| 研究生: |
陳憲璁 Chen, Sian-Cong |
|---|---|
| 論文名稱: |
3-氯丙醇在銅(100)和氧/銅(100)表面上的熱化學研究 Thermal Chemistry of 3-Chloro-1-propanol on Cu(100) and O/Cu(100) Surfaces |
| 指導教授: |
林榮良
Lin, Jong-Liang |
| 學位類別: |
碩士 Master |
| 系所名稱: |
理學院 - 化學系 Department of Chemistry |
| 論文出版年: | 2013 |
| 畢業學年度: | 101 |
| 語文別: | 中文 |
| 論文頁數: | 65 |
| 中文關鍵詞: | 超高真空系統 、3-氯丙醇 、銅(100) 、氧/銅(100) 、程序控溫反應/脫附 |
| 外文關鍵詞: | ultra-high vacuum system, 3-chloro-1-propanol, Cu(100), O/Cu(100), temperature-programmed reaction/desorption |
| 相關次數: | 點閱:184 下載:1 |
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本論文是以程溫反應/脫附(TPR/D)探討超高真空系統中3-氯丙醇在Cu(100)和O/Cu(100)的反應。3-氯丙醇在Cu(100)表面上會分解形成丙烷、丙烯、乙烷、一氧化碳、水和氫脫附,其中丙烷、丙烯、乙烯在120 K就已經形成。我們推測3-氯丙醇在120 K就部份斷C-Cl、C-OH、O-H鍵形成-CH2CH2CH2-、-OCH2CH2CH2-中間物。-CH2CH2CH2- 獲得表面上的H(a)形成丙烷或脫去β-H形成-CH2CH=CH2後再獲得表面上的H(a)形成丙烯。-OCH2CH2CH2-在表面形成η3(C,C,O)中間物,經由電子轉移造成C-C斷裂,產生乙烯及一氧化碳。
3-氯丙醇在O/Cu(100)表面上會分解形成丙醛、水、氫、二氧化碳,由於氧未覆蓋整個表面,故也會產生無氧表面時的產物,如丙烷、丙烯、乙烯、一氧化碳。我們推測3-氯丙醇在低溫可形成-OCH2CH2CH2-和-OCH2CH2CH2Cl中間物,以致在~400 K產生丙醛脫附。
In this research, temperature-programmed reaction/desorption (TPR/D) has been employed to investigate the thermal reactions of ClCH2CH2CH2OH on Cu(100) and on O/Cu(100) in an ultra-high vacuum chamber. Propane, propene, ethene, CO, H2O and H2 are the reaction products found from ClCH2CH2CH2OH decomposition on Cu(100). At 120 K, propane, propene and ethene have already been formed. We suggest that ClCH2CH2CH2OH is dissociatively adsorbed in the forms of -CH2CH2CH2- and -OCH2CH2CH2- due to C-Cl, C-OH and O-H bond scission. -CH2CH2CH2- recombines with surface H (H(a)) to form propane or undergoes β-H elimination to form -CH2CH=CH2, which reacts with H(a) to form propene. -OCH2CH2CH2-, in η3(C,C,O) bonding structure, produces ethene and CO(a) via C-C breakage.
Propionaldehyde, H2O, H2 and CO2 are the reaction products from ClCH2CH2CH2OH decomposition on the oxygen-precovered surface. Since the Cu(100) surface is not fully covered with oxygen atoms in our case, propane, propene, ethene and CO are still produced. We suggest that on O/Cu(100) ClCH2CH2CH2OH is adsorbed in the forms of -OCH2CH2CH2- and -OCH2CH2CH2Cl at low temperatures. These intermediates are responsible for the product of propionaldehyde at ~400 K.
1. Somorjai, G. A. “Introduction to Surface Chemistry and Catalysis” Wiley & Sons, New York, 1994.
2. Gregg, S. J.; Sing, K. S. “Adsorption, Surface Area and Porosity” Academic Press, New York, 1967.
3. Lin, J.-L.; Teplyakov, A. V.; Bent, B. E. J. Phys. Chem. 1996, 100, 10721.
4. Lin, J.-L.; Bent, B. E. J. Phys. Chem. 1993, 97, 9713.
5. Lin, J.-L.; Bent, B. E. J. Am. Chem. Soc. 1993, 115, 2849.
6. Lin, J.-L.; Bent, B. E. J. Phys. Chem. 1992, 96, 8529.
7. Richter, L. J.; Ho, W. J. Chem. Phys. 1985, 83, 2569.
8. Russell, J. N., Jr.; Chorkendorff, I.; Yates, J. T., Jr. Surf. Sci. 1987, 183, 316.
9. Bare, S. R.; Stroscio, J. A.; Ho, W. Surf. Sci. 1985, 150, 399.
10. Gate, S. M.; Russell, J. N., Jr.; Yates, J. T., Jr. Surf. Sci. 1986, 171, 111.
11. Madix, R. J. Adv. Catal. 1980, 29, 1.
12. Wachs, I. E.; Madix, R. J. Appl. Surf. Sci. 1978, 1, 303.
13. Friend, C. M.; Xu, X. Annu. Rev. Phys. Chem. 1991, 42, 251.
14. Dai, Q.; Gellman, A. J. J. Phys. Chem. 1993, 97, 10783.
15. Sexton, B. A. Surf. Sci. 1979, 88, 299.
16. Bowker, M.; Madix, R. J. Surf. Sci. 1982, 116, 549.
17. Camplin, J. P.; McCash, E. M. Surf. Sci. 1996, 360, 229.
18. Gellman, A. J.; Dai, Q. J. Am. Chem. Soc. 1993, 115, 714.
19. Houtman, C. J.; Barteau, M. A. J. Catal. 1991, 130, 528.
20. Brown, N. F.; Barteau, M. A. Langmuir 1995, 11, 1184.
21. Zhao, Q.; Zaera, F. J. Am. Chem. Soc. 2003, 125, 10776.
22. Zhao, Q.; Deng, R.; Zaera, F. J. Phys. Chem. C 2010, 114, 7913.
23. Zhao, Q.; Zaera, F. J. Phys. Chem. B 2003, 107, 9047.
24. Wu, G.; Stacchiola, D.; Kaltchev, M.; Tysoe, W. T. Surf. Sci. 2000, 463, 81.
25. Jones, G. S.; Barteau, M. A. J. Vac. Sci. Technol. A 1997, 15, 1667.
26. Jones, G. S.; Barteau, M. A. J. Am. Chem. Soc. 1998, 120, 3196.
27. Brown, N. F.; Barteau, M. A. J. Phys. Chem. 1994, 98, 12727.
28. Liao, Y.-H.; Chen, C.-Y.; Fu, T.-W.; Wang, C.-Y.; Fan, L.-J.; Yang, Y.-W.; Lin, J.-L. Surf. Sci. 2006, 600, 417.
29. Chang, P.-T.; Shih, J.-J.; Kuo, K.-H.; Chen, C.-Y.; Fu, T.-W.; Shieh, D.-L.; Liao, Y.-H.; Lin, J.-L. J. Phys. Chem. B 2004, 108, 13320.
30. Fu, T.-W.; Liao, Y.-H.; Chen, C.-Y.; Chang, P.-T.; Wang, C.-Y.; Lin, J.-L. J. Phys. Chem. B 2005, 109, 18921.
31. Chen, C.-Y.; Chang, P.-T.; Kuo, K.-H.; Shih, J.-J.; Lin, J.-L. J. Phys. Chem. B 2003, 107, 10488.
32. Chang, P.-T.; Kuo, K.-H.; Shih, J.-J.; Chen, C.-Y.; Lin, J.-L. Surf. Sci. 2004, 561, 208.
33. 陳嘉淵“2-鹵化乙醇在Cu(100)表面上的熱化學研究”國立成功大學化學所,2002.
34. Auger, P. J. Phys. Radium 1925, 6, 205.
35. Vickerman, J. C. “Surface Analysis-The Principle Technique” Wiley & Sons, New York, 1997.
36. Ertl, G.; Küppers, J. “Low Energy Electrons and Surface Chemistry” Verlag Chemie, Germany, 22, 1974.
37. Redhead, P. A. Vacuum 1962, 12, 203.
38. Lin, J.-L. “Carbon-Halogen Bond Dissociation at Copper Surface: Alkyl Radicals versus Metal Alkyls” Columbia University, P29-30, 1993.
39. 陳誌偉“3-氯丙醇在Ni(111)表面上的熱反應與吸附位向的研究”國立成功大學化學所,2010.
40. Sexton, B. A. Surf. Sci. 1979, 88, 299.
41. Jenks, C. J.; Bent, B. E.; Bernstein, N.; Zaera, F. Surf. Sci. Lett. 1992, 277, L89.
42. Bryden, T. R.; Garrett, S. J. J. Phys. Chem. B 1999, 103, 10481.
43. Rasmussen, P. B.; Chorkendorff, I. Surf. Sci. 1991, 248, 35.
44. Brosseau, R.; Brustein, M. R.; Ellis, T. H. Surf. Sci. 1993, 294, 243.
45. Ellis, T. H.; Kruus, E. J.; Wang, H. J. Vac. Sci. Technol. A 1993, 11, 2117.
46. Kolovos-Vellianitis, D.; Kammler, T.; Küppers, J. Surf. Sci. 2001, 482, 166.
47. Tjandra, S.; Zaera, F. J. Phys. Chem. B 1997, 101, 1006.
48. Childs, K. D.; Carlson, B. A.; LaVanier, L. A.; Moulder, J. F.; Paul, D. F.; Stickle, W. F.; Watson, D. G. Hedberg, C. L. “Handbook of Auger Electron Spectroscopy, 3rd” Physical Electronics, Minnesota, 1995.
49. Mavrikakis, M.; Barteau, M. A. J. Mol. Catal. A-Chem. 1998, 131, 135.
50. Pan, M.; Pozun, Z. D.; Brush, A. J.; Henkelman, G.; Mullins, C. B. ChemCatChem 2012, 4, 1241.
51. Stacchiola, D.; Wu, G.; Kaltchev, M.; Tysoe, W. T. Surf. Sci. 2001, 486, 9.
52. Rasmussen, P. B.; Taylor, P. A.; Chorkendorff, I. Surf. Sci. 1992, 269/270, 352.
53. Szanyi, J.; Goodman, D. W. Catal. Lett. 1993, 21, 165.