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
1. [1]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
2. [2]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
3. [3]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
4. [4]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
5. [5]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
6. [6]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
7. [7]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
8. [8]
  Baitong Wei , Jinxin Guo , Xigong Liu , Rongxiu Zhu , Lei Liu . Theoretical Study on the Structure, Stability of Hydrocarbon Free Radicals and Selectivity of Alkane Chlorination Reaction. University Chemistry, 2025, 40(3): 402-407. doi: 10.12461/PKU.DXHX202406003
9. [9]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
10. [10]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
11. [11]
  Yunhao Zhang , Yinuo Wang , Siran Wang , Dazhen Xu . Progress in Selective Construction of Functional Aromatics from Nitrogenous Cycloalkanes. University Chemistry, 2024, 39(11): 136-145. doi: 10.3866/PKU.DXHX202401083
12. [12]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
13. [13]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, 2024, 39(11): 158-173. doi: 10.12461/PKU.DXHX202403106
14. [14]
  Jiakun BAI , Ting XU , Lu ZHANG , Jiang PENG , Yuqiang LI , Junhui JIA . A red-emitting fluorescent probe with a large Stokes shift for selective detection of hypochlorous acid. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1095-1104. doi: 10.11862/CJIC.20240002
15. [15]
  .
  CCS Chemistry | 超分子活化底物为自由基促进高效选择性光催化氧化
  . CCS Chemistry, 2025, 7(10.31635/ccschem.025.202405229): -.
16. [16]
  Jun LUO , Baoshu LIU , Yunchang ZHANG , Bingkai WANG , Beibei GUO , Lan SHE , Tianheng CHEN . Europium(Ⅲ) metal-organic framework as a fluorescent probe for selectively and sensitively sensing Pb²⁺ in aqueous solution. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2438-2444. doi: 10.11862/CJIC.20240240
17. [17]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
18. [18]
  Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V₂O₅/TiO₂ catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210
19. [19]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
20. [20]
  Yinuo Wang , Siran Wang , Yilong Zhao , Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063

Get Citation

PDF

XML

Metrics

PDF Downloads(538)
Abstract views(631)
HTML views(8)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142