Revealing electrocatalytic CN coupling for urea synthesis with metal-free electrocatalyst

Urea is ubiquitous in agriculture and industry, but its production consumes a lot of energy. The conversion of nitrogen (N₂) and carbon dioxide (CO₂) into urea via an electrocatalytic CN coupling reaction under ambient conditions would be a major boon to sustainable development. However, designing a metal - free catalyst with high activity and selectivity for urea remains a major challenge. Herein, by means of density functional theory (DFT) and ab - initio molecular dynamics (AIMD) computations, the B₁₂ cluster doped on nitrogenated graphene (C₂N) substrate catalyst (B₁₂@C₂N) with superior stability was designed for electrocatalytic urea synthesis starting from the CO₂ and N₂ through four reaction mechanisms. The nature of the co-adsorption activation of CO₂ and N₂ on the B₁₂@C₂N catalyst was investigated, the electrochemical proton - electron transfer steps and the CN thermochemical coupling led to the synthesis of urea. The study showed that the B₁₂@C₂N catalyst exhibited high catalytic activity for urea synthesis with the lowest limiting potential of - 1.01 V following the *HNNH mechanism compared with other mechanisms. The potential - determining step (PDS) is the formation of the *CO+*NH₂NH₂ species. However, the two - step CN coupling barriers of *NCON species are 0.13 eV and 0.60 eV using AIMD and a "slow - growth" sampling approach in an explicit water molecules model. Calculations also showed that the byproducts of carbon monoxide (CO), methane (CH₄), methanol (CH₃OH), ammonia (NH₃), and hydrogen (H₂) can be inhibited on the B₁₂@C₂N catalyst. Therefore, the metal - free catalyst not only has a good performance for the hydrogenation of CO₂ and N₂ promoting the electrochemical reaction, but also facilitates CN thermochemical coupling for urea synthesis. This work provides new insights into the synthesis of urea via the CN coupling reaction on a metal - free electrocatalyst, a process that could contribute to greenhouse gas mitigation to help meet carbon neutrality targets.