CO2和一些簡單的含氮化合物進行共還原是一個具有前景的方法來產生具有C-N鍵的產物，這個方法還可以擴展過往只單獨進行二氧化碳還原(CO2ER)時所獲得的產物範圍。在此份研究中，我們使用密度泛函數理論(Density functional theory，DFT)搭配定電極電位模型進行計算，探討了CO2和NO3-/NO2-在Cu(111)產生尿素的過程中C-N鍵生成的路徑。令人驚訝的是，我們發現第一支C-N鍵是由CO2和NO3-/NO2-還原成NH3時產生的表面N1中間體(*NO2、*NO、*NOH、*N、NH、NH2)耦合生成的，這個反應遵循Eley-Rideal機制，且是可發生於單一活性位點上。這些發現和過往文獻中的假設不同，先前的文獻指出是CO2ER產生的含碳物種(*COOH和*CO)作為碳氮鍵耦合的中間體。藉由Barrier decomposition analysis，我們了解到CO2參與的碳氮鍵耦合有著較低的活化能是由於CO2跟N1中間體形成過渡態時所需要付出的形變能較低，以及他們之間存在著引力所導致。此外我們發現CO2+N1的碳氮鍵耦合活化能會跟N1中間體的形變能具有很好的線性關係。基於這些研究內容，我們提出了兩種優化碳氮鍵耦合的方法。

The co-electrolysis of CO2 with nitrogen compounds provides a promising approach for the production of molecules that contain C-N bonds. As a result, this approach expands the spectrum of products obtained solely from CO2 electrochemical reduction (CO2ER). To examine the mechanisms of C-N bond formation during the co-reduction of CO2 and NO3-/NO2- on Cu(111) to generate urea, this study utilized density functional theory (DFT) calculations in conjunction with a constant electrode potential model. Surprisingly, we discovered the initial C-N bond is formed through the coupling of gaseous CO2 with surface-bound N1 intermediates (*NO2, *NO, *NOH, *N, *NH, and *NH2), which are generated during the reduction of NO3-/NO2- to NH3. The Eley-Rideal mechanism governs this reaction, which can take place at a single active site. These findings contradict previous literature assumptions that carbon species from CO2ER to CO (i.e., *COOH and *CO) act as intermediates for C-N coupling. The favorable kinetics observed in CO2-involved C-N coupling arise from the reduced energy requirements associated with the deformation of CO2 and the N1 intermediate towards the transition state structure. Additionally, the attractive interaction between CO2 and the N1 intermediate, as revealed by barrier decomposition analysis, contributes to the overall favorable kinetics. Furthermore, our findings indicate a strong correlation between the kinetic barrier of C-N coupling in the essential CO2+N1 reactions and the deformation energy of the N1 intermediate. Taking these insights into consideration, we suggest two approaches to enhance the efficiency of C-N coupling.

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