• The heterogeneous interface of NiO/Co3O4 regulates urea adsorption behavior, enhancing UOR kinetics.
• DFT and TPD experiments confirm the mechanism of charge redistribution and functional group adsorption.
• AEMWE with NiO/Co3O4 anode and NiCoP cathode achieves scalable urea wastewater treatment at 600 mA cm−2 with ~53% efficiency.
• Hydrogen production rate is 3.5 times higher than overall water splitting, offering energy-saving and cost-effective wastewater treatment.
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