<trans-title xml:lang="en">Mo/S Co-doped Graphene for Ammonia Synthesis: a Density Functional Theory Study</trans-title>

Honglan LI; Junmiao ZHANG; Erhong SONG; Xinglin YANG

doi:10.15541/jim20230433

Journal of Inorganic Materials, Volume. 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

Abstract Get PDF(in Chinese)

Figures & Tables(10)

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 Article

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 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 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 Article

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

Download full size

View in 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 Article

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

Download full size

View in Article

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 table

View in Article

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

	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 2.
Binding energy E_b(TMX) (in eV), interaction energy E_int (in eV) and deformation energy E_def (in eV)

View table

View in Article

Table 2.
Binding energy E_b(TMX) (in eV), interaction energy E_int (in eV) and deformation energy E_def (in eV)

	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 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

View table

View in Article

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

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

Tools

Get Citation

Copy Citation Text

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

EndNote(RIS)BibTex Plain Text

Set citation alerts for article

Save article for my favorites

Paper Information

Category:

Received: Sep. 21, 2023

Accepted: --

Published Online: Jul. 8, 2024

The Author Email: Erhong SONG (ehsong@mail.sic.ac.cn), Xinglin YANG (hcyangxl2010@163.com)

DOI:10.15541/jim20230433

Topics

laser devices and laser physics

Lasers and Laser Optics

Laser physics

laser manufacturing

Instrumentation, Measurement and Metrology

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

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

Table 2. Binding energy Eb(TMX) (in eV), interaction energy Eint (in eV) and deformation energy Edef (in eV)

Table 2. Binding energy Eb(TMX) (in eV), interaction energy Eint (in eV) and deformation energy Edef (in eV)

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

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

Table 2.
Binding energy E_b(TMX) (in eV), interaction energy E_int (in eV) and deformation energy E_def (in eV)

Table 2.
Binding energy E_b(TMX) (in eV), interaction energy E_int (in eV) and deformation energy E_def (in eV)