Citation: ZHANG Lian-Yang, SHI Wei, XIA Sheng-Jie, NI Zhe-Ming. Hydrodesulfurization Mechanisms of Thiophene Catalyzed by Au/Pd(111) Bimetallic Surfa[J]. Acta Physico-Chimica Sinica, ;2014, 30(10): 1847-1854. doi: 10.3866/PKU.WHXB201407141 shu

Hydrodesulfurization Mechanisms of Thiophene Catalyzed by Au/Pd(111) Bimetallic Surfa

1.
Laboratory of Advanced Catalytic Materials, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, P. R. China

Received Date: 3 June 2014
Available Online: 14 July 2014

The formation energy of different ensembles on Pd(111) surfaces containing N (N=1-4) Au atoms were investigated using a density functional theory model. The best model for exploring the adsorption of thiophene was selected, and the mechanism of competitive hydrodesulfurization on a Au/Pd(111) bimetallic surface was investigated. The results showed that Au/Pd(111) has the lowest formation energy, and adsorption at the hexa nal close-packed site is most stable when the thiophene plane is tilted at 30° to the Au/Pd(111) bimetallic surface with S atom. The reactions are exothermic, and desulfurization can be either direct or indirect. The direct desulfurization pathway has a low activation energy, but it is difficult to control the products. The indirect desulfurization pathway is the best fit for the cis-hydrogenation process; C―S cleavage has the highest reaction energy barrier, and is the rate-determining step. The activation energy barrier of the rate-determining step on Au/Pd(111) is lower than those on Au(111) and Pd(111). This indicates that bimetallic AuPd is more active than single Au and Pd in the hydrodesulfurization of thiophene.
- Density functional theory,
- Thiophene,
- Au/Pd(111) bimetallic surface,
- Adsorption,
- Hydrodesulfurization
1. [1]
  
  (1) Diaz, Y.; Sevilla, A.; Mónaco, A.; Méndez, F. J.; Rosales, P.; García, L.; Brito, J. L. Fuel 2013, 110, 235. doi: 10.1016/j.fuel.2013.01.044
2. [2]
  (2) Liao, H.; Xu, X. L.; Chen,W. Q.; Shi, Q. J.; Liu,W. M.;Wang, X. Acta Phys. -Chim. Sin. 2012, 28 (12), 2924. [廖辉, 徐香兰, 谌伟庆, 石秋杰, 刘文明, 王翔. 物理化学学报, 2012, 28 (12), 2924.] doi: 10.3866/PKU.WHXB201209281
3. [3]
  (3) Villasana, Y.; Ruscio-Vanalesti, F.; Pfaff, C.; Méndez, F. J.; Luis-Luis, M. Á.; Brito, J. L. Fuel 2013, 110, 259. doi: 10.1016/j.fuel.2012.11.055
4. [4]
  (4) Zhao, D. S.; Li, F. T.; Zhou, E. P.; Sun, Z. M. Chem. Res. Chin. Univ. 2008, 24, 96. doi: 10.1016/S1005-9040(08)60020-3
5. [5]
  (5) Ma, C. Y.; Li, X. H.; Jin, M. S.; Liao,W. P.; Guan, R. G.; Suo, Z. H. Chin. J. Catal. 2007, 28 (6), 535. [麻春艳, 李新华, 金明善, 廖卫平, 管仁贵, 索掌怀. 催化学报, 2007, 28 (6), 535.] (6) Parola, V. L.; Testa, M. L.; Venezia, A. M. Appl. Catal. B: Environ. 2012, 119 -120, 248. (7) Evangelisti, C.; Schiavi, E.; Aronica, L. A.; Caporusso, A. M.; Vitulli, G.; Bertinetti, L.; Martra, G.; Balerna, A.; Mobilio, S. J. Catal. 2012, 286, 224. doi: 10.1016/j.jcat.2011.11.007
6. [6]
  (8) Boscoboinik, J. A.; Plaisance, C.; Neurock, M.; Tysoe,W. T. Phys. Rev. B 2008, 77 (4), 045422. doi: 10.1103/ PhysRevB.77.045422
7. [7]
  (9) Gu, H. Z.; Xu, X. S.; Chen, A. A.; Ao, P.; Yan, X. H. Catal. Commun. 2013, 41, 65. doi: 10.1016/j.catcom.2013.07.015
8. [8]
  (10) Pongthawornsakun, B.; Fujita, S.; Arai, M.; Mekasuwandumrong, O.; Panpranot, J. Appl. Catal. A-Gen. 2013, 467 (2), 132. (11) Suo, Z. H.; Ma, C. Y.; Liao,W. P.; Jin, M. S.; Lv, H. Y. Fuel Pro. Tech. 2011, 92, 1549. doi: 10.1016/j.fuproc.2011.03.018
9. [9]
  (12) Zhang, J.; Jin, H. M.; Sullivan, M. B.; Chiang, F.; Lim, H.;Wu, P. Phys. Chem. Chem. Phys. 2009, 11 (9), 1441. doi: 10.1039/b814647k
10. [10]
  (13) Chen, Z. H.; Ding, K. N.; Xu, X. L.; Li, J. Q. Chin. J. Struct. Chem. 2010, 29 (1), 93. (14) Zhu, H. Y.; Lu, X. Q.; Guo,W. Y.; Li, L. F.; Zhao, L. M.; Shan, H. H. J. Mol. Catal. A-Chem. 2012, 363-364, 18. (15) Ni, Z. M.; Shi,W.; Xia, M. Y.; Xue, J. L. Chem. J. Chin. Univ. 2013, 34 (10), 2353. [倪哲明, 施炜, 夏明玉, 薛继龙. 高等学校化学学报, 2013, 34 (10), 2353.] (16) Peyghan, A. A.; Baei, M. T.; Torabi, P.; Hashemian, S. Phosphorus Sulfur Silicon Relat. Elem. 2013, 188, 1172. doi: 10.1080/10426507.2012.737879
11. [11]
  (17) Zheng, X. Z.; Zhang, Y. H.; Huang, S. P.; Liu, H.;Wang, P.; Tian, H. P. Comput. Theor. Chem. 2012, 979, 64. doi: 10.1016/j.comptc.2011.10.016
12. [12]
  (18) 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, 1498. doi: 10.1021/cs2002548
13. [13]
  (19) Moses, P. G.; Hinnemann, B.; Topsoe, H.; Norskov, J. K. J. Catal. 2009, 268 (2), 201. doi: 10.1016/j.jcat.2009.09.016
14. [14]
  (20) Delley, B. J. Chem. Phys. 2000, 113 (18), 7756. doi: 10.1063/1.1316015
15. [15]
  (21) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77 (18), 3865. doi: 10.1103/PhysRevLett.77.3865
16. [16]
  (22) Ge, Q.; Jenkins, S. J.; King, D. A. Chem. Phys. Lett. 2000, 327(3/4), 125. (23) Delley, B. J. Phys. Chem. 1996, 100 (15), 6107. doi: 10.1021/jp952713n
17. [17]
  (24) Chen, Z. H.; Ding, K. N.; Xu, X. L.; Li, J. Q. Chin. J. Struct. Chem. 2010, 29 (3), 365. (25) Besenbacher, F.; Brorson, M.; Clausen, B. S.; Helveg, S.; Hinnemann, B.; Kibsgaard, J.; Lauritsen, J. V.; Moses, P. G.; Norskov J. K.; Topsøe, H. Catal. Today 2008, 130 (1), 86. doi: 10.1016/j.cattod.2007.08.009
18. [18]
  (26) Moses, P. G.; Hinnemann, B.; Topsøe, H.; Nørskov, J. K. J. Catal. 2007, 248 (2), 188. doi: 10.1016/j.jcat.2007.02.028
19. [19]
  (27) Yao, X. Q.; Li, Y.W.; Jiao, H. J. J. Mol. Struct. –Theochem 2005, 726 (1-3), 81. doi: 10.1016/j.theochem.2005.02.074
20. [20]
  (28) Huang, Y. L.; Liu, Z. P. Acta Phys. -Chim. Sin. 2008, 24 (9), 1662. [黄永丽, 刘志平. 物理化学学报, 2008, 24 (9), 1662.] doi: 10.3866/PKU.WHXB20080923
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