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.

Electrochemical synthesis has garnered attention as a promising alternative to the traditional Haber–Bosch process to enable the generation of ammonia (NH3) under ambient conditions. Current electrocatalysts for the nitrogen reduction reaction (NRR) to produce NH3 are comprised of noble metals or transitional metals. Here, an efficient metal‐free catalyst (BCN) is demonstrated without precious component and can be easily fabricated by pyrolysis of organic precursor. Both theoretical calculations and experiments confirm that the doped BN pairs are the active triggers and the edge carbon atoms near to BN pairs are the active sites toward the NRR. This doping strategy can provide sufficient active sites while retarding the competing hydrogen evolution reaction (HER) process; thus, NRR with high NH3 formation rate (7.75 µg h−1 mgcat. −1) and excellent Faradaic efficiency (13.79%) are achieved at −0.3 V versus reversible hydrogen electrode (RHE), exceeding the performance of most of the metallic catalysts.

The industrial urea synthesis consists of two consecutive processes, nitrogen + hydrogen → ammonia followed by ammonia + carbon dioxide → urea. The electrocatalytic coupling of carbon source (carbon dioxide) and nitrogen source (nitrogen, nitrite, nitrate) by skipping the ammonia synthetic process might be a promising alternative to achieve the efficient urea synthesis; in this case, two industrial steps with high energy consumption and high pollution are optimized into one renewable energy‐driving electrocatalytic process. Herein, the progress of green urea synthesis is summarized, focusing on the electrocatalytic coupling of carbon source and nitrogen source for direct urea synthesis under ambient conditions. The mechanism researches for urea synthesis are also reviewed, and the future development directions of electrocatalytic urea synthesis are prospected. The electrocatalytic C–N coupling reaction realizes the efficient resource utilization and provides guidance and reference for molecular coupling reactions.

Electrocatalytic urea synthesis via coupling N2 and CO2 provides an effective route to mitigate energy crisis and close carbon footprint. However, the difficulty on breaking N≡N is the main reason that caused low efficiencies for both electrocatalytic NH3 and urea synthesis, which is the bottleneck restricting their industrial applications. Herein, a new mechanism to overcome the inert of the nitrogen molecule was proposed by elongating N≡N instead of breaking N≡N to realize one‐step C−N coupling in the process for urea production. We constructed a Zn−Mn diatomic catalyst with axial chloride coordination, Zn−Mn sites display high tolerance to CO poisoning and the Faradaic efficiency can even be increased to 63.5 %, which is the highest value that has ever been reported. More importantly, negligible N≡N bond breakage effectively avoids the generation of ammonia as intermediates, therefore, the N‐selectivity in the co‐electrocatalytic system reaches100 % for urea synthesis. The previous cognition that electrocatalysts for urea synthesis must possess ammonia synthesis activity has been broken. Isotope‐labelled measurements and Operando synchrotron‐radiation Fourier transform infrared spectroscopy validate that activation of N−N triple bond and nitrogen fixation activity arise from the one‐step C−N coupling process of CO species with adsorbed N2 molecules.

Electrocatalytic urea synthesis via coupling of nitrate with CO2 is considered as a promising alternative to the industrial urea synthetic process. However, the requirement of sub‐reaction (NO3RR and CO2RR) activities for efficient urea synthesis is not clear and the related reaction mechanisms remain obscure. Here, the construction, breaking, and rebuilding of the sub‐reaction activity balance would be accompanied by the corresponding regulation in urea synthesis, and the balance of sub‐reaction activities was proven to play a vital role in efficient urea synthesis. With rational design, a urea yield rate of 610.6 mg h−1 gcat.−1 was realized on the N‐doped carbon electrocatalyst, superior to that of noble‐metal electrocatalysts. Based on the operando SR‐FTIR measurements, we proposed that urea synthesis arises from the coupling of *NO and *CO to generate the key intermediate of *OCNO. This work provides new insights and guidelines into urea synthesis from the aspect of activity balance.

Electrocatalytic urea synthesis via coupling N 2 and CO 2 provides an effective route to mitigate energy crisis and close carbon footprint. However, the difficulty on breaking N�N is the main reason that caused low efficiencies for both electrocatalytic NH 3 and urea synthesis, which is the bottleneck restricting their industrial applications. Herein, a new mechanism to overcome the inert of the nitrogen molecule was proposed by elongating N�N instead of breaking N�N to realize one-step CÀ N coupling in the process for urea production. We constructed a ZnÀ Mn diatomic catalyst with axial chloride coordination, ZnÀ Mn sites display high tolerance to CO poisoning and the Faradaic efficiency can even be increased to 63.5 %, which is the highest value that has ever been reported. More importantly, negligible N�N bond breakage effectively avoids the generation of ammonia as intermediates, therefore, the N-selectivity in the coelectrocatalytic system reaches100 % for urea synthesis. The previous cognition that electrocatalysts for urea synthesis must possess ammonia synthesis activity has been broken. Isotope-labelled measurements and Operando synchrotronradiation Fourier transform infrared spectroscopy validate that activation of NÀ N triple bond and nitrogen fixation activity arise from the one-step CÀ N coupling process of CO species with adsorbed N 2 molecules.