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研究生: 呂文禎
Wen-Chen Lu
論文名稱: 取代型金屬酞花青氣體感測行為之研究
Studies on the Gas Sensing Properties of Substituted Metallophthalocyanines
指導教授: 劉進興
Chin-Hsin Liu
口試委員: 江志強
Jyh-Chiang Jiang
朱義旭
Yi-Hsu Ju
施正雄
Jeng-Shong Shin
學位類別: 碩士
Master
系所名稱: 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年: 2005
畢業學年度: 93
語文別: 中文
論文頁數: 130
中文關鍵詞: 旋轉塗佈揮發性有機氣體光學感測器取代型金屬酞花青
外文關鍵詞: VOCs, Spin Coating, Substituted metallophthalocyanines, Optical sensor
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  • 本研究以旋轉塗佈法將六種取代型金屬酞花青(MPc)鍍於玻璃基板上,以光學感測方法進行薄膜對胺類、酸類感測行為之研究,並利用分子模擬方法探討薄膜材料之穩態結構、氣體分子最佳吸附位置及電子光譜。
    在胺類感測部分,探討(oct)ZnPc薄膜吸附不同結構之胺類氣體時,對UV-vis光譜吸收特性之影響。實驗結果顯示:
    (1)胺分子碳鏈越長,其推電子能力越強。
    (2)級數越低之胺類分子,N原子提供電子之能力越佳。
    (3)雙胺的胺基數目較多,有效碰撞頻率也較高。
    (4)戊胺異構物中,正戊胺之立體障礙效應最小。
    (5) Aniline因具苯環共振結構,而降低N原子之lone pair密度。
    上述(1)-(4)因素都能提高氣體靈敏性;反之,(5)會降低感測之靈敏度。另外,金屬酞花青薄膜對胺類之感測特性也受中間金屬與外緣取代基的影響。
    在酸類感測部分,探討(oct)MPc與取代型ZnPc薄膜吸附不同碳鏈之酸類氣體時,對UV-vis光譜吸收特性之影響。研究結果顯示中間金屬以及外緣取代基皆會影響酞花青對酸類光學感測之靈敏性與選擇性。


    In this study, thin films of six substituted metallophthalocyanines were spun unto glass substrates, and the changes of their UV-Visible spectra were investigated upon exposure to amine and acid vapors. Computational chemistry methods were also employed to simulate the gas adsorption process and the accompanying changes in the electronic spectra.

    Changes of absorbance in the visible region were observed as the (oct)ZnPc film was exposed to organic amine vapors. Our results show that:
    Effects of structure of the amines on sensitivity were studied to elucidate the sensing mechanism. The amine sensitivity is the largest for the primary amine, less for the secondary, and the least for the tertiary amines. For primary amines, the effect is in parallel to the alkyl chain length. Diamine shows a larger effect as compared to the simple amine, and some results can be explained in terms of the steric-hindrance effect of the amine substituents.

    Changes of absorbance in the visible region were observed as thin films of the (oct)MPcs and substituted ZnPc were exposed to organic acid vapors. Our results show that both central metals and substituents play an important role in their optical gas sensing.

    中文摘要 I 英文摘要 III 誌謝 IV 目錄 V 表目錄 VIII 圖目錄 IX 第一章 緒論 1 1-1 前言 1 1-2 氣體感測器 2 1-2.1原理 2 1-2.2種類 3 1.3 研究目的與動機 4 第二章 文獻回顧 7 2-1 酞花青簡介 7 2-1.1 Langmuir-Blodgett 技術(Langmuir-Blodgett Technique) 8 2-1.2 旋轉塗佈法(Spin-Coating Method) 9 2-1.3 自行組態法(Self-Assembly Method) 12 2-2 酞花青之光學性質 13 2-2.1 中間金屬效應 13 2-2.2 外緣取代基效應 17 2-3 取代型金屬酞花青之感測應用 22 2-3.1 質量式感測器 22 2-3.2 電化學感測器 23 2-3.3 光學式感測器 24 2-3.3.1 光纖基本構造 25 2-3.3.2 光纖傳輸原理 25 2-3.3.3 光學式氣體感測應用 27 2-4 總結 28 第三章 實驗方法 30 3-1 實驗試藥 30 3-2 實驗設備 32 3-3 分析儀器 32 3-4 玻璃基板之處理程序 33 3-5 薄膜製備 34 3-6 UV-Visible Spectroscopy操作 34 3-7 有機揮發性氣體(VOCs)濃度計算 36 3-8 實驗之基本假設 36 3-9 實驗流程 37 3-10 計算化學原理及方法 39 3-10.1 計算化學簡介 39 3-10.2 量子化學 41 3-10.3 薛丁格方程式(Schrödinge Equations) 42 3-10.4 波爾-歐本海莫(Born-Oppenheimer)近似法 44 3-10.5 分子軌域理論(Molecular Orbital Theory) 46 3-10.6 Hartree-Fock方程式 48 3-10.7半經驗計算方法 52 3-10.8 基底函數組(Basis Set) 54 3-10.9 最小基底函數 (Minimal Basis Sets), STO-3G 57 3-10.10 極化基底函數(Polarization Basis Sets),3-21G* 58 3-10.11 軟體設備 59 3-10.12 實驗計算方法 60 第四章 結果與討論 61 4-1 取代型金屬酞花青 61 4-1.1 取代型金屬酞花青薄膜表面型態 61 4-1.2 取代型金屬酞花青之吸收光譜 64 4-1.2.1 (oct)MPc之吸收光譜 64 4-1.2.2 SZnPc之吸收光譜 67 4-1.3 (oct)ZnPc對VOCs之感測 68 4-2 (oct)ZnPc對胺類氣體之感測 70 4-2.1 再現性 72 4-2.2 不同碳數之影響 73 4-2.3 己胺異構物之影響 75 4-2.4 官能基數目之影響 79 4-2.5 戊胺立體異構物 81 4-2.6 對Aniline之感測 85 4-2.7 偵測極限 88 4-3 其他(oct)MPc對胺類之感測 89 4-3.1 (oct)H2Pc對胺類之感測 89 4-3.2 (oct)NiPc對胺類之感測 90 4-3.3 (oct)CuPc對胺類之感測 91 4-3.4 胺類吸附位置探討 92 4-4 (oct)ZnPc對酸類之感測 96 4-5 其他(oct)MPc對酸類之感測 101 4-5.1 (oct)H2Pc對酸類之感測 101 4-5.2 (oct)NiPc對酸類之感測 103 4-5.3 (oct)CuPc對酸類之感測 107 4-6 其他SZnPc對胺、酸類之感測 111 4-6.1 SZnPc對胺類之感測 111 4-6.2 SZnPc對酸類之感測 116 第五章 結論 120 5-1 胺類氣體感測 120 5-1.1 (oct)ZnPc對胺類感測性質之探討 120 5-1.2 (oct)MPcs對胺類感測性質之探討 122 5-1.3 SZnPcs對胺類感測性質之探討 122 5-2 酸類氣體感測 123 5-2.1 (oct)MPcs對酸類感測性質之探討 123 5-2.2 SZnPcs對酸類感測性質之探討 124 5-3 總結 124 參考文獻 125

    Barger, W. R., Wohltjen, H., Snow, A. W., Lint, J., Jarvis, N. L., “Microsensor Vapor Detectors based on coating films of phthalocyanine and several of its metal complexes”, ACS Symp. Ser., (1986), 155-165

    Bassoul, P., Toupance, T., Simon, J., “Semiconductivity and gas-sensing properties of crown-ether-substituted lutetium disphthalocyanines”, Sens. and Actuators B, 26-27, (1995), 150-152

    Binks, B.P., “Insoluble monolayers of weakly ionizing low molar mass materials and their deposition to form Langmuir-Blodgett multilayers”, Adv. Colloid Interface Sci., 34, (1991), 343-432

    Braun, S., Rappoport, S., Zusman, R., Anvir, O., Ottoolenghi, M., “Biochemically active sol-gel glasses. The trapping of enzymes”, Mater. Lett., 10, (1990), 1-5

    Cook, M. J., Roxana, H., Jim, M. M., David, A. R., “Self-assembled monolayers of phthalocyanine derivatives on glass and silicon”, J. Mater. Chem., 6, (1996), 149-154

    Cook, M. J., “Thin film formulation of substituted phthalocyanines”, J. Mater. Chem., 6, (1996), 677-689

    Cook, M. J., “Phthalocyanine thin films”, Pure Appl. Chem., 71, (1999), 2145-2151

    Critchley, S. M., Martin, R. W., Cook, M. J., Jim, M. M., Maruyama, Y., “Desorption of ordered phthalocyanine films by spin coating”, J. Mater. Chem., 2, (1992), 157-159

    Crouch, D., Thorpe, S. C., Cook, M. J., Chambrier, I., Ray, A. K., “Langmuir-Blodgett films of an asymmetrically substituted phthalocyanine improved gas-sensing properties”, Sens. and Actuators B, 18-19, (1994), 411-414

    Dakin, J., Culshaw, B., Optical Fiber Sensor : Principles and Components, Artech House, (1988)

    David, R. L., Handbook of chemistry and physics 83rd, Cleveland, Ohio: CRC Press, (2002)

    Gaines, G. L., Insoluble Monolayers at the Liquid-Gas Interface, Wiley-Interscience, New York, (1966)

    Germain, J. P., Pauly, A., Maleysson, C., Blanc, J.P., and Schollhorn, B., “Influence of peripheral electron-withdrawing substituents on the conductivity of zinc phthalocyanine in the presence of gases. Part 2: oxidizing gases”, Thin Solid Films, 333, (1998), 235-239

    Giallorenzi, T. G., Bucaro, J. A., Dandridge, A., Sigel, G. H., “Optical Fiber Sensor Technology”, IEEE J. Quantum Electron, QE-18, (1982), 626-665

    Grate, J. W., Martin, S. J., White, R. M., “Acoustic wave microsensors”, Anal. Chem., 65, (1993), 940A-948A

    Guilbault, G. G., Jordan, J. M., Analytical uses of piezoelectric crystals︰A review, CRC Critical Review in Analytical Chemistry, 19, (1988), 1-28

    Gupta, B. D., Sharma, D. K., “Evanescent wave absorption based fiber optic pH sensor prepared by dye doped sol-gel immobilization technique”, Optics Commun., 140, (1997), 32-35

    Hu, W. P., Liu, Y. Q., Liu, S. G., Zhu, D. B., “The response mechanism of aminotri-tert-butylphthalocyanine thin films to nitrogen dioxide”, Thin Solid Films, 324, (1998), 285-291

    Huang, J. D., Zhang, Y. F., Li, J. Q., “Ab Initio Study on Some Metal Phthalocyanines”, Chinese J. Struct. Chem., 21, (2002), 214-217

    Ju, Y. H., Hsieh, J. C., Liu, C. J., “The Surface Reaction and Diffusion of NO2 in Lead Phthalocyanine Thin Film”, Thin Solid Films, 342, (1999), 238-243

    Kim, S. R., Choi, S. A., Kim, J. D., Choi, K. H., Park, S. K., Chang, Y. H., “Characteristics of metallophthalocyanine mono-, multilayer and application to the gas sensor for NO2”, Synthetic Metals, 71, (1995), 2293-2294

    Kobayashi, N., Ogata, H., Nonaka, N., Luk’yanets, E. A., “Effect of Peripheral Substitution on the Electronic Absorption and Fluorescence Spectra of Metal-Free and Zinc Phthalocyanines”, Chem. Eur. J., 9, (2003), 5123-5134

    Kurosawa, S., Tawara K. E., Minoura N., Kamo N., “Detection of polycyclic compounds as mutagens using piezoelectric quartz crystal coated with plasma-polymerized phthalocyanine derivatives”, Sens and Actuators B, 43, (1997), 175-179

    Leznoff, C. C., Lever, A. B. P., Phthalocyanines Properties and Applications, VCH: New York, 3, (1989), 188-191

    Li, X. Y., Shen, S. Y., Zhou, Q. F., Xu, H. J., Jiang, D. P., Lu, A. D., “The gas sensing behavior of spin-coated phthalocyanine films to NO2”, Thin Solid Films, 324, (1998a), 274-276

    Li, X. Y., Xu, H. J., Zhou, Q. F., Jiang, D. P., Zhang, L. G., Lu, A. D., “Gas sensing properties of asymmetrically substituted phthalocyanines bearing one crown ether ring”, Thin Solid Films, 324, (1998b), 277-280

    Liu, C. J., Hsieh, J. C., Ju, Y. H., “Response Characteristics of Lead Phthalocyanine Gas Sensor : Effect of Operating Temperature and Postdeposition Annealing”, J. Vac. Sci. Technol., A14, (1996), 753-756

    Liu, C. J., Lin, J. T., Wang, S. H., Jiang, J. C., Lin, L. G., “Chromogenic calixarene sensors for amine detection”, Sens. and Actuators B, 108, (2005), 521-527

    Liu, Z. T., Kwok, H.S., Djurišić, A. B., “The optical functions of metal phthalocyanines”, J. Phys. D: Appl. Phys., 37, (2004), 678-688

    Natale, C.D., Salimbeni, D., Paolesse, R., Macagnano, A., D’Amico, A., “Porphyrins-based opto-electronic nose for volatile compounds detection”, Sens and Actuators B, 65, (2000), 220-226

    Nikitin, P. I., Beloglazov, A. A., Valeiko, M. V., Creighton, J. A., Smith, A. M., Sommerdijk, J. M., Wright, J. D., “Silicon-based surface plasmon resonance chemical sensors”, Sens. and Actuators B, 38-39, (1997), 53-57

    Pilar, F. L., Elementary Quantum Chemistry 2nd, McGraw Hill Publishing Company, New York, (1990)

    Potyrailo, R. A., Hobbs, S. E., Hieftje, G. M., “Near-ultraviolet evanescent-wave absorption sensor based on a multimode optical fiber”, Anal. Chem., 70, (1998), 1639-1645

    Qiu, X. H., Wang, C., Zeng, Q. D., Xu, B., Yin, S. X., Wang, H. G., Xu, S. D., Bai, C. L., “Alkane-Assisted Adsorption and Assembly of Phthalocyanines and Porphyrins”, J. Am. Chem. Soc., 122, (2000), 5550-5536

    Ricciardi, G., Rosa, A., Baerends, E. J., “Ground and excited states of zinc phthalocyanine studied by density functional methods”, J. Phys. Chem.,105, (2001), 5242-5254

    Roberts, G., Ed. Langmuir-Blodgett Films, Plenum Press, New York, (1990)

    Sauerbrey, G., “Use a quartz vibrator from weigh thin films on a microbalance”, Z. Physik, 155, (1959), 206-222

    Schierbaum, K. D., Zhou, R., Knecht, S., Dieing, R., Hanack, M., Goepel, W., “Interaction of transition metal phthalocyanines with organic molecules: A quartz-microbalance study”, Sens and Actuators B, 24-25, (1995), 69-71

    Schöllhorn, B., Germain, J. P., Pauly, A., Maleysson, C., and Blanc, J. P., “Influence of peripheral electron-withdrawing substituents on the conductivity of zinc phthalocyanine in the presence of gases. Part 1: reducting gases”, Thin Solid Films, 326, (1998), 245-250
    Senior, J. M., Optical Fiber Communication: Principles and Practice, (1985)

    Spadavecchia, J., Ciccarella, G., Vasapollo, G., Siciliano, P., Rella, R., “UV-Vis absorption optosensing materials based on metallo- phthalocyanines thin films”, Sens. Actuators B, 100, (2004), 135-138

    Tai, H., Tanaka, H., “Fiber-optic evanescent-wave methane-gas sensor using optical absorption for the 3.392-μm line of a He-Ne laser”, Optics Letts., 12, (1987), 437-439

    Takahashi, K., Kawashima, M., Tomita, Y., Itoh, M., “Synthesis and spectral and electrochemical properties of 2,3,9,10,16,17,23,24- octabutylthio-phthalocyaninatozinc (II)”, Inorganica Chimica Acta, 232, (1995), 69-73

    Wöhrle, D., Schmidt, V., “Octabutoxyphthalocyanine, a new electron donor”, J. Chem., Soc. Dalton Trans., (1988), 549-551

    Wolfbeis, S., “Fiber optic biosensing based on molecular recognition”, Sens. and Actuators B, 5, (1991), 1-6

    Yoshida, H., Tsutsumi, K., Sato, N., “Unoccupied electronic states of 3d-transition metal phthalocyanines studied by inverse photoemission spectroscopy”, J. Electron Spectroscopy Related Phenomena, 121, (2001), 83-91

    Zeug, A., Paul, A., Röder, B., “Observation of the phase transition in phospholipid liposomes taking advantage of the particular optical properties of octa-α-butyloxy-H2Phthalocyanines”, J. Porphyrins Phthalocyanines, 5, (2001), 663-667

    Zhou, X. C., Zhou, R., Li, S. F. Y., Ng, S. C., Chan, H. S. O., Sens. and Actuators B, 26-27, (1995), 208

    王志達, “旋轉塗佈之研究”, 國立臺灣大學化學工程所博士論文, (1995)

    江志強, “理論計算及間質隔離紅外線光譜對呲咯分子間氫鍵及酚類分子內轉與分子內氫鍵的研究”, 國立台灣大學化學所博士論文, (1994)

    李勝利, “以壓電石英晶體法對金屬酞花青薄膜氣體感測特性之研究”, 國立台灣科技大學化學工程系碩士論文, (2002)

    林立德, 光纖概論, 科技圖書出版, (1987)

    林炯廷, “Nitrophenylazo Calix[4]arenes對胺類氣體感測特性之研究”, 國立台灣科技大學化學工程系碩士論文, (2004)

    林靜怡, “取代型金屬酞花青薄膜氣體感測性質之研究”, 國立台灣科技大學化學工程系碩士論文, (1999)

    施佳金, “鎳酞花青薄膜型態與氣體感測性質之研究”, 國立台灣科技大學化學工程系碩士論文, (1999)

    廖得照, 光纖技術手冊, 全華科技出版, (1995)

    蔡嬪嬪、曾明漢, 材料與社會, 68(50), (1992)

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