• Journal of Inorganic Materials
  • Vol. 39, Issue 5, 561 (2024)
Honglan LI1, Junmiao ZHANG1, Erhong SONG2,*, and Xinglin YANG1,*
Author Affiliations
  • 11. School of Energy and Power Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China
  • 22. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
  • show less
    DOI: 10.15541/jim20230433 Cite this Article
    Honglan LI, Junmiao ZHANG, Erhong SONG, Xinglin YANG. Mo/S Co-doped Graphene for Ammonia Synthesis: a Density Functional Theory Study[J]. Journal of Inorganic Materials, 2024, 39(5): 561 Copy Citation Text show less
    Structure, optimized lengths, binding energy and partial density of states (PDOS)of TMX(a) Atomic structure diagram of TMX doped graphene; (b) Optimized lengths, lTMB, of the TM-X bonds; (c) Binding energy, Eb(TMX), of TMX doped graphene; (d) PDOS between the d band of Mo and the p band of X for MoX doped graphene; Colorful figures are available on website
    1. Structure, optimized lengths, binding energy and partial density of states (PDOS)of TMX(a) Atomic structure diagram of TMX doped graphene; (b) Optimized lengths, lTMB, of the TM-X bonds; (c) Binding energy, Eb(TMX), of TMX doped graphene; (d) PDOS between the d band of Mo and the p band of X for MoX doped graphene; Colorful figures are available on website
    Adsorption behavior of the nitrogen molecule on graphene(a) Schematic diagram of N2 adsorption structures; (b) Difference in the adsorption free energy of N2 and H, ΔΔGads= Gads(*N2)-Gads(*H), as a function of Gads(*N2); (c) PDOS between the d band of Mo and the p band of N2 for MoB, MoP, and MoS doped graphene; (d) Charge, QN2, and bond length, lN2, of the N2 adsorbate; Colorful figures are available on website
    2. Adsorption behavior of the nitrogen molecule on graphene(a) Schematic diagram of N2 adsorption structures; (b) Difference in the adsorption free energy of N2 and H, ΔΔGads= Gads(*N2)-Gads(*H), as a function of Gads(*N2); (c) PDOS between the d band of Mo and the p band of N2 for MoB, MoP, and MoS doped graphene; (d) Charge, QN2, and bond length, lN2, of the N2 adsorbate; Colorful figures are available on website
    Free energy and plotting UL(NRR) vs UL(HER) of the catalysts(a, b) Free energy profiles for NRR of MoS doped graphene via (a) distal pathway and (b) alternating pathway; (c) Free energy profiles for HER of WS, WP, MoS, MoP, and NbB doped graphene; (d) Comparison between limiting potential of NRR and reduction potential of HER; Colorful figures are available on website
    3. Free energy and plotting UL(NRR) vs UL(HER) of the catalysts(a, b) Free energy profiles for NRR of MoS doped graphene via (a) distal pathway and (b) alternating pathway; (c) Free energy profiles for HER of WS, WP, MoS, MoP, and NbB doped graphene; (d) Comparison between limiting potential of NRR and reduction potential of HER; Colorful figures are available on website
    Variation of Mulliken charge and energy of the catalysts(a-c) Mulliken charge variation of (a) MoB, (b) MoP, and (c) MoS via the distal pathway; (d) Variation of temperature and energy of MoS during the AIMD simulation
    4. Variation of Mulliken charge and energy of the catalysts(a-c) Mulliken charge variation of (a) MoB, (b) MoP, and (c) MoS via the distal pathway; (d) Variation of temperature and energy of MoS during the AIMD simulation
    H adsorption structures of (a) FeX, (b) NbX, (c) MoX, (d) RuX, and (e) WX
    S1. H adsorption structures of (a) FeX, (b) NbX, (c) MoX, (d) RuX, and (e) WX
    Reaction coordinate of N2 splitting catalyzed by MoP doped grapheneRight up: structure of initial state (IS); Right middle: structure of transition state (TS); Right down: structure of final state (FS)
    S2. Reaction coordinate of N2 splitting catalyzed by MoP doped grapheneRight up: structure of initial state (IS); Right middle: structure of transition state (TS); Right down: structure of final state (FS)
    Fitting between UL(NRR) and N2* Mulliken charge Q(N2*) of TMX-doped graphene
    S3. Fitting between UL(NRR) and N2* Mulliken charge Q(N2*) of TMX-doped graphene
    QTMQXɛd
    BPSBPSBPS
    Fe-0.133-0.0150.0610.1720.427-0.100-1.007-1.330-1.383
    Nb0.5660.4860.6280.1230.437-0.147-1.489-2.475-2.157
    Mo0.2340.1470.2670.1880.479-0.107-1.556-1.930-1.820
    Ru-0.187-0.207-0.0320.3150.721-0.046-1.632-2.078-1.787
    W0.2470.1370.2650.1890.482-0.108-1.669-2.135-1.915
    Table 1.

    Mulliken charge Q (in e) of TM and X and the d band center ɛd (in eV) of TM in TMX-doped graphene

    BPS
    EbEintEdefEbEintEdefEbEintEdef
    Fe-6.46-8.692.23-6.26-7.491.23-5.35-6.581.23
    Nb-5.19-8.062.86-5.69-8.422.73-4.44-7.362.92
    Mo-6.71-9.833.12-6.95-9.952.99-5.80-8.893.09
    Ru-7.99-10.092.09-7.76-9.401.64-6.36-7.941.58
    W-5.67-9.043.37-5.71-8.963.26-4.52-7.893.37
    Table 2.

    Binding energy Eb(TMX) (in eV), interaction energy Eint (in eV) and deformation energy Edef (in eV)

    SystemPathwayGads(N2) ΔG1ΔG2ΔG3ΔG4ΔG5ΔG6Gads(H) UL(NRR)UL(HER)
    FeBDistal-0.450.27-0.361.11-2.22-0.740.46-0.380.810.38
    Alternating-0.450.270.81-1.380.58-2.230.46
    FePDistal-0.570.98-0.350.60-0.84-1.28-0.880.030.980.03
    Alternating-0.570.980.152.42-0.32-4.12-0.88
    FeSDistal-0.460.82-0.250.67-0.91-1.36-0.76-0.060.820.06
    Alternating-0.460.820.17-0.52-0.35-1.16-0.76
    NbBDistal-0.15-1.99-0.150.54-1.63-1.21-0.530.150.540.15
    Alternating-0.15-1.99-0.07-0.59-0.44-1.36-0.53
    NbPDistal-0.20-2.002.410.57-1.62-0.81-0.540.152.410.15
    Alternating-0.20-2.003.02-0.75-0.11-1.63-0.54
    NbSDistal-0.310.74-0.500.39-1.47-0.78-0.42-0.160.740.16
    Alternating-0.310.740.16-0.69-0.08-1.74-0.42
    MoBDistal-0.690.85-0.390.01-1.01-0.80-0.60-0.290.850.29
    Alternating-0.690.85-0.04-0.56-0.31-1.28-0.60
    MoPDistal-0.670.49-0.24-0.41-0.58-0.65-0.45-0.420.490.42
    Alternating-0.670.490.35-0.790.03-1.46-0.45
    MoSDistal-0.690.47-0.22-0.54-0.42-0.67-0.33-0.510.470.51
    Alternating-0.690.470.51-0.900.14-1.59-0.33
    RuBDistal-0.270.760.20-0.470.14-1.22-1.000.140.760.14
    Alternating-0.270.760.52-0.63-0.37-0.88-1.00
    RuPDistal-0.341.26-0.090.05-0.53-1.33-0.920.431.260.43
    Alternating-0.341.260.02-0.19-0.76-0.97-0.92
    RuSDistal-0.581.38-0.550.32-0.48-1.36-0.99-0.231.380.23
    Alternating-0.581.38-0.24-0.20-0.70-0.92-0.99
    WBDistal-0.640.66-0.49-0.09-1.06-0.71-0.25-0.560.660.56
    Alternating-0.640.660.07-0.700.12-1.84-0.25
    WPDistal-0.790.32-0.45-0.35-0.80-0.45-0.10-0.840.320.84
    Alternating-0.790.320.46-0.840.34-2.01-0.10
    WSDistal-0.780.22-0.33-0.59-0.62-0.450.11-0.950.220.95
    Alternating-0.780.220.77-1.070.47-2.150.11
    Table 3.

    Free energy changes of protonation steps ΔGi (i = 1,2, …, 6). Gads(N2) and Gads(H) are the free energy (in eV) of nitrogen and hydrogen adsorption, respectively. UL(NRR) and UL(HER) are the limiting potentials (in V) of the nitrogen reduction reaction (NRR) and hydrogen evolution reaction (HER), respectively

    Honglan LI, Junmiao ZHANG, Erhong SONG, Xinglin YANG. Mo/S Co-doped Graphene for Ammonia Synthesis: a Density Functional Theory Study[J]. Journal of Inorganic Materials, 2024, 39(5): 561
    Download Citation