Citation: XIAO Xue-Chun, SHI Wei, NI Zhe-Ming. Selective Hydrogenation Mechanism of Cinnamaldehyde on Au(111) Surface[J]. Acta Physico-Chimica Sinica, ;2014, 30(8): 1456-1464. doi: 10.3866/PKU.WHXB201406091 shu

Selective Hydrogenation Mechanism of Cinnamaldehyde on Au(111) Surface

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

Received Date: 24 March 2014
Available Online: 9 June 2014

The adsorption behavior and selective hydrogenation reaction mechanisms (C=O addition, C=C addition, and 1,4-conjugate addition) of cinnamaldehyde on an Au(111) surface were investigated by density functional theory combined with a periodic slab model. The adsorption energies of various adsorption models were obtained to determine the preferred adsorption configuration. The calculated results indicate that the most stable adsorption configuration involved the C=O and C=C double bond adsorbed on the Au(111) surface, with an average adsorption energy of 140.0 kJ·mol^-1. The transition states of each elementary reaction for all possible reaction mechanisms were also located. Comparison of the activation energy barriers revealed hydrocinnamaldehyde (HCAL) to be the most likely selective hydrogenation product of cinnamaldehyde on an Au(111) surface. In addition, the 1,4- conjugate addition mechanism, which generates 3-phenyl-1-propen-1-ol (ENOL) that readily tautomerizes to HCAL, required less activation energy than did the C=C direct addition mechanism. The dominant reaction pathway involved an O atom of cinnamaldehyde preferentially hydrogenating to generate a more stable allyl intermediate. Another H atom then added to a C atom directly connected to the phenyl ring of the allyl intermediate to yield ENOL. Finally, ENOL tautomerized to HCAL. Throughout the process, the generation of ENOL is the rate-determining step, for which the highest activation energy barrier was required.
- Au(111) surface,
- Cinnamaldehyde,
- Density functional theory,
- Hydrocinnamaldehyde,
- Selective hydrogenation mechanism
1. [1]
  
  (1) Li, G. Fine Chemical Intermediates Used Manual; Chemical Industry Press: Beijing, 2009; pp 565-566. [黎钢. 精细化工常用中间体手册. 北京: 化学工业出版社, 2009: 565-566.]
2. [2]
  (2) Castellans, A. M. C. F.; Hogeweg, J. M.; Van Nispen, S. P. J. M. Process for the Preparation of 3-Phenylpropanal. PCT Int. Appl. 5811588, 1998.
3. [3]
  (3) Galletti, A. M. R.; Toniolo, L.; Antonetti, C.; Evangelisti, C.; Forte, C. Appl. Catal. A-Gen. 2012, 447, 49.
4. [4]
  (4) Bertolini, G. R.; Cabello, C. I.; Munoz, M.; Casella, M.; Gazzoli, D.; Pettiti, I.; Ferraris, G. J. Mol. Catal. A-Chem. 2013, 366, 109. doi: 10.1016/j.molcata.2012.09.013
5. [5]
  (5) Nguyen, T. T.; Serp, P. ChemCatChem 2013, 5, 3595. doi: 10.1002/cctc.201300527
6. [6]
  (6) Piqueras, C. M.; Gutierrez, V.; Vega, D. A.; Volpe, M. A. Appl. Catal. A-Gen. 2013, 467, 253. doi: 10.1016/j.apcata.2013.07.028
7. [7]
  (7) Zhang, X.; Guo, Y. C.; Zhang, Z. C.; Gao, J. S.; Xu, C. M. J. Catal. 2012, 292, 213. doi: 10.1016/j.jcat.2012.05.017
8. [8]
  (8) 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
9. [9]
  (9) Manyar, H. G.; Yang, B.; Daly, H.; Moor, H.; McMonagle, S.; Tao, Y.; Yadav, G. D.; guet, A.; Hu, P.; Hardacre, C. ChemCatChem 2013, 5, 506. doi: 10.1002/cctc.201200447
10. [10]
  (10) Ide, M. S.; Hao, B.; Neurock, M.; Davis, R. J. ACS Catal. 2012, 2, 671. doi: 10.1021/cs200567z
11. [11]
  (11) Delbecq, F.; Sautet, P. J. Catal. 1995, 152, 217. doi: 10.1006/jcat.1995.1077
12. [12]
  (12) Delbecq, F.; Sautet, P. J. Catal. 2002, 211, 398. doi: 10.1016/S0021-9517(02)93744-9
13. [13]
  (13) Liu, B.W.; Gao, M.; Dang, L.; Zhao, H. T.; Marder, T. B.; Lin, Z. Y. Organometallics 2012, 31, 3410. doi: 10.1021/om3002153
14. [14]
  (14) Tang, F.W.; Guo,W. M.; Tang, N. N.; Pei, J. Y.; Xu, X. Acta Phys. -Chim. Sin. 2013, 29, 2198. [唐法威, 郭为民, 唐楠楠,裴俊彦, 许旋. 物理化学学报, 2013, 29, 2198.] doi: 10.3866/PKU.WHXB201307294
15. [15]
  (15) Ni, Z. M.; Xia, M. Y.; Shi,W.; Qian, P. P. Acta Phys. -Chim. Sin. 2013, 29, 1916. [倪哲明, 夏明玉, 施炜, 钱萍萍. 物理化学学报, 2013, 29, 1916.] doi: 10.3866/PKU.WHXB201307101
16. [16]
  (16) Delley, B. J. Chem. Phys. 2000, 113 (18), 7756. doi: 10.1063/1.1316015
17. [17]
  (17) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. B 1992, 46, 6671. doi: 10.1103/PhysRevB.46.6671
18. [18]
  (18) Ge, Q.; Jenkins, S. J.; King, D. A. Chem. Phys. Lett. 2000, 327 (3-4), 125. doi: 10.1016/S0009-2614(00)00850-2
19. [19]
  (19) Kittel, C. Introduction to Solid State Physics; Chemical Industry Press: Beijing, 2005; p 35; translated by Xiang, J. Z.,Wu, X. H. [Kittel, C. 固体物理导论. 项金钟, 吴兴惠, 译. 北京: 化学工业出版社, 2005: 35.]
20. [20]
  (20) Liu, X. M.; Ni, Z. M.; Yao, P.; Xu, Q.; Mao, J. H.;Wang, Q. Q. Acta Phys. -Chim. Sin. 2010, 26, 1599. [刘晓明, 倪哲明,姚萍, 胥倩, 毛江洪, 王巧巧. 物理化学学报, 2010, 26, 1599.] doi: 10.3866/PKU.WHXB20100625
21. [21]
  (21) Delley, B. J. Chem. Phys. 1990, 92 (1), 508. doi: 10.1063/1.458452
22. [22]
  (22) Wang, J. J.; Lefebvre, I. J. Phys. Chem. C 2013, 117, 9887. doi: 10.1021/jp4013976
23. [23]
  (23) Solis-Calero, C.; Ortega-Castro, J.; Hernandez-Laguna, A.; Munoz, F. J. Phys. Chem. C 2013, 117, 8299. doi: 10.1021/jp401488j
24. [24]
  (24) Luo, Q. Q.;Wang, T.; Beller, M.; Jiao, H. J. J. Phys. Chem. C 2013, 117, 12715. doi: 10.1021/jp403972b
25. [25]
  (25) Loffreda, D.; Delbecq, F.; Vigne, F.; Sautet, P. J. Am. Chem. Soc. 2006, 128, 1316. doi: 10.1021/ja056689v
26. [26]
  (26) Capon, B.; Guo, B. Z.; Kwok, F. C.; Siddhanta, A. K.; Zucco, C. Accounts Chem. Res. 1988, 21, 135. doi: 10.1021/ar00148a001
27. [27]
  (27) Cao, X. M.; Burch, R.; Hardacre, C.; Hu, P. J. Phys. Chem. C 2011, 115, 19819. doi: 10.1021/jp206520w
28. [28]
  (28) Ala na, G.; Ghio, C.; Nagy, P. I. Phys. Chem. Chem. Phys. 2010, 12, 10173. doi: 10.1039/c003999c
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