from β-Ni(OH)2 to β-NiOOH, UOR, and OER pathways using density functional theory (DFT) calculations. The introduction of Mn and Fe dopants facilitates the formation of catalytically active β-NiOOH phase, and also favors the adsorption of urea compared to the undoped β-NiOOH surface, thereby significantly benefitting the overall UOR. Moreover, comparison of the effect of dopants on UOR and OER provides fundamental understanding of the competition between UOR and OER and how the dopants influence the reaction selectivity and competition. This work sheds light on the structure-property relationship of Ni-catalysts in urea oxidation and provides design principles for functional Ni-based materials, which will help accelerate the development of efficient UOR catalysts. 

Abstract Electrochemical two-electron water oxidation reaction (2e-WOR) has drawn significant attention as a promising process to achieve the continuous on-site production of hydrogen peroxide (H₂O₂). However, compared to the cathodic H₂O₂generation, the anodic 2e-WOR is more challenging to establish catalysts due to the severe oxidizing environment. In this study, we combine density functional theory (DFT) calculations with experiments to discover a stable and efficient perovskite catalyst for the anodic 2e-WOR. Our theoretical screening efforts identify LaAlO₃perovskite as a stable, active, and selective candidate for catalyzing 2e-WOR. Our experimental results verify that LaAlO₃achieves an overpotential of 510 mV at 10 mA cm⁻²in 4 M K₂CO₃/KHCO₃, lower than those of many reported metal oxide catalysts. In addition, LaAlO₃maintains a stable H₂O₂Faradaic efficiency with only a 3% decrease after 3 h at 2.7 V vs. RHE. This computation-experiment synergistic approach introduces another effective direction to discover promising catalysts for the harsh anodic 2e-WOR towards H₂O₂.