钼吸附二维硼氮单层材料催化氮还原反应的密度泛函理论计算

doi:10.15541/jim20260021

摘要/Abstract

摘要：

电催化氮还原反应被视为可持续合成氨的重要路径, 开发高活性、高选择性的催化剂是该技术的核心挑战。本研究通过密度泛函理论计算, 系统探究了钼修饰B₂N、B₃N及B₄N单层材料的氮还原反应性能。钼与基底间的强相互作用确保了体系稳定性, Mo-B₂N、Mo-B₃N和Mo-B₄N的结合能分别为-8.39、-5.91和-6.75 eV。研究表明, 钼活性位点能有效活化氮气分子, 吸附后N≡N键长由气相中的1.108 Å分别延长至1.128 Å (Mo-B₂N)、1.132 Å (Mo-B₃N)和1.132 Å (Mo-B₄N)。自由能分析表明, Mo-B₂N、Mo-B₃N和Mo-B₄N的热力学能垒分别为1.21、1.07和0.61 eV, 其中Mo-B₄N展现出最优催化活性, 证实配位环境可有效调控钼的反应活性。电子结构分析揭示了N≡N键强度与热力学能垒的关联性, N≡N键越弱, 氮还原反应活性越强。此外, 300 K室温下的结构刚性保持验证了Mo-B₄N优异的热力学稳定性。综上, Mo-B₄N在电催化氮还原反应中兼具高活性与稳定性。本研究为氮还原电催化剂的设计提供了理论指导, 并提出了具有实验可行性的候选体系。本文数据集可在 https://www.doi.org/10.57760/sciencedb.jim.00043中访问获取。

关键词: 氮还原反应, 密度泛函理论, 单原子催化

Abstract:

Electrocatalytic nitrogen reduction reaction (NRR) is regarded as a promising route for sustainable ammonia synthesis, but developing highly active and selective catalysts remains a critical challenge. In this work, the density functional theory calculations were performed to investigate the NRR performance of Mo-adsorbed B₂N, B₃N and B₄N monolayers. The strong interaction between Mo and its substrate ensures the good stability, as reflected by the binding energies of -8.39, -5.91 and -6.75 eV for Mo-adsorbed B₂N, B₃N and B₄N monolayers, respectively. The adsorbed Mo sites are able to activate the N₂ molecule, elongating the N≡N bond length from 1.108 Å in the gas phase to 1.128, 1.132 and 1.132 Å on Mo-B₂N, Mo-B₃N and Mo-B₄N, respectively. Free energy profile analysis reveals that the thermodynamic barriers are 1.21, 1.07 and 0.61 eV for Mo-B₂N, Mo-B₃N and Mo-B₄N, with Mo-B₄N exhibiting the highest activity. This trend clearly demonstrates that the Mo reactivity is well-tuned by its coordination. Furthermore, the electronic structure analysis shows a relation between the strength of N≡N bond and the thermodynamic energy, where a weaker strength of N≡N bond indicates a better NRR activity. Mo-B₄N material also exhibits a high thermodynamic stability, as reflected by the robustness of the structural rigidity wherein no structural collapse is observed under the room temperature of 300 K. Therefore, Mo-B₄N is expected to be an active and durable catalyst for the NRR. This study provides theoretical guidance for the design of NRR electrocatalysts and proposes viable candidate systems for experimental synthesis. The datasets in this article are listed in Science Data Bank at https://www.doi.org/10.57760/sciencedb.jim.00043.

Key words: nitrogen reduction reaction, density functional theory, single-atom catalysis

中图分类号:

TQ174

李智, 张俊苗, 冯紫阳, 肖蓓蓓, 宋二红. 钼吸附二维硼氮单层材料催化氮还原反应的密度泛函理论计算[J]. 无机材料学报, 2026, 41(10): 1517-1524.

LI Zhi, ZHANG Junmiao, FENG Ziyang, XIAO Beibei, SONG Erhong. Density Functional Theory Computation of Mo-adsorbed Two-dimensional Boron-nitrogen Monolayers for Nitrogen Reduction Reaction[J]. Journal of Inorganic Materials, 2026, 41(10): 1517-1524.

图/表 10

Fig. 1 (a) Model structures; (b) Linear relationship between d-band center and binding energy; (c) Iso-surface plots of the charge density difference (CDD) and charge transfer quantities; (d) Partial density of states (PDOS) analysis for Mo interacting with B2N, B3N and B4N substrates, respectively, with the p-band contributions from B2N, B3N and B4N represented the combined p-bands of B and N atoms directly bonded to metal atoms in each structure

Fig. 2 (a) Adsorption free energies of N2 under two adsorption configurations; (b) PDOS of Mo with N2 adsorbate; (c) Charge transfer quantity for N2 adsorbed on Mo-B4N; (d) Crystal orbital Hamilton population (COHP) analysis of N≡N bond in adsorbed *N2

Table 1 Free energy changes ΔG of elementary steps and thermodynamic barriers ΔGmax

Structure	Mechanism	ΔG/eV						ΔG_max/eV
Mo-B₂N	Distal	1.21	−0.32	−0.19	−0.44	−0.01	−0.90	1.21
	Alternating	1.21	0.08	−0.07	1.25	−2.29	−0.82	1.25
	Enzymatic	1.75	−0.43	−0.65	−0.67	−0.01	−0.50	1.75
Mo-B₃N	Distal	1.07	0.48	−0.76	−0.74	0.53	−0.12	1.07
	Alternating	1.07	1.23	−1.28	0.44	−1.71	0.70	1.23
	Enzymatic	0.64	−0.03	−0.65	−1.51	−0.32	1.34	1.34
Mo-B₄N	Distal	0.61	−0.04	−0.01	−0.74	−0.51	0.13	0.61
	Alternating	0.61	0.63	−0.88	0.82	−2.35	0.61	0.82
	Enzymatic	0.98	−0.07	−0.63	−1.33	−0.34	0.66	0.98

Fig. 3 (a) Distal pathway of Mo-B4N; (b) Alternating pathway of Mo-B4N; (c) Enzymatic pathway of Mo-B4N; (d) Thermodynamic barriers of Mo-B2N, Mo-B3N and Mo-B4N

Fig. 4 (a) Total density of states (TDOS) of Mo-B4N with varied N-containing intermediates along the distal pathway; (b) Linear relationship between -ICOHP of N≡N bond and thermodynamic energy barrier; (c) Bond lengths of N-N and Mo-N; (d) AIMD simulation of Mo-B4N at room temperature of 300 K

Table 2 Bond length between Mo and B/N atom

Time/ps		0	1	2	3	4	5	6	7	8	9	10
Bond length/Å	Mo-B1	2.325	2.270	2.210	2.258	2.368	2.321	2.317	2.342	2.198	2.298	2.242
	Mo-B2	2.209	2.141	2.174	2.211	2.194	2.215	2.267	2.148	2.161	2.162	2.325
	Mo-B3	2.249	2.245	2.209	2.317	2.148	2.277	2.239	2.204	2.261	2.181	2.257
	Mo-B4	2.029	2.048	2.030	2.023	2.017	2.048	2.006	2.043	2.069	2.004	2.091
	Mo-B5	2.081	2.087	2.178	2.179	2.111	2.053	2.082	2.084	2.188	2.089	2.102
	Mo-N	2.236	2.169	2.251	2.222	2.247	2.206	2.266	2.389	2.149	2.141	2.217

Table S1 Comparison of adsorption energies with and without vdW corrections

Energy	NN	NNH	NNH₂	N	NH	NH₂	NH₃
With corrections/eV	−1.235	−2.925	−3.920	−8.270	−5.318	−4.230	−1.882
Without corrections/eV	−1.139	−2.820	−3.789	−8.232	−5.251	−4.133	−1.779
Difference/eV	−0.096	−0.105	−0.131	−0.038	−0.067	−0.097	−0.103

Table S2 Comparison of ΔGmax cited from the previous reports

Catalyst	ΔG_max/eV	Ref.
Mo-B₄N	0.61	This work
Mo₃(HAB)₂	0.66	[11]
Mo-C₄N₃	0.76	[13]
MoPc-TFPN	0.21	[15]
Mo-C₃N₃	0.41	[14]
Mo-BN	1.01	[12]
Mo-GR	0.71	[12]
Mo-GDY	0.43	[12]
Mo-C₉N₄	0.40	[26]

Fig. S1 Free energies of hydrogen adsorption ΔGH under different potentials

Fig. S2 Labeled coordination environment of Mo-B4

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