Page 64 - Read Online

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

Table 1. Summary of the Mo/Fe/V-based SACs towards NRR investigated by DFT calculations
Systems Limiting potential/V Reaction mechanism Year of publication
Mo-BN -0.35 Enzymatic 2017 [32]
[33]
Mo@C N -0.17 Distal 2018
2
[34]
Mo-MoS 2 -0.53 Distal/alternating 2018
[35]
Mo@GDY -0.33 Distal 2020
[36]
Mo-Pp -0.58 Distal/alternating 2020
Mo@BM-β 12 -0.26 Enzymatic 2021 [37]
[38]
Mo@BM-α -0.32 Enzymatic 2022
Mo -N C -0.40 Enzymatic 2018 [39]
1
1 2
[40]
Mo /N -G -0.50 Distal-to-alternating hybrid 2019
1 3
[41]
MoN @555-777 graphene -0.57 Distal 2020
3
-0.57 Enzymatic
[42]
Mo/g-CN -0.39 Distal 2020
Mo-MoSSe with S vacancy -0.49 Alternating 2019 [43]
[44]
Mo-based MOFs -0.34 Distal/alternating 2019
Mo@BCN -0.59 Enzymatic 2019 [45]
[46]
Mo/G with Se doping -0.41 Enzymatic 2019
Mo N -BP -0.18 Distal 2019 [47]
3
1
[48]
Mo/CeO -S -0.52 Distal/alternating 2019
2
Mo-PTA -0.42 Distal 2019 [49]
[50]
Mo -PMA -0.35 Enzymatic 2022
1
[51]
FeB (β) -0.68 Distal 2019
6
V@BN -0.41 Enzymatic 2020 [52]
[53]
V @Ti CO -0.20 Mixed 2023
1 2 2
V@g-C N 4 -0.55 Distal 2023 [54]
3
[55]
Fe-C N -0.7 Distal/alternating 2020
2
Ti@N 4 -0.69 Distal 2018 [56]
V@N -0.87 Distal
4
V/β -BM -0.28 Enzymatic 2019 [57]
12
V@GDY -0.67 Distal/alternating 2020 [58]
[59]
V/Ars -0.26 Enzymatic 2020
SACs: Single-atom catalysts; NRR: nitrogen reduction reaction; DFT: density functional theory; GDY: graphdiyne monolayer; Pp: porphyrin; BM-β :
12
metal-doped β-borophene; BM-α: metal-doped α-borophene; N C : N-doped carbon; N -G: N-doped graphene; MOFs: metal-organic
2
3
1
frameworks; N -BP: N-doped black phosphorus; PTA: phosphotungstic acid; PMA: phosphomolybdic acid; Ti@N : Ti on defective graphene
3 4
derivatives; V-β -BM: V anchored on boron monolayer (β ); Ars: arsenene nanosheet.
12 12
influences catalytic activity due to differences in the coordination environment of the Mo center.
Specifically, the intrinsic nitrogen reduction catalytic activity and selectivity of SACs are strongly influenced
by the surrounding environment of the active metal atoms and the geometry of the support, just as they are
in the oxygen reduction reaction (ORR) .
[60]
Mo-based SACs supported by graphene-like 2D materials are expected to combine the advantages of Mo
atoms (the active center of natural nitrogenase) and 2D substrates (acting as electron bridges and
reservoirs), showing great potential for NRR applications. Zhai et al. reported that Mo embedded in a
graphdiyne (GDY) monolayer (Mo@GDY) [Figure 3B] stood out among a series of TM-embedded GDY
monolayer (TM@GDY, TM = Sc, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, and Ag), exhibiting high
stability, excellent conductivity, and superior NRR activity through the distal mechanism. This behavior was
attributed to the strong interactions between hydrogen and the neighboring nitrogen atoms (H-N ) during
2
[35]
the first hydrogenation step .