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研究生:謝君逸
研究生(外文):Chun-Yi Shieh
論文名稱:碘苯和芳杯分子在二氧化鈦粉末上的吸附與反應
論文名稱(外文):Adsorption and Reactions of Iodobenzene and p-tert-Butylcalix[6]arene on Powdered TiO2
指導教授:林榮良
指導教授(外文):Jong-Liang Lin
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學系碩博士班
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2008
畢業學年度:96
語文別:中文
論文頁數:74
中文關鍵詞:碘苯芳杯分子二氧化鈦傅氏轉換紅外光譜
外文關鍵詞:p-tert-butylcalix[6]areneTiO2iodobenzeneFTIR
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本篇論文是研究在真空系統中利用傅氏轉換紅外光譜(FTIR)探討iodobenzene和p-tert-butylcalix[6]arene在二氧化鈦粉末表面上的吸附與反應。Iodobenzene在35˚C時,完整地(不分解)吸附於TiO2表面上。加熱至275˚C,iodobenzene會斷裂C-I鍵形成苯氧基吸附於表面上。更高溫度的熱反應產物為CO(a)、CO2(a)、CO3(a)、HCO3(a)。Iodobenzene在有氧環境下,受UV光照射後分解形成CO(a)、CO2(a)、CO3(a)、H2O(a)、C6H5O(a)和HCOO(a)。而無氧情況下,只觀察到CO3(a)和C6H5O(a)。預吸附的水能提升iodobenzene的光分解。p-tert-Butylcalix[6]arene在35˚C時,不分解地吸附於TiO2表面。此p-tert-butylcalix[6]arene在450˚C加熱後會產生苯氧基。p-tert-Butylcalix[6]arene在有氧下光分解生成CO(a)、CO2(g)、CO3(a)和HCO3(a)。
Fourier-transformed infrared spectroscopy has been employed to investigate the adsorption and reactions of iodobenzene and p-tert-butylcalix[6]arene on powdered TiO2. Iodobenzene (C6H5I) is adsorbed molecularly on TiO2 surface at 35˚C. Upon increasing the temperature to 275˚C, iodobenzene undergoes C-I bond cleavage, forming phenoxy groups on the surface. The products from the thermal decomposition of C6H5I include CO(a), CO2(a), CO3(a) and HCO3(a). Iodobenzene on TiO2 subjected UV irradiation in the presence of O2 decomposes into CO(a), CO2(a), CO3(a), H2O(a), C6H5O(a) and HCOO(a) However, in the absence of O2, CO3(a) and C6H5O(a) are generated. Preadsorbed H2O can enhance the photoreaction of C6H5I on TiO2. p-tert-Butylcalix[6]arene is adsorbed molecularly on TiO2 surface at 35˚C. When the surface is heated to 450˚C, it forms phenoxy groups on the surface. p-tert-Butylcalix[6]arene on TiO2 decomposes to form CO(a), CO2(g), CO3(a), and HCO3(a) under photoirradiation in the presence of O2.
第一章 緒論………………………………………………………………1
1-1 TiO2光催化的起源………………………………………………………….1
1-2 TiO2光催化原理…………………………………………………………….1
1-3 電荷載子捕捉………………………………………………………………4
1-4 TiO2晶體結構……………………………………………………………….5
1-5 TiO2光催化反應的發展…………………………………………………….6

第二章 實驗系統及實驗方法……………………………………………9
2-1實驗系統概述……………………………………………………………….9
2-1-1 儀器………………………………………………………………….10
2-1-2 藥品………………………………………………………………….11
2-2傅式轉換紅外光譜系統……...…………………………………………….12
2-2-1 MCT偵檢器……..……………………………………………………12
2-2-2 IR光源………………………………………………………………..12
2-3 汞燈系統…………………………………………………………………..13
2-4 真空系統…………………………………………………………………..13
2-5 紅外光譜樣品槽的設計…………………………………………………..14
2-6 二氧化鈦/鎢網(TiO2/W)的製備…………………………………………..16
2-6-1 TiO2/W的製備……………………………………………………….16
2-6-2 TiO2/W在紅外光譜樣品槽的擺放位向…………………………….17
2-6-3 TiO2/W的前處理…………………………………………………….18
2-7 藥品的前處理……………………………………………………………..18
2-8 理論計算…………………………………………………………………..19
2-9 Iodobenzene的應用及研究動機…………………………………………..20

第三章 Calix[n]arenes 芳杯分子相關介紹……………………………21
3-1 Calix[n]arenes起源及命名………………………………………………..21
3-2 Calix[n]arenes構形………………………………………………………..22
3-3 Calix[n]arenes發展與應用………………………………………………..24
3-4 p-tert-Butylcalix[6]arene研究動機………………………………………..26

第四章 結果與討論……………………………………………………..27
4-1 Iodobenzene………………………………………………………………...27
4-1-1 Iodobenzene的吸附和熱反應研究…………………………………..27
4-1-2 Iodobenzene在密閉系統中的熱反應研究…………………………..28
4-1-3 Iodobenzene在有氧密閉系統的熱反應研究………………………..29
4-1-4 有氧下低覆蓋率的Iodobenzene/TiO2光反應及熱對照……………33
4-1-5 有氧同位素下低覆蓋率的Iodobenzene/TiO2光反應………………35
4-1-6 無氧下低覆蓋率的Iodobenzene/TiO2光反應及熱對照……………36
4-1-7 有水存在下低覆蓋率的Iodobenzene/TiO2光反應…………………37
4-2 p-tert-Butylcalix[6]arene………………………………………………...…40
4-2-1 p-tert-Butylcalix[6]arene的吸附和熱反應研究………………..……40
4-2-2 p-tert-Butylcalix[6]arene/TiO2有氧光反應………………..…………42

第五章 結論…………………………………………………..…………68
5-1 Iodobenzene在TiO2表面上的吸附與反應…………………………..……68
5-2 p-tert-Butylcalix[6]arene的吸附與光反應………………………...………68

參考文獻…………………………………………………………………69
1.S. J. Gregg, K. S. Sing, Adsorption, Surface area and Porosity. Academic Press, New York, 1967.
2.A. Fujishima, K. Honda, "Electrochemical photolysis of water at a semiconductor electrode" Nature 37, 238, 1972.
3.A. J. Bard, "Design of semiconductor photoelectrochemical systems for solar energy conversion" J. Phys. Chem. 86, 172, 1982.
4.A. J. Bard, "Photoelectrochemistry" Science 207, 139, 1980.
5.S. N. Franks, A. J. Bard, "Heterogeneous photocatalytic oxidation of cyanide and sulfite in aqueous solutions at semiconductor powders" J. Phys. Chem. 81, 1484, 1977.
6.J. K. Leland, A. J. Bard, "Photochemistry of colloidal semiconducting iron oxide polymorphs" J. Phys. Chem. 91, 5076, 1987.
7.Q. S. Li, "Photocatalytic synthesis and photodecomposition of ammonia over SrTiO3 and BaTiO3 based catalysts" Chem. Lett. 135, 321, 1983.
8.A. L. Linsebigler, G. Lu, J. T. Yates, Jr., "Photocatalysis on TiO2 surfaces: principles, mechanisms, and selected results" Chem. Rev. 95, 735, 1995.
9.J. Fan, J. T. Yates, Jr., "Mechanism of photooxidation of trichloroethylene on TiO2: detection of intermediates by infrared spectroscopy" J. Am. Chem. Soc. 118, 4686, 1996.
10.M. A. Fox, M. T. Dulay, "Heterogeneous photocatalysis" Chem. Rev. 93, 341, 1993.


11.J. K. Burdett, T. Hughbands, J. M. Gordon, J. W. Richardson, Jr., J. V. Smith, "Structural-electronic relationships in inorganic solids: powder neutron diffraction studies of the rutile and anatase polymorphs of titanium dioxide at 15 and 295 K" J. Am. Chem. Soc. 109, 3639, 1987.
12.J. Augustynski, "The role of the surface intermediates in the photoelectrochemical behaviour of anatase and rutile TiO2" Electrochim. Acta 38, 43, 1993.
13.L. Cao, F.–J. Spiess, A. Huang, S. L. Suib, " Heterogeneous photocatalytic oxidation of 1-butene on SnO2 and TiO2 films " J. Phys. Chem. B 103, 2912, 1999.
14.D. F. Ollis, E. Pelizzetti, N. Serpone, "Photocatalyzed destruction of water contaminants" Environ. Sci. Technol. 25, 1522, 1991.
15.O. Legrini, E. Oliveros, A. M. Braun, "Photochemical processes for water treatment" Chem. Rev. 93, 671, 1993.
16.K.-C. G. Low, S. R. McEvoy, R. W. Matthews, "Formation of nitrate and ammonium ions in titanium dioxide mediated photocatalytic degradation of organic compounds containing nitrogen atoms" Environ. Sci. Technol. 25, 460, 1991.
17.A. Wold, "Photocatalytic properties of titanium dioxide" Chem. Mater. 5, 280, 1993.
18.M. Scgiavello, Ed. Photocatalysis and Environment, Kluwer Academic Publishers, Dordrecht, 1988.
19.J.-J. Yang, D.-X. Li, Q-L. Li, Z.-J. Zhang, H.-Q. Wang, "甲醛光催化氧化的反應機制" Acta Phys. Chim. Sin. 17, 278, 2001.
20.P. W. Atkins, Physical Chemistry, Oxford University, p997, 1994.
21.何佳勳, 碩士論文,國立成功大學化學研究所, p13, 2007.
22.J. Fan, J. T. Yates, Jr., "Infrared study of the oxidation of hexafluoropropene on TiO2" J. Phys. Chem. 98, 10621, 1994.
23.C.-C. Chuang, J.-S. Shiu, J.-L. Lin, "Interaction of hydrazine and ammonia with TiO2" Phys. Chem. Chem. Phys. 2, 2629, 2000.
24.J. C. S. Wong, A. Linsebigler, G. Lu, J. Fan, J. T. Yates, Jr., "Photooxidation of CH3Cl on TiO2(110) single crystal and powdered TiO2 surfaces" J. Phys. Chem. 99, 335, 1995.
25.P. Bou , C. N. Tam, J. Sopková, F. R. Trouw, "Measurement and ab initio modeling of the inelastic neutron scattering of solid N-methylformamide" J. Chem. Phys. 108, 351, 1998.
26.林育峰, 碩士論文, 國立成功大學化學研究所, p23, 2004.
27.P. Hohenberg, W. Kohn, "Inhomogeneous electron gas" Phys. Rev. 136, B864, 1964.
28.W. Kohn, L. J. Sham, "Self-consistent equations including exchange and correlation effects" Phys. Rev. 140, A1133, 1965.
29.M. Xi, B. E. Bent, "Mechanisms of the Ullmann coupling reaction in adsorbed monolayers" J. Am. Chem. Soc. 115, 7426, 1993.
30.M. Xi, B. E. Bent, "Iodobenzene on Cu(111): formation and coupling of adsorbed phenyl groups" Surf. Sci. 278, 19, 1992.
31.G. J. Szulczewski, J. M. White, "Thermal and photon-stimulated reactions of iodobenzene on Ag(111)" Surf. Sci. 399, 305, 1998.
32.D. Syomin, B. E. Koel, "Adsorption of iodobenzene (C6H5I) on Au(111) surfaces and production of biphenyl (C6H5–C6H5)" Surf. Sci. 490, 265, 2001.
33.H. Cabibil, H. Ihm, J. M. White, "The thermal chemistry of iodobenzene on Pt(111)" Surf. Sci. 447, 91, 2000.

34.D. M. Jaramillo, D. E. Hunka, D. P. Land, "Iodobenzene on Pd(111) studied by thermal desorption spectroscopy and laser-induced thermal desorption–Fourier transform mass spectrometry" Surf. Sci. 445, 23, 2000.
35.C. D. Gustche, Calixarene, The Royal Society of Chemistry, Cambridge, England, 1989.
36.C. D. Gustche, "Calixarene" Acc. Chem. Res. 16, 161, 1983.
37.蕭文修, 碩士論文, 國立清華大學化學研究所, p15, 2005.
38.A. Ikeda, S. Shinkai, "Novel cavity design using calix[n]arene skeletons: toward molecular recognition and metal binding" Chem. Res. 97, 1713, 1997.
39.江佩珍, 鍾文聖, "超分子化學的發展及應用" Chemistry, 61, 551, 2003.
40.L. Wang, X. F. Shi, X. J. Hu, Y. Liu, "Research and application of the calixarene-containing polymer materials" Progress In Chemistry, 14. 3. 2002.
41.B. Xu, T. M. Swager, "Rigid bowlic liquid crystals based on tungsten-oxo calix[4]arenes: host-guest effects and head-to-tail organization" J. Am. Chem. Soc. 115, 1159, 1993.
42.B. H. Hong, S. C. Bae, C. –W. Lee, S. Jeong, K. S. Kim, "Ultrathin Single-Crystalline Silver Nanowire Arrays Formed in an Ambient Solution Phase" Science 294, 348, 2001.
43.National Institute of Standards and Technology
44.D. H. Whiffen. "Vibrational frequencies and thermodynamic properties of fluoro-, chloro-, bromo-, and iodo-benzene" J. Chem. Soc. 273, 1350, 1956.


45.D. Syomin, B. E. Koel, "Adsorption of iodobenzene (C6H5I) on Au(111) surfaces and production of biphenyl (C6H5-C6H5)" Surf. Sci. 490, 265, 2001.
46.W.-C. Wu, L.-F. Liao, C.-F. Lien, J.-L. Lin, "FTIR study of adsorption, thermal reactions and photochemistry of benzene on powdered TiO2" Phys. Chem. Chem. Phys. 3, 4456, 2001.
47.J. Lichtenberger, M. D. Amiridis, "Catalytic oxidation of chlorinated benzenes over V2O5/TiO2 catalysts" J. Catal. 223, 296, 2004.
48.A. Ramstetter, M. Baerns, "Infrared spectroscopic investigation of the adsorption states of 1-butene, 1,3-butadiene, furan, 2,5-h-furanone, and maleic anhydride on alumina-supported V2O5-P2O5 catalyst" J. Catal. 109, 303, 1988.
49.G. Busca, G. Ramis, V. Lorenzelli, "On the mechanism of the selective oxidation of C4 linear hydrocarbons to maleic anhydride: an FT-IR study of the adsorption and oxidation of 1,3-butadiene on vanadia-titania" J. Mol. Catal. 55, 11, 1989.
50.F. Boccuzzi, A. Chiorino, "FTIR study of carbon monoxide oxidation and scrambling at room temperature over copper supported on ZnO and TiO2" J. Phys. Chem. 100, 3617, 1996.
51.M. A. Henderson, "Evidence for bicarbonate formation on vacuum annealed TiO2(110) resulting from a precursor-mediated interaction between CO2 and H2O " Surf. Sci. 400, 203, 1998.
52.L.-F. Liao, C.-F. Lien, D.-L. Shieh, M.-T. Chen, J.-L. Lin, "FTIR study of adsorption and photoassisted oxygen isotopic exchange of carbon monoxide, carbon dioxide, carbonate, and formate on TiO2" J. Phys. Chem. B 106, 11240, 2002.
53.P. Meriaudeau, J. C. Vedrine, "Electron paramagnetic resonance investigation of oxygen photoadsorption and its reactivity with carbon monoxide on titanium dioxide: the O3–3 species" J. Chem. Soc. Faraday Trans. 2. 72, 472, 1976.
54.O. I. Micic, Y. Zhang, K. R. Cromack, A. D. Trifunac, M. C. Thurnauer, "Photoinduced hole transfer from TiO2 to methanol molecules in aqueous solution studied by electron paramagnetic resonance" J. Phys. Chem. 97, 13284, 1993.
55.L.-F. Liao, W.-C. Wu, C.-Y. Chen, J.-L. Lin, "Photooxidation of formic acid vs formate and ethanol vs ethoxy on TiO2 and effect of adsorbed water on the rates of formate and formic acid photooxidation" J Phys. Chem. B 105, 7678, 2001.
56.M. A. Fox, M. T. Dulay, "Heterogeneous photocatalysis" Chem Rev. 93, 341, 1993.
57.M. R. Hoffmann, S. T. Martin, W. Choi, D. W. Bahnemann, "Environmental applications of semiconductor photocatalysis" Chem. Rev. 95, 69, 1995.
58.S. Horikoshi, H. Hidaka, N. Serpone, "Hydroxyl radicals in microwave photocatalysis. Enhanced formation of OH radicals probed by ESR techniques in microwave-assisted photocatalysis in aqueous TiO2 dispersion" Chem. Phys. Lett. 376, 475, 2003.
59.G. A. Somorjai, Introduction to surface chemistry and catalysis, Wiley & Sons, New York, p1, 1994.
60.J. C. Vickerman, Surface Analysis, Wiley & Sons, New York, p2, 1997.
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