The electrocatalytic C–N coupling for one-step urea synthesis under ambient conditions serves as the promising alternative to the traditional urea synthetic protocol. However, the hydrogenation of intermediate species hinders the efficient urea synthesis. Herein, the oxygen vacancy-enriched CeO2 was demonstrated as the efficient electrocatalyst with the stabilization of the crucial intermediate of *NO via inserting into vacant sites, which is conducive to the subsequent C–N coupling process rather than protonation, whereas the poor selectivity of C–N coupling with protonation was observed on the vacancy-deficient catalyst. The oxygen vacancy-mediated selective C–N coupling was distinguished and validated by the in situ sum frequency generation spectroscopy. The introduction of oxygen vacancies tailors the common catalyst carrier into an efficient electrocatalyst with a high urea yield rate of 943.6 mg h–1 g–1, superior than that of partial noble-metal-based electrocatalysts. This work provides novel insights into the catalyst design and developments of coupling systems.

Electrocatalytic urea synthesis emerged as the promising alternative of Haber–Bosch process and industrial urea synthetic protocol. Here, we report that a diatomic catalyst with bonded Fe–Ni pairs can significantly improve the efficiency of electrochemical urea synthesis. Compared with isolated diatomic and single-atom catalysts, the bonded Fe–Ni pairs act as the efficient sites for coordinated adsorption and activation of multiple reactants, enhancing the crucial C–N coupling thermodynamically and kinetically. The performance for urea synthesis up to an order of magnitude higher than those of single-atom and isolated diatomic electrocatalysts, a high urea yield rate of 20.2 mmol h−1 g−1 with corresponding Faradaic efficiency of 17.8% has been successfully achieved. A total Faradaic efficiency of about 100% for the formation of value-added urea, CO, and NH3 was realized. This work presents an insight into synergistic catalysis towards sustainable urea synthesis via identifying and tailoring the atomic site configurations.

Electrocatalytic oxidation of 5‐hydroxymethylfurfural (HMF) provides an efficient way to obtain high‐value‐added biomass‐derived chemicals. Compared with other transition metal oxides, CuO exhibits poor oxygen evolution reaction performance, leading to high Faraday efficiency for HMF oxidation. However, the weak adsorption and activation ability of CuO to OH− species restricts its further development. Herein, the CuO–PdO heterogeneous interface is successfully constructed, resulting in an advanced onset‐potential of the HMF oxidation reaction (HMFOR), a higher current density than CuO. The results of open‐circuit potential, in situ infrared spectroscopy, and theoretical calculations indicate that the introduction of PdO enhances the adsorption capacity of the organic molecule. Meanwhile, the CuO–PdO heterogeneous interface promotes the adsorption and activation of OH− species, as demonstrated by zeta potential and electrochemical measurements. This work elucidates the adsorption enhancement mechanism of heterogeneous interfaces and provides constructive guidance for designing efficient multicomponent electrocatalysts in organic electrocatalytic reactions.