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Page 8 of 25 Meng et al. J. Mater. Inf. 2025, 5, 3 https://dx.doi.org/10.20517/jmi.2024.74

N H species and the nanosheet, resulting in high catalytic efficiency for V-doped arsenide (V/Ars) with a
y
x
[59]
low U of -0.26 V .
L
The study of bio-inspired catalysts with Mo-, Fe-, and V-like nitrogenase active centers for ammonia
synthesis at room temperature and atmospheric pressure holds great potential but presents significant
challenges. Much work remains to be done, particularly concerning the underlying mechanisms.

Nobel metal-based SACs
Noble metal-based catalysts, such as Ru and Pt, have been extensively studied for NRR due to their strong
electron-donating properties, which arise from their unfilled d orbitals.

Liu et al. proposed that single Ru atoms anchored in hexagonal pores of boron monolayers (Ru/B α-sheet
and Ru/B β -sheet) could serve as promising monoatomic NRR catalysts, with reaction energy barriers less
12
[70]
than half that of flat Ru(0001) catalysts . Yin et al. found that Pt/g-C N exhibited outstanding NRR
4
3
catalytic activity at room temperature, with a low U of -0.24 V, attributed to the synergistic interaction
L
*
between Pt atoms and the g-C N substrate, which optimized the energetics of N H and NH
*
2
2
4
3
intermediates .
[71]
SACs with other TMs
While noble metal catalysts have shown promise for NRR, their high cost limits their large-scale application.
TMs, such as W, Co, Nb, and Ni, are also being considered as active centers for NRR.
Chen et al. evaluated the catalytic performance of a series of single metal atoms loaded on g-C N . The
[72]
3
4
NRR catalytic activity of five TMs (Ti, Co, Mo, W, and Pt) supported on g-C N monolayers exceeded that
3
4
of Ru(0001) stepped surfaces. W@ g-C N , in particular, showed the highest catalytic activity with a U of
4
L
3
-0.35 V, attributed to the significant positive charge and large spin moment on the W atom, resulting in a
moderate adsorption strength for NRR intermediates.
Wang et al. studied the NRR behavior of SACs formed by a series of single TM atoms (from Sc to Zn)
anchored on g-C N . They found that Mn/g-C N exhibited excellent NRR activity with a low U of
L
10
9
10
9
-0.295 V through the distal pathway . Saeidi et al. reported that Co/N -Gr (Co atoms incorporated into N-
[73]
3
modified graphene) is a promising NRR catalyst with lower energy consumption and better stability,
preferring the alternating associative pathway with a U of -0.53 eV .
[74]
L
The Ni@Ti NO MXene structure, which satisfies orbital symmetry matching, could achieve an acceptor-
2
2
donor interaction, allowing N to be transformed via a novel “enzyme-distal” mechanism due to the
2
synergistic interaction between Ti and Ni atoms .
[24]
Additionally, Nb and W embedded in defective boron phosphide (BP) monolayers with boron
monovacancies (Nb/BP and W/BP) were documented as promising NRR electrocatalysts with low U (-0.25
L
and -0.19 V), attributed to the favorable matching between the d-orbitals of Nb or W atoms and the p-
orbitals of the N molecule above the Fermi level (E ) .
[75]
2
F
Gao et al. reported a theory-guided design of Nb catalysts supported on anatase TiO (110) for NRR.
2
Theoretical calculations showed that dispersing Nb atoms on anatase TiO (110) significantly increased
2
electron density at the E , enhancing conductivity and facilitating the proton-coupled electron transfer
F
process, thus leading to excellent NRR activity and selectivity for Nb-TiO (110) .
[76]
2