臺灣博碩士論文加值系統

碳六十/大環胺醚表面聲波感測器研製與應用
摘要
本研究中利用C60-cryptand[2,2]與Co2+/C60-cryptand[2,2]做為表面聲波(SAW, Surface Acoustic Wave)感測器之塗佈物質，分別來對一些揮發性有機氣體及CO氣體進行感測，並將C60-cryptand[2,2]表面聲波晶體應用於氣相層析系統。藉由表面聲波晶片上塗佈物質(C60-cryptand[2,2])吸附這些有機物或CO導致表面聲波感測器頻率下降來進行偵測。並以本實驗室自撰之程式讀取數據和繪圖。
在靜相系統研究中首先選擇了三種化合物(C60, cryptand [2,2] 及C60-cryptand [2,2] )做為表面聲波晶體之塗佈物質，用以偵測有機氣體。其中以C60-cryptand [2,2]作為塗佈物質具有較高之靈敏度。本研究中也對各種待測有機化合物之不同分子量大小、官能基的種類、異構物的立體障礙、及極性大小進行探討研究，此表面聲波對各種有機物偵測靈敏度順序如下：Alcohols (ROH) > Aldehydes (RCHO) > Ketones (RCOR’); 1-Hexyne>1-Hexene >n-Hexane; Aromatic > cyclo-Alkane > Alkane; 10alcohol > 20alcohol > 30alcohol。此研究結果顯示出C60-cryptand[2,2]塗佈表面聲波晶體對於高極性分子（尤其是易形成氫鍵者）、較大分子量、立體障礙小之化合物有著較高之靈敏度。對大部分之有機待測氣體分子而言，其感測現象皆為可逆性之吸附且可用通入N2來進行脫附。對一般有機氣體而言偵測下限範圍為0.2~2 mg/L。
在動相表面聲波感測系統研究上，其感測結果大致與靜相表面聲波感系統類似。在氣相層析表面聲波感測系統(GC-SAW)研究方面，碳六十-大環胺醚表面聲波偵測器對於分子極性大小、碳數多寡及同分異構物具有分辨能力，比一般商業化之常用於氣相層析的熱導偵測器偵(TCD, Thermal Conductivity Dector)只能從導熱係數來區分化合物更具有選擇性。
在表面聲波感測系統對CO氣體偵測方面，研究中曾利用各種金屬離子/碳六十-大環胺醚錯合物（如Ti4+/C60-cryptand [2,2]、Co2+/C60-cryptand [2,2]、Al3+/C60-cryptand等）做為表面聲波晶體之塗佈物，用以偵測CO氣體。其中以Co2+/C60-cryptand[2,2]之錯合方式對CO氣體具有較高之靈敏度。本研究中發現不同陰離團之金屬鹽類陰離子對於CO氣體之感測訊號並無顯著之影響。而此Co2+/C60-cryptand[2,2]表面聲波感測器對CO之偵測下限可達0.13ppm。

Preparation and Application of C60-Cryptand Coated Surface Acoustic Wave Sensor
Abstract
A C60-cryptand [2,2] coated surface acoustic wave (SAW) detection system was prepared and applied as Gas Chromatographic detector for various vapors. The frequency of surface acoustic wave oscillator decrease due to the adsorption of gas molecules on C60-cryptand [2,2] . The C60-cryptand [2,2] coated surface acoustic wave sensor was used to measure various organic moleculesr and CO gas. A software was written to control the interface and data acquisition.
In the stationary system, three coating materials (C60, cryptand [2,2] and C60-cryptand [2,2] ) was tested in organic molecules. The C60-cryptand [2,2] coated SAW dector exhibited more sensitive to polar molecule than Fullerene or cryptand [2,2] coated system respectively. Effect of functional groups, molecular weight, steric hindrance and polarity of organic molecules in both static and flow cell on frequency response of surface acoustic wave sensor had been investigated. The frequency shifts of the C60-cryptand [2,2] coated SAW sensor for various organic molecules and isomer in the order: Alcohols (ROH) > Aldehydes (RCHO) > Ketones (RCOR’); 1-Hexyne>1-Hexene >n-Hexane; Aromatic > cyclo-Alkane > Alkane; 10alcohol > 20alcohol > 30alcohol. The greater frequency shift of a molecule with large molecular weight, less steric hindrance and more polar molecule (especially can form hydrogen bond) was funded. The adsorption of C60-cryptand [2,2] to most organic molecules was found to be physical adsorption(a reversible type) ,which could be desorbed by introducing N2 gas. The detection system also showed the good detection limit of 0.2~3 mg/L for organic molecules.
The frequency response of C60-cytptand[2,2] coated SAW for various organic molecules in the flow system showed quite accordance with that in static system. In the application of Gas Surface acoustic Wave (GC-SAW) in GC, the C60-cryptand[2,2] SAW sensor showed higher selectivity than the TCD for polar organic molecules.
In CO gas study, various metal-ion/C60-cryptand[2,2] adsorbents, e.g. Ti4+/C60-cryptand [2,2]; Co2+/C60-cryptand [2,2]; Al3+/C60-cryptand, were used to adsorb and detect CO gas. The Co2+/C60-cryptand [2,2] coated SAW sensor exhibited more sensitive than another adsorbent for CO gas. It also showed no significant effect for anion group (e.g. SO42-; NO3-; Cl-). The detection limit of the SAW sensor for CO was found to be about 0.13 ppm.

第一章 緒論 1
1-1 冠狀醚及大環胺醚 1
1-1-1 冠狀醚及大環胺醚簡介 1
1-1-2 大環胺醚的應用 3
1-2 碳六十 5
1-2-1 碳六十的發現 5
1-2-2 碳六十的基本性質 7
1-2-3 碳六十的化學反應 10
1-2-3.1 碳六十的有機化學反應 11
(1) 與胺類化合物之反應 11
(2) 鹵化反應 13
(3) 氫化反應 13
(4) 氧化反應 13
(5) 環化加成反應 14
a.[1+2]環化加成 14
b.[2+2]環化加成 15
c.(3+2)環化加成反應 15
d.[4+2]環化加成 16
1-2-3.2 碳六十的無機反應 16
1-2-4 碳六十和氣體分子的交互作用 17
1-2-5 碳六十的應用 18
1-2-5.1 高溫超導之應用 18
1-2-5.2 藥物上的應用 19
1-2-5.3 在感測器上的應用 19
1-3 聲波偵測器 20
1-3-1 壓電晶體 20
1-3-2 聲波感測器之分類 22
1-3-2.1 TSM感測器 22
1-3-2.2 SH-APM感測器 23
1-3-2.3 表面聲波感測器 24
1-3-2.4 SH-SAW感測器 24
1-4 表面聲波 27
1-4-1 表面聲波之簡介 27
1-4-2 表面聲波之特性 27
1-4-3 SAW偵測方式 32
1-4-4 表面聲波之原理 34
1-5 表面聲波元件在感測器上之應用 38
1-5-1 表面聲波元件在氣相上的應用 38
1-6 實驗目的與動機 42
第二章 實驗部分 43
2-1藥品及儀器 43
2-2 碳六十-大環胺醚化合物之合成 43
2-3 表面聲波原件的處理 44
2-3-1 表面聲波元件 44
2-3-2 表面塗佈液之配製 45
2-4 實驗系統 46
2-4-1 靜相系統 46
2-4-2 動相模擬系統 47
2-4-4 一氧化碳(CO)偵測系統 49
2-4-5 電腦系統程式 50
第三章 結果與討論 51
3-1 揮發性有機氣體感測系統 51
3-1-1 有機氣體之感應頻率變化情形 51
3-1-2 表面塗佈物種效應 53
3-1-3 表面塗佈量對訊號的影響 53
3-1-4 不同形式SAW與QCM之比較 56
3-1-5 氣體分子碳鏈長度效應 58
3-1-6 分子立體結構效應 61
3-1-7 醇醚同分異構物之感測訊號探討 63
3-1-8 不同官能基之感應訊號比較 65
3-1-9 低極性有機氣體感應研究 68
3-1-10 待測有機物濃度效應及偵測下限 70
3-1-11 動相SAW感測系統 72
3-1-12 SAW動相系統對有機環狀化合物感應研究 76
3-1-13 SAW動相系統中之待測物濃度效應 76
3-1-14 碳六十-大環胺醚SAW氣體偵測器的再現性 80
3-1-15 氣體流速效應 80
3-1-16有機物官能基效應 84
3-1-17 動相及靜相SAW系統之比較 84
3-1-18 碳六十-大環胺醚SAW偵測器與熱導偵測器（TCD）偵測比較 86
3-1-19 有機溶劑在碳六十-大環胺醚表面聲波偵測器與熱導偵測器（TCD）之偵測比較 86
3-1-20 SAW及TCD偵測器感測氯甲烷混合物之比較 89
3-2 CO氣體SAW感測器統 91
3-2-1 CO氣體之感應頻率變化情形 91
3-2-2 不同塗佈物對CO感應頻率變化影響 91
3-2-3 塗佈物中不同陰離子團對CO感應頻率變化影響 94
3-2-4 塗佈物中不同金屬離子對CO感應頻率變化影響 94
3-2-5不同塗佈量對CO感應頻率變化影響 97
3-2-6 CO濃度效應對感應頻率變化的影響 97
3-2-7 表面聲波晶體對CO氣體偵測之再現性 100
3-3 碳六十-大環胺醚在液相的應用 100
第四章 結論 102
參考資料 103
附錄 108

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