二核铌钼硫簇NbMoSn-/0(n=3~7)掺杂体系的结构与成键性质的理论研究

doi:10.6023/A16110578

摘要/Abstract

近年来，过渡金属硫化物作为催化材料在许多化学反应中扮演着重要角色，特别是在石油化工领域的加氢脱硫与加氢脱氮等环节中被广泛应用.本工作采用密度泛函理论结合高精度的耦合簇[CCSD（T）]计算方法，对掺杂类型的铌钼硫簇NbMoS_n^-/0（n=3~7）进行系统研究，确定其最稳定的几何结构，并探讨掺杂、调节硫含量、改变团簇所带电荷等手段，对掺杂类型铌钼硫簇几何构型、电子结构与化学成键等性质的影响.本工作采用广义Koopmans定理计算NbMoS_n^-（n=3~7）阴离子基态的电子垂直逸出能（VDEs），模拟相应的阴离子光电子能谱图（PES），并结合对分子轨道的分析来进一步阐述该体系在几何结构与化学成键等性质上的演变规律.本工作可为进一步开展铌钼硫簇掺杂体系的理论与实验研究提供较为可靠的理论依据.

关键词: 过渡金属硫簇, 密度泛函理论, 结构演化, 光电子能谱模拟

Recently, transition metal sulfides (TMS) have played an important role in many catalytic reactions. In particular, they are widely used in the petrochemical industry, such as the hydrodesulfurization (HDS) and the hydrodenitrogenation (HDN) processes. In this work, density functional theory (DFT) and coupled cluster theory[CCSD(T)] calculations were used to study the niobium-mixed di-nuclear molybdenum sulfide clusters NbMoS_n^-/0(n=3~7). In our calculations, their ground-state structures were determined and the effects of doping metal, adjusting the sulfur content (n) and changing the charge states of clusters were discussed on the geometries, electronic structures and chemical bonding of NbMoS_n^-/0(n=3~7). NbMoS_n^-/0(n=3~7) clusters can be viewed as linking different sulfur ligands to the NbMoS₂ four-membered rings. Among them, diverse poly-sulfur ligands, such as bridging S₂, terminal S₂ and terminal S₃ groups, emerged in the sulfur-rich clusters. Generalized Koopmans' Theorem was employed to predict the vertical detachment energies (VDEs), and simulate the corresponding anionic photoelectron spectra (PES). The first VDEs (VDE_1st) of NbMoS_n^-(n=3~6) increased gradually as a function of n, and then decreased suddenly when the sulfur content (n) reached 7. The VDE_1st reached the maximum by 4.69 eV when the sulfur content equaled to 6. The driving forces (-ΔG) of the reduction reactions between NbMoS_n^-/0(n=3~7) and H₂ were evaluated. The NbMoS₇^- anion with the terminal S₂^2- group yielded the negative value of ΔG, which indicated that the reaction is thermodynamically favored even at the room temperature. We predicted that doping niobium into the molybdenum sulfides may improve the emergence of S₂ group which may be helpful in producing the coordinatively unsaturated sites (CUS) under the H₂/H₂S atmosphere. Molecular orbital analyses are performed to improve our understanding on the structural evolution and the chemical bonding of NbMoS_n^-/0(n=3~7) clusters.

Key words: transition metal sulfide cluster, density functional theory, structural evolution, simulation of photoelectron spectrum

引用此文

王彬, 王剑福, 张晓菲, 陈文杰, 章永凡, 黄昕. 二核铌钼硫簇NbMoS_n^-/0(n=3~7)掺杂体系的结构与成键性质的理论研究[J]. 化学学报, 2017, 75(3): 307-320.

Wang Bin, Wang Jianfu, Zhang Xiaofei, Chen Wenjie, Zhang Yongfan, Huang Xin. Theoretical Investigations on the Structures and the Chemical Bonding of NbMoS_n^-/0 (n=3~7) Clusters[J]. Acta Chim. Sinica, 2017, 75(3): 307-320.

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参考文献

[1] Shi, J. P.; Ma, D. L.; Zhang, Y. F.; Liu, Z. F. Acta Chim. Sinica 2015, 73, 877. (史建平, 马冬林, 张艳锋, 刘忠范, 化学学报, 2015, 73, 877.)
[2] Transition Metal Sulfur Chemistry:Biological and Industrial Significance, Eds.:Stiefel, E. I.; Matsumoto, K., American Chemical Society, Washington, 1996.
[3] Lee, S. C.; Li, J.; Mitchell, J. C.; Holm, R. H. Inorg. Chem. 1992, 31, 4333.
[4] Nasretdinova, V.; Zaitsev-Zotov, S. Physica B 2012, 407, 1874.
[5] Wang, Q.; Zhao, J.; Wang, X. F. J. Phys. Chem. A 2015, 119, 2244.
[6] Pettarin, V.; Churruca, M. J.; Felhos, D.; Karger-Kocsis, J.; Frontini, P. M. Wear 2010, 269, 31.
[7] Basharina, K. Y.; Terekhin, D. V.; Kuz'mina, G. N.; Bordubanova, A. E.; Ezhov, G. A.; Parenago, O. P. Petrol. Chem. 2009, 49, 339.
[8] Chhowalla, M.; Amaratunga, G. A. J. Nature (London) 2000, 407, 164.
[9] Ye, L. N.; Wu, C. Z.; Guo, W.; Xie, Y. Chem. Commun. 2006, 45, 4738.
[10] Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.; Mi, Q.; Santori, E. A.; Lewis, N. S. Chem. Rev. 2010, 110, 6446.
[11] Jaramillo, T. F.; Jørgensen, K. P.; Bonde, J.; Nielsen, J. H.; Horch, S.; Chorkendorff, I. Science 2007, 317, 100.
[12] Tian, Y.; He, Y.; Shang, J.; Zhu, Y. F. Acta Chim. Sinica 2004, 62, 1807. (田野, 何俣, 尚静, 朱永法, 化学学报, 2004, 62, 1807.)
[13] Xing, L.; Jiao, L. Y. Acta Phys.-Chim. Sin. 2016, 32, 2133. (邢垒, 焦丽颖, 物理化学学报, 2016, 32, 2133.)
[14] Raybaud, P.; Hafner, J.; Kresse, G.; Kasztelan, S.; Toulhoat, H. J. Catal. 2000, 189, 129.
[15] Toulhoat, H.; Raybaud, P.; Kasztelan, S.; Kresse, G.; Hafner, J. Catal. Today 1999, 50, 629.
[16] Jaramillo, T. F. Nature Chem. 2014, 6, 248.
[17] Jaramillo, T. F.; Jørgensen, K. P.; Bonde, J.; Nielsen, J. H.; Horch, S.; Chorkendorff, I. Science 2007, 317, 100.
[18] Guo, X.; Tong, X.; Wang, Y.; Chen, C.; Jin, G.; Guo, X. Y. J. Mater. Chem. A 2013, 1, 4657.
[19] Liao, L.; Zhu, J.; Bian, X.; Zhu, L.; Scanlon, M. D.; Girault, H. H.; Liu, B. Adv. Funct. Mater. 2013, 23, 5326.
[20] Kockerling, M.; Johrendt, D.; Finckh, E. W. J. Am. Chem. Soc. 1998, 120, 12297.
[21] Hernandez-Molina, R.; Gili, P.; Sokolov, M. N.; Safont, V. S. Inorg. Chim. Acta 2011, 376, 10.
[22] Liao, Y. H.; Park, K. S.; Singh, P.; Li, W.; Goodenough, J. B. J. Power Sources 2014, 245, 27.
[23] Divigalpitiya, W. M. R.; Frindt, R. F.; Morrison, S. R. J. Phys. D:Appl. Phys. 1990, 23, 966.
[24] Oviedo-Roa, R.; Martinez-Magadan, J. M.; Illas, F. J. Phys. Chem. B 2006, 110, 7951.
[25] Lewis, D. A.; Kenney, C. N. Trans. Inst. Chem. Eng. 1981, 59, 186.
[26] Aray, Y.; Zambrano, D.; Cornejo, M. H.; Ludeña, E. V.; Iza, P.; Vidal, A. B.; Coll, D. S.; Jimenez, D. M.; Henriquez, F.; Paredes, C. J. Phys. Chem. C 2014, 118, 27823.
[27] Allali, N.; Marie, A. M.; Danot, M.; Geantet, C.; Breysse, M. J. Catal. 1995, 156, 279.
[28] Geantet, C.; Afonso, J.; Breysse, M.; Danot, M. Catal. Today 1996, 28, 23.
[29] Allali, N.; Prouzet, E.; Michalowicz, A.; Gaborit, V.; Nadiri, A.; Danot, M. Appl. Catal. A-GEN. 1997, 159, 333.
[30] Cattenot, M.; Portefaix, J. L.; Afonso, J.; Breysse, M.; Lacroix, M.; Perot, G. J. Catal. 1998, 173, 366.
[31] Danot, M.; Afonso, J.; Portefaix, J. L.; Breysse, M.; Courieres, T. D. Catal. Today 1991, 10, 629.
[32] Afanasiev, P.; Bezverkhyy, I. Appl. Catal. A-GEN. 2007, 322, 129.
[33] Gaborit, V.; Allali, N.; Geantet, C.; Breysse, M.; Vrinat, M.; Danotl, M. Catal. Today 2000, 57, 267.
[34] Chai, Y. M.; An, G. J.; Liu, Y. Q.; Liu, C. G. Prog. Chem. 2007, 19, 234. (柴永明, 安高军, 柳云骐, 刘晨光, 化学进展, 2007, 19, 234.)
[35] Besenbacher, F.; Brorson, M.; Clausen, B. S.; Helveg, S.; Hinnemann, B.; Kibsgaard, J.; Lauritsen, J. V.; Moses, P. G.; Nørskovc, J. K.; Topsøe, H. Catal. Today 2008, 130, 86.
[36] Drescher, T.; Niefind, F.; Bensch, W.; Grünert, W. J. Am. Chem. Soc. 2012, 134, 18896.
[37] Prodhomme, P. Y.; Raybaud, P.; Toulhoat, H. J. Catal. 2011, 280, 178.
[38] Dinter, N.; Rusanen, M.; Raybaud, P.; Kasztelan, S.; Silva, P.; Toulhoat, H. J. Catal. 2010, 275, 117.
[39] Lauritsen, J. V.; Nyberg, M.; Nørskov, J. K.; Clausen, B. S.; Topsøe, H.; Lægsgaard, E.; Besenbacher, F. J. Catal. 2004, 224, 94.
[40] Wen, X. D.; Zeng, T.; Li, Y. W.; Wang, J.; Jiao, H. J. Phys. Chem. B 2005, 109, 18491.
[41] Lu, J. X. Chinese J. Struct. Chem. 1989, 5, 327. (卢嘉锡, 结构化学, 1989, 5, 327.)
[42] Huang, R. B.; Zhang, P.; Zhu, Y. B.; Zheng, L. S. Acta Phys-Chim. Sin. 1991, 8, 8. (黄荣彬, 张鹏, 朱永宝, 郑兰荪, 物理化学学报, 1991, 8, 8.)
[43] Popov, I.; Kunze, T.; Gemming, S.; Seifert, G. Eur. Phys. J. D. 2007, 45, 439.
[44] Popov, I.; Gemming, S.; Seifert, G. Phys. Rev. B 2007, 75, 245436.
[45] Seifert, G.; Tamuliene, J.; Gemming, S. Comput. Mater. Sci. 2006, 35, 316.
[46] Gemming, S.; Seifert, G. Appl. Phys. A 2006, 82, 175.
[47] Jiao, H. J.; Li, Y. W.; Delmon, B.; Halet, J. F. J. Am. Chem. Soc. 2001, 123, 7334.
[48] Bertram, N.; Kim, Y. D.; Ganteför, G.; Sun, Q.; Jena, P.; Tamliene, J.; Seifert, G. Chem. Phys. Lett. 2004, 396, 341.
[49] Liang, B.; Andrews, L. J. Phys. Chem. A 2002, 106, 3738.
[50] Liang, B.; Andrews, L. J. Phys. Chem. A 2002, 106, 6945.
[51] Yu, S. W.; Yin, L. Q.; Yao, L. F.; Li, M.; Xie, X. G. Chin. Chem. Lett. 2008, 19, 1008.
[52] Yin, S.; Xie, Y.; Bernstein, E. R. J. Phys. Chem. A 2011, 115, 10266.
[53] Saha, A.; Raghavachari, K. J. Chem. Phys. 2013, 139, 204301.
[54] Saha, A.; Raghavachari, K. J. Chem. Phys. 2014, 141, 074305.
[55] Afanasiev, P.; Fischer, L.; Beauchesne, F.; Danot, M.; Gaborit, V.; Breysse, M. Catal. Lett. 2000, 64, 59.
[56] Gaborit, V.; Allali, N.; Danot, M.; Geantet, C.; Cattenot, M.; Breysse, M.; Diehl, F. Catal. Today 2003, 78, 499.
[57] Aray, Y.; Zambrano, D.; Cornejo, M. H.; Ludeña, E. V.; Iza, P.; Vidal, A. B.; Coll, D. S.; Jimenez, D. M.; Henriquez, F.; Paredes, C. J. Phys. Chem. C 2014, 118, 27823.
[58] Ivanovskaya, V. V.; Heine, T.; Gemming, S.; Seifert, G. Phys. Status. Solidi. 2006, 243, 1757.
[59] Ivanovskaya, V. V.; Zobelli, A.; Gloter, A.; Brun, N.; Serin, V.; Colliex, C. Phys. Rev. B:Condens. Matter 2008, 78, 134104.
[60] Deepak, F. L.; Cohen, H.; Cohen, S.; Feldman, Y.; Popovitz-Biro, R.; Azulay, D.; Millo, O.; Tenne, R. J. Am. Chem. Soc. 2007, 129, 12549.
[61] Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A., Gaussian 03, Revision D. 01, Gaussian, Inc.:Wallingford, CT, 2004.
[62] Becke, A. D. J. Chem. Phys. 1993, 98, 1372.
[63] Lee, C.; Yang, W. T.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
[64] Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. Phys. Chem. 1994, 98, 11623.
[65] Schafer, A.; Huber, C.; Ahlrichs, R. J. Chem. Phys. 1994, 100, 5829.
[66] Weigend, F.; Ahlrichs, R. Phys. Chem. Chem. Phys. 2005, 7, 3297.
[67] Eichkorn, K.; Weigend, F.; Treutler, O.; Ahlrichs, R. Theor. Chem. Acc. 1997, 97, 119. The exponents (included those of the polarization functions) and contraction coefficients can be retrieved from the following web-site:https://bse.pnl.gov/bse/portal.
[68] Andrae, D.; Häußermann, U.; Dolg, M.; Stoll, H.; Preuß, H. Theor. Chim. Acta 1990, 77, 123.
[69] Kuchle, W.; Dolg, M.; Stoll, H.; Preuss, H. Pseudopotentials of the Stuttgart/Dresden Group 1998, revision August 11, 1998; .
[70] Dunning, T. H. Jr. J. Chem. Phys. 1989, 90, 1007.
[71] Martin, J. M. L.; Sundermann, A. J. Chem. Phys. 2001, 114, 3408.
[72] Woon, D. E.; Dunning, T. H. Jr. J. Chem. Phys. 1993, 98, 1358.
[73] Dunning, T. H. Jr.; Peterson, K. A.; Wilson, A. K. J. Chem. Phys. 2001, 114, 9244.
[74] Purvis, G. D.; Bartlett, R. J. J. Chem. Phys. 1982, 76, 1910.
[75] Scuseria, G. E.; Janssen, C. L.; Schaefer III, H. F. J. Chem. Phys. 1988, 89, 7382.
[76] Raghavachari, K.; Trucks, G. W.; Pople, J. A.; Head-Gordon, M. Chem. Phys. Lett. 1989, 157, 479.
[77] Watts, J. D.; Gauss, J.; Bartlett, R. J. J. Chem. Phys. 1993, 98, 8718.
[78] Bartlett, R. J.; Musial, M. Rev. Mod. Phys. 2007, 79, 291.
[79] Werner, H. J.; Knowles, P. J.; Knizia, G.; Manby, F. R.; Schütz, M.; Celani, P.; Györffy, W.; Kats, D.; Korona, T.; Lindh, R.; Mitrushenkov, A.; Rauhut, G.; Shamasundar, K. R.; Adler, T. B.; Amos, R. D.; Bernhardsson, A.; Berning, A.; Cooper, D. L.; Deegan, M. J. O.; Dobbyn, A. J.; Eckert, F.; Goll, E.; Hampel, C.; Hesselmann, A.; Hetzer, G.; Hrenar, T.; Jansen, G.; Köppl, C.; Liu, Y.; Lloyd, A. W.; Mata, R. A.; May, A. J.; McNicholas, S. J.; Meyer, W.; Mura, M. E.; Nicklaß, A.; O'Neill, D. P.; Palmieri, P.; Peng, D.; Pflüger, K.; Pitzer, R.; Reiher, M.; Shiozaki, T.; Stoll, H.; Stone, A. J.; Tarroni, R.; Thorsteinsson, T.; Wang, M., MOLPRO, Version 2010. 1, a package of ab initio programs, .
[80] Dennington, R. II; Keith, T.; Millam, J. GaussView, Version 4. 1. 2., Semichem Inc., Shawnee Mission, 2007.
[81] Tozer, D. J.; Handy, N. C. J. Chem. Phys. 1998, 109, 10180.
[82] Zhang, S.; Luo, C. G.; Li, H. Y.; Lu, C.; Li, G. Q.; Lu, Z. W. Mater. Chem. Phys. 2015, 160, 227.
[83] Zhang, S.; Zhang, Y.; Lu, Z.; Shen, X.; Li, G.; Peng, F.; Bu, X. J. Mater. Sci. 2016, 51, 9440.
[84] Merki, D.; Fierro, S.; Vrubel, H.; Hu, X. Chem. Sci. 2011, 2, 1262.
[85] Duchet, J. C.; Van-Oers, E. M.; De-Beer, V. H. J.; Prins, R. J. Catal. 1983, 80, 386.
[86] Afanasiev, P.; Jobic, H.; Lorentz, C.; Leverd, P.; Mastubayashi, N.; Piccolo, L.; Vrinat, M. J. Phys. Chem. C 2009, 113, 4139.
[87] Afanasiev, P. J. Catal. 2010, 269, 269.
[88] Allali, N.; Leblanc, A.; Danot, M.; Geantet, C.; Vrinat, M.; Breysse, M. Catal. Today 1996, 27, 137.
[89] Christe, K. O.; Dixon, D. A.; Mclemore, D.; Wilson, W. W.; Sheehy, J. A.; Boatz, J. A. J. Fluorine Chem. 1999, 101, 151.
[90] Li, S.; Dixon, D. A. J. Phys. Chem. A 2006, 110, 6231.