Theoretical Studies on Reaction Mechanism of Hydrodesulfurization of Thiophene Catalyzed by Au(111) Plane

doi:10.7503/cjcu20130385

Abstract

Abstract:

The adsorption of thiophene molecule at Au(111) and its mechanism of hydrodesulfurization were elucidated by desity functional theory(DFT) method. All the pertinent species of different mechanisms have been gathered to obtain their preferred adsorption sites. The activation energy and reaction energy of each steps in different mechanisms also have been calculated. The results show that the adsorption at the Top site is most stable when the thiophene plane tilt to the Au(111) surface with S atom. The direct hydrodesulfurization mechanism has a low energy of activation and high temperature is helpful for the hydrodesulfurization reaction, but it is difficult to control the products. The mechanism of indirect hydrodesulfurization is best fit for the hydroisomerization process. The reaction heat of hydrodesulfurization is negative, so reducing the temperature is helpful for the reaction. During the process, the bond length of C—S in thiophene increases gradually when the bond energy of C—S decreases. All of these changes are helpful to the cleavage of C—S. The most feasible reaction pathway is (1) C₄H₄S+H₂α,α-C₄H₆S, (2) α,α-C₄H₆S+H₂C₄H₈S, (3) C₄H₈S+H₂C₄H₁₀+S. Among different steps, the removal of S is the rate-determining step.

Key words: Density functional theory, Au(111) plane, Hydrodesulfurization of thiophene, Reaction mechanism

CLC Number:

O643

TrendMD:

NI Zhe-Ming, SHI Wei, XIA Ming-Yu, XUE Ji-Long. Theoretical Studies on Reaction Mechanism of Hydrodesulfurization of Thiophene Catalyzed by Au(111) Plane[J]. Chem. J. Chinese Universities, 2013, 34(10): 2353.

References

[1] Qi H. R. M., Zhao X. G., Zhang W. H., Yuan H., Xu G. T., Chem. J. Chinese Universities, 2012, 33(2), 383—388(齐和日玛, 赵晓光, 张韫宏, 袁蕙, 徐广通. 高等学校化学学报, 2012, 33(2), 383—388)

[2] Jin G. Z., Fan X. J., Sun G. D., Gao J. B., Zhu J. H., Chem. J. Chinese Universities, 2007, 28(6), 1169—1174(靳广洲, 樊秀菊, 孙桂大, 高俊斌, 朱建华. 高等学校化学学报, 2007, 28(6), 1169—1174)

[3] Liu H., Gao J. S., Zhao L., Petrkchem. Techno., 2010, 39(9), 1059—1065(刘卉, 高金森, 赵亮. 石油化工, 2010, 39(9), 1059—1065)

[4] Pan M., Flaherty D. W., Mullins C. B., J. Phys. Chem. Lett., 2011, 2(12), 1363—1367

[5] Gluhoi A. C., Bakker J. W., Nieuwenhuys B. E., Catal. Today, 2010, 154, 13—20

[6] Bond G. C., Thompson D. T., Cat. Rev. Sci. Eng., 1999, 41(3/4), 319—388

[7] Besenbacher F., Chorkendorff I., Clausen B. S., Hammer B., Molenbroek A. M., Norskov J. K., Stensgaard I., Science, 1998, 279(5358), 1913—1915

[8] Heermann D. W., Computer Simulation Methods in Theoretical Physics, Springer-Verlag Press, Heidelberg, 1990, 387—439

[9] Leach A. R., Molecular Modelling:Principles and Applications, Addison Wesley Longman Limitted Press, Essex, 2001, 26—454

[10] Meng Q. S., Shen Y. L., Xu J., Ma X. B., Gong J. L., Surf. Sci., 2012, 606(21/22), 1608—1617

[11] Zhu H. Y., Lu X. Q., Guo W. Y., Li L. F., Zhao L. M., Shan H. H., J. Mol. Catal. A, Chem., 2012, 363, 18—25

[12] Zhu H. Y., Guo W. Y., Li M., Zhao L. M., Li S. R., Li Y., Lu X. Q., Shan H. H., ACS Catal., 2011, 1(11), 1498—1510

[13] Zhou J., Yang Y. X., Liu P., Camillone N., White M. G., J. Phys. Chem. C, 2010, 114(32), 13670—13677

[14] Delley B., J. Chem. Phys., 2000, 113(18), 7756—7764

[15] Perdew J. P., Burke K., Ernzerhof M., Phys. Rev. Lett., 1996, 77(18), 3865—3868

[16] Ge Q., Jenkins S. J., King D. A., Chem. Phys. Lett., 2000, 327(3/4), 125—130

[17] Delley B., J. Chem. Phys., 2000, 113(18), 7756—7764

[18] Kittel C., Solid State Physics, John Wiley & Sons, New York, 1976, 56—57

[19] Delley B., J. Chem. Phys., 1990, 92(1), 508—517

[20] Delley B., J. Phys. Chem., 1996, 100(15), 6107—6110

[21] Chen Z. H., Ding K. N., Xu X. L., Li J. Q., Chinese J. Struct. Chem., 2010, 29(3), 365—376

[22] Wang H. M., Iglesia E., Chemcatchem., 2011, 3(7), 1166—1175

[23] Shafi R., Hutchings G. J., Catal. Today, 2000, 59(3/4), 423—442

[24] Besenbacher F., Brorson M., Clausen B. S., Helveg S., Hinnemann B., Kibsgaard J., Lauritsen J. V., Moses P. G., Norskov J. K., Topse H., Catal. Today, 2008, 130(1), 86—96

[25] Dong L. Z., Duckett S. B., Ohman K. F., Jones W. D., J. Am. Chem. Soc., 1992, 114(1), 151—160

[26] Benjamin C. W., Cynthia M. F., Chem. Rev., 1992, 92(4), 491—504

[27] Huang Y. L., Liu Z. P., Acta Phys. Chim. Sin., 2008, 24(9), 1662—1668(黄永丽, 刘志平. 物理化学学报, 2008, 24(9), 1662—1668)

[28] Yang M. L., Zhu Y. A., Fan C., Sui Z. J., Chen D., Zhou X. G., J. Mol. Catal. A, Chem., 2010, 321(1/2), 42—49