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Han et al. J Mater Inf 2023;3:24 https://dx.doi.org/10.20517/jmi.2023.32 Page 9 of 11

orbitals [Supplementary Figure 9], which further leads to more efficient activation of N−N as demonstrated
by the lower ΔG of the first hydrogenating step. Besides, both the d-band center and the p-band center of Fe 2
-bonded C/N in Fe @N C have moderate values among Fe @N C (x = 0~4), showing an inverse volcano
4
20-x
x
3
3
16
relationship [Figure 5 and Supplementary Table 6].
CONCLUSIONS
In summary, we theoretically investigated the eNRR performance of Mo @C and Fe @C monolayers
3
20
20
3
based on the experimentally synthesized 2D Ag @C structure. Our calculations revealed that Fe @C
3
20
3
20
exhibits good activity and selectivity for eNRR with a predicted limiting potential of -0.59 V. By further
investigation of the synergy between the active Fe site and its coordination, we found that the N-containing
2
environment would tune the electronic properties and, thus, enhance the catalytic efficiency, where 2D
Fe @N C is demonstrated as the superior electrocatalyst with a limiting potential of -0.45 V. Moreover, the
4 16
3
Fe sites in our designed Fe @N C materials have much smaller ΔG than those of Fe-based SACs such
20-x
max
x
3
2
as FeN /G (1.30 eV) , FeCN (0.94 eV) and FeCN (0.92 eV) , and the best candidate Fe @N C also has
[63]
[59]
4
3
2
16
4
3
smaller ΔG than that of the Fe-based triple-atom catalyst Fe @C N (0.57 eV) . These findings provide
[65]
3
2
max
new ideas for the development of new eNRR catalysts following experimental fabrication to theoretical
prediction to experimental guidelines and highlight the important role of the metal-coordination
environment.
DECLARATIONS
Authors’ contributions
Performed the computations and drafted the manuscript: Han B
Provided guidance and revised the manuscript: Li F
Availability of data and materials
Supplementary materials are available from the Journal of Materials Informatics or from the authors.
Financial support and sponsorship
This work was supported by the National Natural Science Foundation of China (11964024), the “Grassland
Talents” project of the Inner Mongolia autonomous region (12000-12102613), and the young science and
technology talents cultivation project of Inner Mongolia University (21200-5223708). We thank the
computational support from Beijing PARATERA.
Conflicts of interest
All authors declared that there are no conflicts of interest.
Ethical approval and consent to participate
Not applicable.
Consent for publication
Not applicable.

Copyright
© The Author(s) 2023.

REFERENCES
1. Foster SL, Bakovic SIP, Duda RD, et al. Catalysts for nitrogen reduction to ammonia. Nat Catal 2018;1:490-500. DOI
2. Wang S, Ichihara F, Pang H, Chen H, Ye J. Nitrogen fixation reaction derived from nanostructured catalytic materials. Adv Funct