Citation: XU Kun, FENG Jie, CHU Qi, ZHANG Li-Li, LI Wen-Ying. Density Functional Theory Study of Thiophene Hydrodesulfurization on γ-Mo₂N(100) Surface[J]. Acta Physico-Chimica Sinica, ;2014, 30(11): 2063-2070. doi: 10.3866/PKU.WHXB201409221 shu

Density Functional Theory Study of Thiophene Hydrodesulfurization on γ-Mo₂N(100) Surface

1.
Training Base of State Key Laboratory of Coal Science and Technology Jointly Constructed by Shanxi Province and Ministry of Science and Technology, Taiyuan University of Technology, Taiyuan 030024, P. R. China

Received Date: 20 June 2014
Available Online: 22 September 2014
Fund Project: 国家高技术研究发展计划项目(863) (2011AA05A204)资助 (863) (2011AA05A204)

The hydrodesulfurization (HDS) of thiophene on an γ-Mo₂N(100) surface was investigated by density functional theory (DFT) and different configurations of thiophene on γ-Mo₂N(100) surface were considered. After geometric optimization, it was confirmed that the η5-Mo₂N configuration was the most stable adsorption model with an adsorption energy of -0.56 eV, where thiophene absorbed on 4-fold hcp vacant sites parallel to the surface with the S atom bonded to a Mo2 atom. The stable coadsorption of H atoms and thiophene on hcp sites showed that the hcp site is the active site for thiophene HDS on γ-Mo₂N(100). A direct desulfurization reaction pathway in HDS of thiophene dominated the process on the γ-Mo₂N(100) surface, which could be divided into the removal of the S atom and the hydrogenation saturation of C₄ species. To identify the intermediate products and the most probable reaction mechanism of thiophene HDS, a transition state search was carried out. The results indicated that the reaction of the first H atom required an activation energy of 1.69 eV, which was the rate-determining step in the HDS of thiophene. The thiol group (―SH) and butadiene were preferentially formed after hydrogenation of thiophene, and ―SH detached from mercaptan was the intermediate of H₂S. 2-Butene and butane were the products of the hydrogenation saturation of butadiene. H₂S, 2-butene, and butane were easily desorbed from γ-Mo₂N(100) to give the products because of weak adsorption.
- Thiophene,
- Molybdenum nitride,
- Hydrodesulfurization,
- Reaction mechanism,
- Density functional theory
1. [1]
  
  (1) Chu, Q.; Feng, J.; Li,W. Y.; Xie, K. C. Chin. J. Catal. 2013, 34 (1), 159. [褚绮, 冯杰, 李文英, 谢克昌. 催化学报, 2013, 34 (1), 159.] doi: 10.1016/S1872-2067(11)60509-3
2. [2]
  (2) Fuks, D.; Vingurt, D.; Landau, M. V.; Herskowitz, M. J. Phys. Chem. C 2010, 114 (31), 13313. doi: 10.1021/jp1031306
3. [3]
  (3) Zhu, Q. L.; Zhao, X. T.; Zhao, Z. X.; Ma, H. J.; Deng, Y. Q. J. Mol. Catal. (China) 2006, 20 (4), 372. [朱全力, 赵旭涛, 赵振兴, 马洪江, 邓友全. 分子催化, 2006, 20 (4), 372.]
4. [4]
  (4) Wu,W. C.;Wu, Z. L.; Feng, Z. C.; Ying, P. L.; Li, C. Phys. Chem. Chem. Phys. 2004, 6, 5596. doi: 10.1039/b414360b
5. [5]
  (5) Hensen, E. J. M.; Vissenberg, M. J.; De Beer, V. H. J.; Van Veen, J. A. R.; Van Santen, R. A. J. Catal. 1996, 163, 429. doi: 10.1006/jcat.1996.0344
6. [6]
  (6) Janak, K. E.; Tanski, J. M.; Churchill, D. G.; Parkin, G. J. Am. Chem. Soc. 2002, 124 (16), 4128.
7. [7]
  (7) Guo, J. H.;Watanabe, S.; Janik, M. J.; Ma, X. L.; Song, C. S. Catal. Today 2010, 149 (1), 218.
8. [8]
  (8) Wang, H. M.; Iglesia, E. J. Catal. 2010, 273, 245. doi: 10.1016/j.jcat.2010.05.019
9. [9]
  (9) Moses, P. G.; Hinnemann, B.; Topsøe, H.; Nørskov, J. K. J. Catal. 2007, 248, 188. doi: 10.1016/j.jcat.2007.02.028
10. [10]
  (10) Ni, Z. M.; Shi,W.; Xia, M. Y.; Xue, J. L. Chem. J. Chin. Univ. 2013, 34 (10), 1353. [倪哲明, 施炜, 夏明玉, 薛继龙. 高等学校化学学报, 2013, 34 (10), 1353.]
11. [11]
  (11) Zhou, 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
12. [12]
  (12) Joshi, Y. V.; Ghosh, P.; Venkataraman, P. S.; Delgass,W. N.; Thomson, K. T. J. Phys. Chem. C 2009, 113 (22), 9698. doi: 10.1021/jp809981c
13. [13]
  (13) Cristol, S.; Paul, J. F.; Schovsbo, C.; Veilly, E.; Payen, E. J. Catal. 2006, 239, 145. doi: 10.1016/j.jcat.2006.01.015
14. [14]
  (14) Tominaga, H.; Nagai, M. Appl. Catal. A 2008, 343, 95.
15. [15]
  (15) Puello-Polo, E.; Ayala-G, M.; Brito, J. M. Catal. Commun. 2014, 53, 9. doi: 10.1016/j.catcom.2014.04.018
16. [16]
  (16) Ruinart de Brimont, M.; Dupont, C.; Daudin, A.; Geantet, C.; Raybaud, P. J. Catal. 2012, 286, 153. doi: 10.1016/j.jcat.2011.10.022
17. [17]
  (17) Gutiérrez, O. Y.; Singh, S.; Schachtl, E.; Kondratieva, E.; Hein, J.; Lercher, J. A. ACS Catal. 2014, 4, 1487. doi: 10.1021/cs500034d
18. [18]
  (18) Sun, M. Y.; Nelson, A. E.; Adjaye, J. J. Catal. 2005, 233, 411. doi: 10.1016/j.jcat.2005.05.009
19. [19]
  (19) Merki, D.; Vrubel, H.; Rovelli, L.; Fierro, S.; Hu, X. Chem. Sci. 2012, 3 (8), 2515. doi: 10.1039/c2sc20539d
20. [20]
  (20) Álvarez-Ramírez, F.; Valencia, D.; Klimova, T.; Escobar, J.; García-Cruz, I. Fuel 2013, 110, 212. doi: 10.1016/j.fuel.2012.10.083
21. [21]
  (21) Markel, E. J.; van Zee, J.W. J. Catal. 1990, 126, 643. doi: 10.1016/0021-9517(90)90027-H
22. [22]
  (22) ng, S.W.; Chen, H. K.; Li,W.; Li, B. Q. Fuel Chem. Div. Prep. 2003, 48 (1), 191.
23. [23]
  (23) Nagai, M. Appl. Catal. A 2007, 322, 178. doi: 10.1016/j.apcata.2007.01.006
24. [24]
  (24) Wu, Z. L.; Li, C.;Wei, Z. B.; Ying, P. L.; Xin, Q. J. Phys. Chem. B 2002, 106 (5), 979. doi: 10.1021/jp011577l
25. [25]
  (25) Ren, J.; Huo, C. F.;Wen, X. D.; Cao, Z.;Wang, J. G.; Li, Y.W.; Jiao, H. J. J. Phys. Chem. B 2006, 100 (45), 22563.
26. [26]
  (26) Aegerter, P. A.; Quigley,W.W.; Simpson, G. J.; Ziegler, D. D.; Logan, J.W.; McCrea, K. R.; Glazier, S.; Bussell, M. E. J. Catal. 1996, 164, 109. doi: 10.1006/jcat.1996.0367
27. [27]
  (27) McCrea, K. R.; Logan, J.W.; Tarbuck, T. L.; Heiser, J. L.; Bussell, M. E. J. Catal. 1997, 171, 255. doi: 10.1006/jcat.1997.1805
28. [28]
  (28) Nagai, M.; Miyao, T.; Tuboi, T. Catal. Lett. 1993, 18 (1), 9.
29. [29]
  (29) Kadono, T.; Kubota, T.; Okamoto, Y. Catal. Today 2003, 87 (1-4), 107. doi: 10.1016/j.cattod.2003.09.009
30. [30]
  (30) Frapper, G.; Pélissier, M. Hafner, J. J. Phys. Chem. B 2000, 104 (50), 11972. doi: 10.1021/jp0026179
31. [31]
  (31) Volpe, L.; Boudart, M. J. Solid State Chem. 1985, 59 (3), 332. doi: 10.1016/0022-4596(85)90301-9
32. [32]
  (32) Dewangan, K.; Patil, S. S.; Joag, D. S.; More, M. A.; Gajbhiye, N. J. Phys. Chem. C 2010, 114 (35), 14710. doi: 10.1021/jp103008f
33. [33]
  (33) Zhao, E.;Wang, J. P.;Wu, Z. J. Phys. Status Solidi B 2010, 247 (5), 1207.
34. [34]
  (34) Zheng,W. Q.; Cotter, T. P.; Kaghazchi, P. Jacob, T.; Frank, B.; Schlichte, K.; Zhang,W.; Su, D. S.; Schuth, F.; Schlögl, R. J. Am. Chem. Soc. 2013, 135 (9), 3458. doi: 10.1021/ja309734u
35. [35]
  (35) Li, G. X.; Chen, X.W.; Bai, J. D.; Lan, Z. Q.; Guo, J. Acta Phys. -Chim. Sin. 2010, 26 (5), 1448. [黎光旭, 陈晓伟, 白加栋, 蓝志强, 郭进. 物理化学学报, 2010, 26 (5), 1448.] doi: 10.3866/PKU.WHXB20100540
36. [36]
  (36) Orita, H.; Uchida, K.; Itoh, N. J. Mol. Catal. A: Chem. 2003, 193 (1), 197.
37. [37]
  (37) Machon, D.; Daisenberger, D.; Soignard, E.; Shen, G.; Kawashima, T.; Takayama Muromachi, E.; McMillan, P. Phys. Status Solidi A 2006, 203 (5), 831. doi: 10.1002/pssa.v203:5
38. [38]
  (38) Gajbhiye, N.; Ningthoujam, R. Phys. Status Solidi C 2004, 1 (12), 3449.
39. [39]
  (39) 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
40. [40]
  (40) Logadóttir, Á.; Moses, P. G.; Hinnemann, B.; Topsøe, N. Y.; Knudsen, K. G.; Topsøe, H.; Nørskov, J. K. Catal. Today 2006, 111 (1), 44.
41. [41]
  (41) Sullivan, D. L.; Ekerdt, J. G. J. Catal. 1998, 178, 226. doi: 10.1006/jcat.1998.2162
42. [42]
  (42) Wu, Z. L.; Li, C.; Ying, P. L.;Wei, Z. B.; Xin, Q. J. Phys. Chem. B 2001, 105 (38), 9183. doi: 10.1021/jp003864f
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沈阳化工大学材料科学与工程学院沈阳 110142

Density Functional Theory Study of Thiophene Hydrodesulfurization on γ-Mo2N(100) Surface

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通讯作者: 陈斌, bchen63@163.com

Density Functional Theory Study of Thiophene Hydrodesulfurization on γ-Mo₂N(100) Surface