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NO2、NH3、芥子气和沙林是具有代表性的化学毒剂, 它们扩散快毒性强, 因此实现学术界和工业界对它们的快速检测极为重要. 本文使用密度泛函理论研究发现过渡金属Mo原子可以稳定掺杂在二维VS2结构中的S空位上, 且掺杂结构与NO2、NH3、沙林和芥子气之间具有较强的相互作用, 进一步影响VS2对NO2、NH3、沙林和芥子气的气敏性. 本文通过吸附能、吸附距离、Mulliken电荷, 差分电荷密度, 能带图与态密度分析等进一步揭示了影响机理, 并依据电导率、能带等计算结果对4种气体进行区分. 因此Mo原子掺杂的VS2结构可以有效吸附有毒气体, 该研究可以为实验研究者提供充足的理论依据.As is well known, the leakage of four toxic gases, NO2, NH3, mustard gas and sarin greatly threaten the environment and human health. Among of them, mustard gas and sarin are two serious chemical and biological weapons agents, and exposure to a small amount can cause skin burns and immediate death. NO2 and NH3 are two common toxic pollutants produced by automobile exhaust, coal combustion and petrochemical industry. The presence of trace amounts of NO2 and NH3 gas in human tissues can cause serious respiratory diseases and damage human brain and other systems. Thus, it is very important to realize the rapid detection of NO2, NH3, mustard gas and sarin in academia and industry. In this study, we use density functional theory to investigate the ability of a transition metal Mo doped two-dimensional VS2 structure to detect the four representative toxic gases. The results reveal that Mo atom doping has a significant effect on the stability and gas-sensitivity of the VS2 structure. The Mo atom can be successfully doped on the S-vacancy in the two-dimensional VS2 structure. Compared with the undoped structure VS2, the doped structure Mo-VS2 has strong interaction with NO2, NH3, sarin, and mustard gas, realizing effective adsorption of them. The presence of Mo atom in the VS2 lattice changes the electronic structure of VS2, also modifies its band gap and density of states. The interaction between the Mo-VS2 structure and the target analytes depends strongly on the nature of the gas molecule. The binding energy values for NO2, NH3, mustard gas, and sarin on the Mo-VS2 are significantly higher than those on the pristine VS2, indicating stronger interaction between the Mo-VS2 structure and these gases. Our calculations show that the Mo atom in VS2 changes its electrical resistance after being exposed to the gases, which can be used to distinguish different gases. Moreover, differences in charge redistribution within the Mo-VS2 structure upon being exposed to different gases can be used to explain their differential gas-sensitivity. Our results can provide sufficient theoretical basis for experimental researchers to design and optimize the performances of sensors in practical applications.
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Keywords:
- VS2 /
- density functional theory /
- adulteration /
- gas-sensitive mechanism
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Google Scholar
[2] Niemann A 1860 Justus Liebigs Annalen der Chemie. 113 288
Google Scholar
[3] Meyer V 1886 Berichte der Deutschen Chemischen Gesellschaft 19 3259
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Xu W S 2021 Ph. D. Dissertation (Hefei: University of Science and Technology of China
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
[19] Perdew J P, Wang Y 1992 Phys. Rev. B 45 13244e9
Google Scholar
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Google Scholar
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Google Scholar
[22] Delly B J 1990 Chem. Phys. 92 508e17
Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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图 1 (a) VS2(001)表面; (b)掺杂结构Mo-VS2; (c) Mo-VS2结构的差分电荷密度图
Fig. 1. (a) Structure of VS2(001); (b) doping structure of Mo-VS2; (c) differential charge density map of Mo-VS2.
图 2 (a) VS2的能带图; (b) Mo-VS2的能带图
Fig. 2. (a) Energy band diagram of VS2; (b) energy band diagram of Mo-VS2.
图 3 (a) NH3和NO2分子位于Mo原子上方与表面平行; (b) NH3和NO2分子位于六元环中心位上方与表面平行; (c) NH3和NO2分子位于六元环中心位上方与表面垂直; (d) NH3和NO2分子位于Mo原子上方与表面垂直
Fig. 3. (a) NH3 and NO2 molecules are located above the Mo atom and parallel to the surface; (b) NH3 and NO2 molecules are located above the center of the six-membered ring and parallel to the surface; (c) NH3 and NO2 molecules are located above the center of the six-membered ring and perpendicular to the surface; (d) NH3 and NO2 molecules are located above the Mo atom and perpendicular to the surface.
图 4 (a), (c) S原子位于Mo原子的上方; (b), (d) C原子位于Mo原子的上方; (a), (b) HD分子沿表面短轴; (c), (d) HD分子沿表面长轴; (e)对结构(c)沿长轴旋转90o; (f) 对结构(c)沿长轴旋转180o; (g) 对结构(c)长轴旋转270o; (h) HD分子长轴垂直于表面
Fig. 4. (a), (c) S atom is above the Mo atom; (b), (d) C atom is above the Mo atom; (a), (b) HD molecules along the short axis of the surface; (c), (d) HD molecules along the long axis of the surface; (e) rotate structure (c) by 90o along its major axis; (f) rotate structure (c) by 180o along its major axis; (g) rotate structure (c) by 270o along its major axis; (h) the major axis of the HD molecule is perpendicular to the surface.
图 5 (a) C原子在Mo原子的上方; (b) F原子在Mo原子的上方; (c) H原子在Mo原子的上方; (d) 与P, C成键的O原子在Mo原子的上方; (e) 对结构4旋转90o; (f) 对结构4旋转180o; (g) 对结构4旋转270o; (h) sarin分子“长边”垂直于表面
Fig. 5. (a) C atom is above the Mo atom; (b) F atom is above Mo atom; (c) H atom is above Mo atom; (d) O atom bonded with P and C is above the Mo atom; (e) rotate structure 4 by 90o; (f) rotate structure 4 by 180o; (g) rotate structure 4 by 270o; (h) the “long side” of the sarin molecule is perpendicular to the surface.
图 6 4种气体在Mo掺杂前后的表面吸附构型 (a) NH3@VS2; (b) NO2@VS2; (c) HD@VS2; (d) sarin@VS2; (e) NH3@Mo-VS2; (f) NO2@Mo-VS2; (g) HD@Mo-VS2; (h) sarin@Mo-VS2.
Fig. 6. Adsorption configurations of four kinds of gas before and after Mo doping: (a) NH3@VS2; (b) NO2@VS2; (c) HD@VS2; (d) sarin@VS2; (e) NH3@Mo-VS2; (f) NO2@Mo-VS2; (g) HD@Mo-VS2; (h) sarin@Mo-VS2
图 7 差分电荷密度图 (a) NH3@Mo-VS2; (b) NO2@Mo-VS2; (c) HD@Mo-VS2; (d) sarin@Mo-VS2
Fig. 7. Differential charge density map: (a) NH3@Mo-VS2; (b) NO2@Mo-VS2; (c) HD@Mo-VS2; (d) sarin@Mo-VS2.
图 8 各体系的能带图 (a) NO2@Mo-VS2; (b) NH3@Mo-VS2; (c) HD@Mo-VS2; (d) sarin@Mo-VS2
Fig. 8. Energy band diagram of different system: (a) NO2@Mo-VS2; (b) NH3@Mo-VS2; (c) HD@Mo-VS2; (d) sarin@Mo-VS2.
图 9 Mo-VS2与NH3, NO2, HD, sarin吸附构型的态密度图
Fig. 9. DOS diagram of Mo-VS2 adsorption configuration with NH3, NO2, HD and sarin.
表 1 4种分子吸附在不同位置时与最低稳定结构之间的能量差ΔE
Table 1. Energy difference between the four molecules adsorbed at different positions and the lowest stable structure (ΔE).
Structure Site ΔE/eV Structure Site ΔE/eV Structure Site ΔE/eV NH3 a 0.000 HD 1 0.858 Sarin 1 1.021 b 0.348 2 0.859 2 1.285 c 0.369 3 0.000 3 0.974 d 0.012 4 0.892 4 0.000 NO2 a 0.000 a 0.902 a 3.163 b 0.455 b 0.557 b 1.217 c 0.354 c 1.552 c 0.128 d 0.011 d 1.461 d 3.843 
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表 2 4种有毒气体在单层VS2结构和Mo原子掺杂结构表面的Ead, 吸附分子的Mulliken电荷(Qmolecule)和Mo原子的Mulliken电荷(QMo)和恢复时间($ \tau $)
Table 2. Four toxic gases in monolayer VS2 structure and Mo atom doped structure surface Ead, adsorbed molecule Mulliken charge (Qmolecule) and Mo atom Mulliken charge (QMo) and recovery time ($ \tau $).
structure Ead/eV Qmolecule/$ e $ $ \tau /{\mathrm{s}} $ QMo/$ e $ NH3@Mo-VS2 2.59 0.207 7.01×1030 0.16 NH3@VS2 0.18 0.035 1.19×10–10 — NO2@Mo-VS2 2.86 –0.342 3.03×1035 0.139 NO2@VS2 –0.06 –0.101 9.14×10–15 — HD@Mo-VS2 2.19 0.302 1.15×1024 –0.004 HD@VS2 0.65 0.084 8.36×10–4 — sarlin@Mo-VS2 1.95 0.205 1.06×1020 0.292 sarlin@VS2 0.50 –0.015 3.73×10–5 —
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[1] Guthrie F 1860 Justus Liebigs Annalen der Chemie. 113 266
Google Scholar
[2] Niemann A 1860 Justus Liebigs Annalen der Chemie. 113 288
Google Scholar
[3] Meyer V 1886 Berichte der Deutschen Chemischen Gesellschaft 19 3259
Google Scholar
[4] Sadeghi M 2015 Basic and Clinical Toxicology of Mustard Compounds (New York: Springer International Publishing) pp1–27
[5] Qin Y, Zhang Z 2020 Phys. E Low-dimens. Syst. Nanostruct. 116 113737
Google Scholar
[6] Jia X, Zhang H, Zhang Z, An L 2019 Superlattice Microst. 134 106235
Google Scholar
[7] Lundberg J O, Weitzberg E, Gladwin M T 2008 Nat. Rev. Drug Discov. 7 156
Google Scholar
[8] Basharnavaz H, Habibi-Yangjeh A, Kamali S H 2019 Mater. Chem. Phys. 231 264
Google Scholar
[9] 刘卫卫, 余建华, 潘勇 2005 化学传感器 4 52
Google Scholar
Liu W W, Yu J H, Pan Y 2005 Chem. Sensors 4 52
Google Scholar
[10] Hill C L 1995 Coord. Chem. Rev. 143 407
Google Scholar
[11] Müller A, Peters F, Pope M T 1998 Chem. Rev. 98 239
Google Scholar
[12] Long D L, Burkholder E, Cronin L 2007 Chem. Soc. Rev. 36 105
Google Scholar
[13] 徐望胜 2021 博士学位论文(合肥: 中国科学技术大学)
Xu W S 2021 Ph. D. Dissertation (Hefei: University of Science and Technology of China
[14] Ali M, Tit N 2019 Surf. Sci. 684 28
Google Scholar
[15] Zhao Z, Yong Y, Hu S, Li C, Kuang Y 2019 AIP Adv. 9 125308
Google Scholar
[16] 梁婷, 王阳阳, 刘国宏, 符汪洋, 王怀璋, 陈静飞 2021 物理学报 70 080701
Google Scholar
Liang T, Wang Y Y, Liu G H, Fu W Y, Wang H Z, Chen J F 2021 Acta Phys. Sin. 70 080701
Google Scholar
[17] Fabian A 2018 arXiv. 1803.07999 [cond-mat. mtrl-sci
[18] Delley B 2000 J. Chem. Phys. 113 7756e64
Google Scholar
[19] Perdew J P, Wang Y 1992 Phys. Rev. B 45 13244e9
Google Scholar
[20] Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865e8
Google Scholar
[21] Krasnov P O, Ding F, Singh A K, Yakobson B I 2007 Phys. Chem. C 111 17977e80
Google Scholar
[22] Delly B J 1990 Chem. Phys. 92 508e17
Google Scholar
[23] Liu Z C, Gui Y G, Xu L N, Chen X P 2022 Surf. Interfaces 30 101883
Google Scholar
[24] Shi Z Y, Zhang J Q, Zeng W, Zhou Q 2023 Langmuir 39 4125
Google Scholar
[25] Eric B I, Chris A M 2016 Phys. Rev. B 94 035120
Google Scholar
[26] Zhang B O, Wang Z, Huang H, Zhang L, Gu M, Cheng Y, Wu K, Zhou J, Zhang J 2020 J. Mater. Chem. A 8 8586
Google Scholar
[27] Xiong H H, Zhang H H, Gan L 2020 J. Phys. E 126 114463
Google Scholar
[28] Zhang Y H, Chen Y B, Zhou K G, Liu C H, Zeng J, Zhang H L, Peng Y 2009 Nanotechnology 20 185504
Google Scholar
[29] Peng S, Cho K, Qi P, Dai H 2004 Chem. Phys. Lett. 387 271
Google Scholar
[30] Chen L, Xiong Z, Cui Y, Luo H, Gao Y 2021 Appl. Surf. Sci. 542 148767
Google Scholar
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