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研究生:呂文禎
研究生(外文):Wen-Chen Lu
論文名稱:取代型金屬酞花青氣體感測行為之研究
論文名稱(外文):Studies on the Gas Sensing Properties of Substituted Metallophthalocyanines
指導教授:劉進興劉進興引用關係
指導教授(外文):Chin-Hsin Liu
學位類別:碩士
校院名稱:國立臺灣科技大學
系所名稱:化學工程系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
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:取代型金屬酞花青光學感測器旋轉塗佈揮發性有機氣體
外文關鍵詞:Substituted MetallophthalocyaninesOptical SensorSpin CoatingVOCs
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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
英文摘要
誌謝
目錄
表目錄
圖目錄

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