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Page 6 of 25 Meng et al. J. Mater. Inf. 2025, 5, 3 https://dx.doi.org/10.20517/jmi.2024.74

Figure 3. Representative optimized structures of Mo-embedded SACs. (A) Mo-BN, reprinted with permission from Ref. [32] . Copyright ©
2017 American Chemical Society; (B) Mo@GDY, reprinted with permission from Ref. [35] . Copyright © 2019 Elsevier B.V.; (C) Mo-Pp,
reprinted with permission from Ref. [36] . Copyright © 2020 American Chemical Society; (D) Mo@BM-β , reprinted with permission from
12
Ref. [37] . Copyright © 2021 American Chemical Society; (E) Mo@BM-α, reprinted with permission from Ref. [38] . Copyright © 2022
Elsevier B.V. SACs: Single-atom catalysts; Mo@GDY: graphdiyne monolayer.

Based on the experimental work by Osuka et al. on the tetrameric porphyrin sheet and linear conjugated
Zn-Pp tapes [61,62] , Liu et al. investigated extended 2D TM porphyrin sheets (TM-Pp, TM = Sc, Ti, V, Cr, Mn,
Fe, Co, Ni, Cu, Zn, Nb, Mo, Ru) for NRR . Their study indicated that Mo-Pp [Figure 3C] is a promising
[36]
NRR electrocatalyst under ambient conditions due to its high thermodynamic stability and low U .
L
The combination of edge fluoridation with Mo dopants endowed Mo single atoms anchored on zigzag
graphene nanoribbons with H/F terminations (Mo-g/H and Mo-g/F) with excellent NRR properties.
Electronic analysis showed that edge termination modulates the binding strength of Mo anchoring,
alternating its affinity for NRR intermediates and boosting NRR selectivity .
[63]

Xu et al. systematically studied the NRR activity of metal-atom-embedded M@BM-β (including 3d/4d TMs
12
and main group metals) SACs, and their results showed that Mo@BM-β [Figure 3D] and Mn@BM-β
12
12
demonstrate promising properties with U of -0.26 and -0.32 V, respectively, and could effectively suppress
L
[37]
the competitive hydrogen evolution reaction (HER) .
Similarly, Li et al. studied the donor-acceptor interaction between TM atoms and N , showing that during
2
N activation, the antibonding orbital of N accumulates significant negative charge transferred from the
2
2
TM atom, thus facilitating the activation of N . Among the 20 TMs (3d/4d TMs) on an α-borobenzene
2
monolayer (BM-α), V@BM-α and Mo@BM-α [Figure 3E] showed the best activity, with U of -0.22 and
L
-0.32 V, respectively .
[38]
Single TM atoms coordinated by N atoms (TM-N ) are also attractive for NRR. Wang et al. reported that
x
the experimentally realized single Mo atoms supported on N-doped carbon (Mo -N C , a Mo atom
2
1
1
coordinated by one N atom and two C atoms) exhibited excellent NRR activity via the enzymatic