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energies were used for comparison. For the C-N coupling process, the changes in free energy were used for
+
*
*
comparison. For - N , the E of the catalyst for N is -0.93 eV, while for H , it is only -0.23 eV; for N - N
*
*
2
2
2
ad
2
*
*
*
*
+
+ CO, the E for CO is -1.28 eV, while for H , it is a positive value of 0.06 eV; for N + CO - NCON, ΔG
ad
2
*
*
for the C-N coupling is -0.18 eV. The formation of N H + CO has a ΔG value of 0.17 eV, and the formation
2
of N + COH has a ΔG value of -0.06 eV. Therefore, HER is difficult to occur. There are two paths for the
*
*
2
[47]
first hydrogenation of CORR . One is the COH formation by hydrogenation on O, and the other is the
CHO formation by hydrogenation on C. The free energy values of the two pathways from N + CO are
*
*
2
-0.06 and 1.17 eV, respectively. Both are higher than the C-N coupling process (-0.18 eV). As to NRR, the
free energy for forming NNH + CO is 0.00 eV, which is higher than the free energy of C-N coupling
*
*
(-0.18 eV), indicating that retrograde C-N coupling is more preferred. The reaction free energy profile for
NRR is depicted in Supplementary Figure 9, where ΔG equals 0.63 eV, significantly higher than that of
max
urea synthesis (0.22 eV). Thus, Fe Mo@γ-GDY has a good selectivity for electrocatalytic urea synthesis.
2
CONCLUSIONS
We have designed a triatomic Fe Mo@γ-GDY catalyst for the electrochemical synthesis of urea by regulating
2
the adsorption energy and adsorption configuration for each step of the reaction process. Through DFT
calculations, we have demonstrated that this catalyst possesses good stability and electronic conductivity.
The catalyst not only gives an excellent catalytic performance in theoretical calculations (U = -0.22 V, E =
L
b
0.34 eV), but also shows a good selectivity through various evaluation metrics. Additionally, the catalyst
exhibits strong antioxidative performance under operational potentials. Compared to the current methods
of urea synthesis under high-temperature and high-pressure conditions, the Fe Mo@γ-GDY catalyst offers a
2
viable route for synthesizing urea under ambient conditions. Overall, the Fe Mo@γ-GDY catalyst provides a
2
new and more sustainable method for the electrocatalytic synthesis of urea, and it is expected to replace
traditional energy-intensive synthesis methods in future industrial applications.
DECLARATIONS
Acknowledgments
We acknowledge the financial support from the National Natural Science Foundation of China (No.
52130101), the “World-class Universities and World-class Disciplines” fund, China, the National Key R&D
Program of China (No. 2023YFB3003001), and the “Xiaomi Young Scholar” Project.
Authors’ contributions
Conceived and designed the DFT calculations: Wang, T.; Jiang, Q.
Performed DFT calculations and the related analysis: Chi, L.; Wang, T.
Wrote the paper, discussed the results, and commented on the manuscript: Chi, L.; Wang, T.; Jiang, Q.
Availability of data and materials
The data supporting our findings can be found in the Supplementary Materials.
Financial support and sponsorship
This work was financially supported by the National Natural Science Foundation of China (No. 52130101),
the “World-class Universities and World-class Disciplines” fund, China, the National Key R&D Program of
China (No. 2023YFB3003001), and the “Xiaomi Young Scholar” Project.
Conflicts of interest
Jiang, Q. serves as an Associate Editor for Journal of Materials Informatics. However, Jiang, Q. was not
involved in any aspect of the editorial process for this manuscript, including reviewer selection, manuscript
handling, or decision-making. The remaining authors declare no conflicts of interest.