Citation: LI Jun-Nan, PU Min, HE Shu-Heng, HE Jing, EVANS David G.. Reaction Mechanism of Acetylene Hydrogenation Catalyzed by Pd₈ Cluster[J]. Acta Physico-Chimica Sinica, ;2011, 27(04): 793-800. doi: 10.3866/PKU.WHXB20110332 shu

Reaction Mechanism of Acetylene Hydrogenation Catalyzed by Pd₈ Cluster

1.
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, P. R. China

Received Date: 19 October 2010
Available Online: 17 February 2011
Fund Project: 国家自然科学基金(20531010, 20773009) (20531010, 20773009)国家重点基础研究发展计划(973) (2009CB939802)资助项目 (973) (2009CB939802)

The mechanism of acetylene hydrogenation catalyzed by Pd₈ cluster was investigated by density functional theory (DFT) method at B3PW91/GEN level. The calculation results showed that H₂ dissociated into H atoms wherever it adsorbed and the H atoms then adsorbed onto the surface of the Pd₈ cluster. The dissociation of H₂ is necessary for the hydrogenation of acetylene to ethane catalyzed by the Pd₈ cluster. The mechanism of acetylene hydrogenation is dependent on two isomers: acetylene and vinylidene on the Pd₈ cluster (Pd₈(2H)－CH＝CH and Pd₈(2H)－C＝CH₂). The two pathways follow a multistep and successive process to complete the hydrogenation of acetylene. However, a difference exists between Pd₈(2H)－CH＝CH and Pd₈(2H)－C＝CH₂. For the Pd₈(2H)－CH＝CH pathway, dissociated H atoms add to the C atom of acetylene on the Pd₈ cluster in different steps until they produce ethane. The Pd₈(2H)－CH＝CH₂ pathway is complex and proceeds by two different transition states to create ethylidyne, and then H atoms add to the C atom until hydrogenation ceases. Many valuable C₂ organic intermediate compounds are produced during the process and some of them transform by proton translocation, which connects the Pd₈(2H)－CH＝CH and Pd₈(2H)－C＝CH₂ pathways.
- Density functional theory,
- Pd₈ cluster,
- Acetylene hydrogenation,
- Ethylene,
- Reaction mechanism
1. [1]
  
  (1) Azizi, Y.; Petit, C.; Pitchon, V. J. Catal. 2008, 256, 338.
2. [2]
  (2) Bosa, A.N.R.; Hofa, E. W.; Westerterp, K. R. Chem. Eng. Sci.1993, 48, 1959.
3. [3]
  (3) Sevin, A.; Yu, H. T.; Evleth, E. M., J. Mol. Struc.-Theochem. 1983, 104, 163.
4. [4]
  (4) Pallassana, V.; Neurock, M.; Lusvardi, V. S.; Lerou, J. J.;Kragten, D. D.; Santen, A. J. Phys. Chem. B 2002, 106, 1656.
5. [5]
  (5) Gi la, C. E.; Aduriz, H. R.; Bodnariuk, P. Appl. Catal. 1986, 27, 133.
6. [6]
  (6) Lei, M.Yi.; Xiao, Y. J.; Liu, W. M.; Fukamizu, K.; Chiba, S.; Ando, K.; Narasaka, K. Tetrahedron 2009, 65, 6888.
7. [7]
  (7) Semagina, N.; Lioubov, K. M. Catal. Lett. 2009, 127, 334.
8. [8]
  (8) Boris, V. L. Thermochim. Acta 2002, 386, 1.
9. [9]
  (9) Sigwalt, P.; Moreau, M. Prog. Polym. Sci. 2006, 31, 44.
10. [10]
  (10) Chen, J. Y.; Wiley, B.; McLellan, J.; Xiong Y. J.; Li, Z. Y.; Xia, Y. N. Nano Lett. 2005, 5, 2058.
11. [11]
  (11) Pol, V. G.; Grisaru, H.; Gedanken, A. Langmuir 2005, 21, 3635.
12. [12]
  (12) Zhang, X. Y.; Li, S. Y.; Yang, L; Fan, C. Q. Spectrochim. Acta A 2007, 68, 763.
13. [13]
  (13) Oh, S. D.; Kim, M. R.; Choi, S. H.; Chun, J. H.; Lee, K. P.; palan, A.; Hwang, C. G.; Kim, S. H. J. Ind. Eng. Chem. 2008, 14, 687.
14. [14]
  (14) Huang, W.; Pyrz, W.; Lobo, R. F.; Chen, J. G. Appl. Catal. A-Gen. 2007, 333, 254.
15. [15]
  (15) Miao, S. J.; Wang, Y.; Ma, D.; Zhu, Q. J.; Zhou, S.; Su, L. L.; Tan, D. L.; Bao, X. H. J. Phys. Chem. B 2004, 108, 17866.
16. [16]
  (16) Zea, H.; Lester, K.; Datye, A. K.; Rightor, E.; Gulotty, R.; Waterman, W.; Smith, M. Appl. Catall. A-Gen. 2005, 282, 237.
17. [17]
  (17) Ismagilov, Z. R.; Yashnik, S. A.; Startsev, A. N.; Boronin, A. I.; Stadnichenko, A. I.; Kriventsov, V.V.; Kasztelan, S.; Guillaume, D.; Makkee, M.; Moulijn, Jacob A. Catal. Today 2009, 144, 235.
18. [18]
  (18) Ghenoa, S. M.; Damyanova, S.; Riguetto, B. A.; Marques, C. M. P.; Leite, C. A. P.; Buenoa, J. M. C. J. Mol. Catal. A-Chem 2003, 198, 263.
19. [19]
  (19) Wang, X. L; Wovchko, E. A. J. Phys. Chem. B 2005, 109, 16363.
20. [20]
  (20) Maloney, S. D.; Zhou, P. L.; Kelley, M. J.; Gates, B. C. J. Phys. Chem. 1991, 95, 5409
21. [21]
  (21) Aboul-Gheit, A. K.; Aboul-Fotouh, S. M.; Aboul-Gheit, N. A. K. Appl. Catal. A-Gen. 2005, 283, 157.
22. [22]
  (22) Sugii, T.; Kamiya, Y.; Okuhara, T. Appl. Catal. A-Gen. 2006, 312, 45.
23. [23]
  (23) Mandal, S.; Roy, D.; Chaudhari, R. V.; Sastry, M. Chem. Mater. 2004, 16, 3714
24. [24]
  (24) Piqueras, C. M.; Ferna′ndez, M. B.; Tonetto, G. M.; Bottini, S.; Damiani, D. E. Catal. Commun. 2006, 7, 344.
25. [25]
  (25) Okumura, K.; Yoshimoto, R.; Uruga, T.; Tanida, H.; Kato, K.; Yokota, S.; Niwa, M. J. Phys. Chem. B 2004, 108, 6250.
26. [26]
  (26) Huang, S. P.; Mainardi, D. S.; Balbuena, P. B. Surf. Sci. 2003, 545, 163.
27. [27]
  (27) Huang, S. Y.; Huang, C. D.; Chang, B. T.; Yeh, C. T. J. Phys. Chem. B, 2006, 110, 21783.
28. [28]
  (28) Gu, Z.; Balbuena, P. B. Catal. Today 2005, 105, 152.
29. [29]
  (29) Borodzinski, A.; ?eübiowski A. Langmuir 1997, 13, 883.
30. [30]
  (30) Borodzinski, A. Catal. Lett. 1999, 63, 35.
31. [31]
  (31) Hong, Y. Y.; Sen, A. Chem. Mater. 2007, 19, 961.
32. [32]
  (32) Kidambi, S.; Dai, J. H.; Li, J.; Bruening, M. L. J. Am. Chem. Soc. 2004, 126, 2658.
33. [33]
  (33) Duca, D.; Varga, Z.; Manna, G. L.; Vidóczy, T. Theor. Chem. Acc. 2000, 104, 302.
34. [34]
  (34) Azad, S.; Kaltchev, M.; Stacchiola, D.; Wu, G.; Tysoe, W. T. J. Phys. Chem. B, 2000, 104, 3107.
35. [35]
  (35) Sheth, P. A.; Neurock, M.; Smith, C. M. J. Phys. Chem. B 2003, 107, 2009.
36. [36]
  (36) Mei, D. P.; Sheth, A.; Neurock, M.; Smith, C. M. J. Catal. 2006, 242, 1.
37. [37]
  (37) Mittendorfer, F.; Thomazeau, C.; Raybaud, P.; Toulhoat, H. J. Phys. Chem. B 2003, 107, 12287.
38. [38]
  (38) Belelli, P. G.; Castellani, N. J. Surf. Rev. Lett. 2008, 15, 249.
39. [39]
  (39) Duca, D.; Varga, Z.; Manna, G. L.; Vidóczy, T. Theor. Chem. Acc. 2000, 104, 302.
40. [40]
  (40) Fahmi, A.; Santen, R. A. J. Phys. Chem. 1996, 100, 5676.
41. [41]
  (41) Kuchle, W.; Dolg, M.; Stoll, H.; Preuss, H. J. Chem. Phys. 1994, 100, 7535.
42. [42]
  (42) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B. et al. Gaussian 03, Revision B.04; Gaussian, Inc.: Pitburgh, PA, 2003.
43. [43]
  (43) Srivastava, V.; Balasubramaniam, R. Materials Science and Engineering A 2001, 304, 897.
44. [44]
  (44) Crespo, E. A.; Claramonte, S.; Ruda, M.; Ramos de Debiaggi, S. International Journal of Hydrogen Energy 2008, 33, 3561.
45. [45]
  (45) Sheth, P. A.; Neurock, M.; Smith, C. M. J. Phys. Chem. B 2003, 107, 2009.
46. [46]
  (46) Moc, J.; Musaev, D. G.; Morokuma, K. J. Phys. Chem. A, 2003, 107, 4929.
47. [47]
  (47) Azad, S.; Kaltchec, M.; Stacchiola, D.; Wu, G.; Tysoe, W. T. J. Phys. Chem. B 2000, 104, 3107.
48. [48]
  (48) Horiuti, J.; Polanyi, M. Trans. Faraday Soc. 1934, 30, 1164.
1. [1]
  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
2. [2]
  Hongting Yan , Aili Feng , Rongxiu Zhu , Lei Liu , Dongju Zhang . Reexamination of the Iodine-Catalyzed Chlorination Reaction of Chlorobenzene Using Computational Chemistry Methods. University Chemistry, 2025, 40(3): 16-22. doi: 10.12461/PKU.DXHX202403010
3. [3]
  Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
4. [4]
  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
5. [5]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
6. [6]
  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
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]
  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
9. [9]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
10. [10]
  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
11. [11]
  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
12. [12]
  Ling Fan , Meili Pang , Yeyun Zhang , Yanmei Wang , Zhenfeng Shang . Quantum Chemistry Calculation Research on the Diels-Alder Reaction of Anthracene and Maleic Anhydride: Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 133-139. doi: 10.3866/PKU.DXHX202309024
13. [13]
  Jiabo Huang , Quanxin Li , Zhongyan Cao , Li Dang , Shaofei Ni . Elucidating the Mechanism of Beckmann Rearrangement Reaction Using Quantum Chemical Calculations. University Chemistry, 2025, 40(3): 153-159. doi: 10.12461/PKU.DXHX202405172
14. [14]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047
15. [15]
  Chengqian Mao , Yanghan Chen , Haotong Bai , Junru Huang , Junpeng Zhuang . Photodimerization of Styrylpyridinium Salt and Its Application in Silk Screen Printing. University Chemistry, 2024, 39(5): 354-362. doi: 10.3866/PKU.DXHX202312014
16. [16]
  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
17. [17]
  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
18. [18]
  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
19. [19]
  Qian Huang , Zhaowei Li , Jianing Zhao , Ao Yu . Quantum Chemical Calculations Reveal the Details Below the Experimental Phenomenon. University Chemistry, 2024, 39(3): 395-400. doi: 10.3866/PKU.DXHX202309018
20. [20]
  Yong Wang , Yingying Zhao , Boshun Wan . Analysis of Organic Questions in the 37th Chinese Chemistry Olympiad (Preliminary). University Chemistry, 2024, 39(11): 406-416. doi: 10.12461/PKU.DXHX202403009

Get Citation

PDF

XML

Metrics

PDF Downloads(1568)
Abstract views(4147)
HTML views(19)

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

Reaction Mechanism of Acetylene Hydrogenation Catalyzed by Pd8 Cluster

Metrics

通讯作者: 陈斌, bchen63@163.com

Reaction Mechanism of Acetylene Hydrogenation Catalyzed by Pd₈ Cluster