Mo/S Co-doped Graphene for Ammonia Synthesis: a Density Functional Theory Study

Honglan LI; Junmiao ZHANG; Erhong SONG; Xinglin YANG

doi:10.15541/jim20230433

Journals >Journal of Inorganic Materials >Volume 39 >Issue 5 >Page 561 > Article

Journal of Inorganic Materials
Vol. 39, Issue 5, 561 (2024)

Mo/S Co-doped Graphene for Ammonia Synthesis: a Density Functional Theory Study

Honglan LI¹, Junmiao ZHANG¹, Erhong SONG^2,*, and Xinglin YANG^1,*

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

EndNote(RIS)

BibTex

Plain 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, l_TMB, of the TM-X bonds; (c) Binding energy, E_b(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

Download full size | View in the Article

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, ΔΔG_ads= G_ads(*N₂)-G_ads(*H), as a function of G_ads(*N₂); (c) PDOS between the d band of Mo and the p band of N₂ for MoB, MoP, and MoS doped graphene; (d) Charge, Q_N2, and bond length, l_N2, of the N₂ adsorbate; Colorful figures are available on website

Download full size | View in the Article

3. Free energy and plotting U_L(NRR) vs U_L(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

Download full size | View in the Article

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

Download full size | View in the Article

S1. H adsorption structures of (a) FeX, (b) NbX, (c) MoX, (d) RuX, and (e) WX

Download full size | View in the Article

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)

Download full size | View in the Article

S3. Fitting between U_L(NRR) and N₂* Mulliken charge Q(N₂*) of TMX-doped graphene

Download full size | View in the Article

	Q_TM			Q_X			ɛ_d
	B	P	S	B	P	S	B	P	S
Fe	-0.133	-0.015	0.061	0.172	0.427	-0.100	-1.007	-1.330	-1.383
Nb	0.566	0.486	0.628	0.123	0.437	-0.147	-1.489	-2.475	-2.157
Mo	0.234	0.147	0.267	0.188	0.479	-0.107	-1.556	-1.930	-1.820
Ru	-0.187	-0.207	-0.032	0.315	0.721	-0.046	-1.632	-2.078	-1.787
W	0.247	0.137	0.265	0.189	0.482	-0.108	-1.669	-2.135	-1.915

Table 1.

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

View in the Article

	B			P			S
	E_b	E_int	E_def	E_b	E_int	E_def	E_b	E_int	E_def
Fe	-6.46	-8.69	2.23	-6.26	-7.49	1.23	-5.35	-6.58	1.23
Nb	-5.19	-8.06	2.86	-5.69	-8.42	2.73	-4.44	-7.36	2.92
Mo	-6.71	-9.83	3.12	-6.95	-9.95	2.99	-5.80	-8.89	3.09
Ru	-7.99	-10.09	2.09	-7.76	-9.40	1.64	-6.36	-7.94	1.58
W	-5.67	-9.04	3.37	-5.71	-8.96	3.26	-4.52	-7.89	3.37

Table 2.

Binding energy E_b(TMX) (in eV), interaction energy E_int (in eV) and deformation energy E_def (in eV)

View in the Article

System	Pathway	G_ads(N₂)	ΔG₁	ΔG₂	ΔG₃	ΔG₄	ΔG₅	ΔG₆	G_ads(H)	U_L(NRR)	U_L(HER)
FeB	Distal	-0.45	0.27	-0.36	1.11	-2.22	-0.74	0.46	-0.38	0.81	0.38
FeB	Alternating	-0.45	0.27	0.81	-1.38	0.58	-2.23	0.46	-0.38	0.81	0.38
FeP	Distal	-0.57	0.98	-0.35	0.60	-0.84	-1.28	-0.88	0.03	0.98	0.03
FeP	Alternating	-0.57	0.98	0.15	2.42	-0.32	-4.12	-0.88	0.03	0.98	0.03
FeS	Distal	-0.46	0.82	-0.25	0.67	-0.91	-1.36	-0.76	-0.06	0.82	0.06
FeS	Alternating	-0.46	0.82	0.17	-0.52	-0.35	-1.16	-0.76	-0.06	0.82	0.06
NbB	Distal	-0.15	-1.99	-0.15	0.54	-1.63	-1.21	-0.53	0.15	0.54	0.15
NbB	Alternating	-0.15	-1.99	-0.07	-0.59	-0.44	-1.36	-0.53	0.15	0.54	0.15
NbP	Distal	-0.20	-2.00	2.41	0.57	-1.62	-0.81	-0.54	0.15	2.41	0.15
NbP	Alternating	-0.20	-2.00	3.02	-0.75	-0.11	-1.63	-0.54	0.15	2.41	0.15
NbS	Distal	-0.31	0.74	-0.50	0.39	-1.47	-0.78	-0.42	-0.16	0.74	0.16
NbS	Alternating	-0.31	0.74	0.16	-0.69	-0.08	-1.74	-0.42	-0.16	0.74	0.16
MoB	Distal	-0.69	0.85	-0.39	0.01	-1.01	-0.80	-0.60	-0.29	0.85	0.29
MoB	Alternating	-0.69	0.85	-0.04	-0.56	-0.31	-1.28	-0.60	-0.29	0.85	0.29
MoP	Distal	-0.67	0.49	-0.24	-0.41	-0.58	-0.65	-0.45	-0.42	0.49	0.42
MoP	Alternating	-0.67	0.49	0.35	-0.79	0.03	-1.46	-0.45	-0.42	0.49	0.42
MoS	Distal	-0.69	0.47	-0.22	-0.54	-0.42	-0.67	-0.33	-0.51	0.47	0.51
MoS	Alternating	-0.69	0.47	0.51	-0.90	0.14	-1.59	-0.33	-0.51	0.47	0.51
RuB	Distal	-0.27	0.76	0.20	-0.47	0.14	-1.22	-1.00	0.14	0.76	0.14
RuB	Alternating	-0.27	0.76	0.52	-0.63	-0.37	-0.88	-1.00	0.14	0.76	0.14
RuP	Distal	-0.34	1.26	-0.09	0.05	-0.53	-1.33	-0.92	0.43	1.26	0.43
RuP	Alternating	-0.34	1.26	0.02	-0.19	-0.76	-0.97	-0.92	0.43	1.26	0.43
RuS	Distal	-0.58	1.38	-0.55	0.32	-0.48	-1.36	-0.99	-0.23	1.38	0.23
RuS	Alternating	-0.58	1.38	-0.24	-0.20	-0.70	-0.92	-0.99	-0.23	1.38	0.23
WB	Distal	-0.64	0.66	-0.49	-0.09	-1.06	-0.71	-0.25	-0.56	0.66	0.56
WB	Alternating	-0.64	0.66	0.07	-0.70	0.12	-1.84	-0.25	-0.56	0.66	0.56
WP	Distal	-0.79	0.32	-0.45	-0.35	-0.80	-0.45	-0.10	-0.84	0.32	0.84
WP	Alternating	-0.79	0.32	0.46	-0.84	0.34	-2.01	-0.10	-0.84	0.32	0.84
WS	Distal	-0.78	0.22	-0.33	-0.59	-0.62	-0.45	0.11	-0.95	0.22	0.95
WS	Alternating	-0.78	0.22	0.77	-1.07	0.47	-2.15	0.11	-0.95	0.22	0.95

Table 3.

Free energy changes of protonation steps ΔG_i (i = 1,2, …, 6). G_ads(N₂) and G_ads(H) are the free energy (in eV) of nitrogen and hydrogen adsorption, respectively. U_L(NRR) and U_L(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

Save the article for my favorites

Paper Information

微信扫一扫：分享

微信扫一扫：分享