Nickel-based electrocatalysts are identified as the promising candidates for both urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) in urea-assisted water electrolysis to accelerate energy saving hydrogen production. However, the high occupation of Ni 3d orbital leads to their constrained adsorption for reactant and multiple intermediates during UOR process. Herein, considering the d-band electron complementation, the bimetallic MoNi4 hollow nanocubes self-assembled with numerous ultrathin nanosheets was constructed by introducing molybdenum with relatively empty d orbital and synergistically boost UOR/HER activities. Notably, the MoNi4 requires a lower cell voltage of 1.462 V to drive a current density of 10 mA cm−2 in urea electrolyzer, superior to that in water electrolyzer (1.796 V) and most of the reported nickel-based electrocatalysts, as well as the urea degradation rate is impressive. In situ technologies including electrochemical impedance spectroscopies and Raman spectra reveal that the favorable UOR pathway can be initiated directly by the reconstructed NiOOH species. Density functional theory (DFT) calculations prove that the urea molecular are preferential absorbed on Ni site and then collaborate with the adjacent Mo site to carry out the subsequently dehydrogenation, N-N coupling, and desorption in energetically favorable pathways, proving their dual site mechanism (synergy between Mo and Ni).
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