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研究生: 黃聖樺
Huang, Sheng-Hua
論文名稱: ZnTPyP 自組裝超分子奈米結構應用於醋酸氣體感測
ZnTPyP self-assembly supramolecular nano material applied in acetic acid gas sensing
指導教授: 呂家榮
Lu, Chia-Jung
口試委員: 呂家榮
Lu, Chia-Jung
陳重佑
Chen, Chong-You
劉茂煌
Liu, Mao-Huang
口試日期: 2024/06/21
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2024
畢業學年度: 112
語文別: 中文
論文頁數: 88
中文關鍵詞: 氣體偵測器醋酸自組裝超分子
英文關鍵詞: Gas Sensor, Acetic Acid, Self-Assembly, Supramolecular
研究方法: 實驗設計法
DOI URL: http://doi.org/10.6345/NTNU202400721
論文種類: 學術論文
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  • 本研究利用界面活性劑溴化十六烷基三甲銨 (CTAB) 促使四吡啶基鋅卟啉 (ZnTPyP) 發生自組裝合成超分子奈米結構。接著我們比較了 ZnTPyP 微米晶體 (ZnTPyP micro crystal) 與奈米結構 (Nano material) 之氣體反應差異,並將其應用於醋酸氣體感測。ZnTPyP 之微米晶體與奈米結構皆能以穩定的形式存在溶液中,並透過 UV-Vis、SEM、TEM 及 XRD 確認結構的生成,在本實驗中將溶液滴覆於黃金指叉電極上,待其乾燥後再固定於 IC 底座上,並連接 LCR Meter 進行不同氣體之電抗測量。
    本研究對 15 種揮發性有機氣體進行電抗之量測,其中發現在二甲基甲醯胺 (Dimethylformamide, DMF) 及醋酸 (Acetic acid, AcOH) 具有良好的選擇性,而對其他氣體之反應較不明顯,並且在低濃度區擁有顯著的線性趨勢 (R2>0.99),以及良好的再現性和穩定性,透過計算後奈米結構對於醋酸的偵測下限可達 14 ppm。比較材料之反應訊號圖可以看出奈米結構的反應性優於 ZnTPyP 微米晶體,因利用界面活性劑使材料達到奈米化,使氣體易脫附於材料,因此,反應更加穩定,進而達到更低的偵測下限及穩定性。

    This study utilized the surfactant cetyltrimethylammonium bromide (CTAB) to induce the self-assembly of Zn(II) meso-Tetra(4-pyridyl) Porphine (ZnTPyP) into supramolecular nano structures. Subsequently, we compared the gas response differences between ZnTPyP micro crystal and nano material, and applied them to acetic acid gas sensing. Both ZnTPyP micro crystal and nano material could exist in solution in a stable form, and their structures were confirmed through UV-Vis, SEM, TEM, and XRD analyses. In this experiment, the solution was drop-casted onto gold interdigital electrodes, dried, then fixed on an IC base, and connected to an LCR Meter for gas reactance measurements.
    We conducted gas reactance measurements on 15 different volatile organic gases (VOCs), and found promising selectivity for dimethylformamide (DMF) and acetic acid (AcOH), with less pronounced responses to other gases. Notably, significant linear trends (R2 > 0.99), reproducibility, and stability were observed in the low concentration range. Nano material exhibited a detection limit of 14 ppm for acetic acid. Comparing the reaction signal graphs of the material, it demonstrates that the nano material exhibits superior reactivity compared to ZnTPyP micro crystal. This is due to the use of surfactants to achieve nano conformation, which facilitates gas desorption from the material, resulting in a more stable reaction, a lower detection limit, and improved stability.

    中文摘要 i Abstract ii 目錄 iv 表目錄 viii 圖目錄 ix 第一章 緒論 1 1.1 前言與研究動機 1 1.2 超分子的起源與定義 3 1.2.1 自組裝 4 1.2.2 分子摺疊 5 1.2.3 主客體化學 6 1.2.4 機械互鎖結構分子 7 1.2.5 氫鍵 9 1.2.6 𝜋-𝜋 作用力 10 1.3 ZnTPyP介紹 11 1.4 電阻、電抗、電感、電容等基本觀念 14 1.4.1 電阻 14 1.4.2 電抗 15 1.4.3 電感 16 1.4.4 電容 17 1.5 氣體偵測器的介紹 19 1.5.1 電阻式 19 1.5.2 電容式 21 1.6 研究目的 22 第二章 實驗部分 23 2.1 實驗藥品、器材與儀器設備 23 2.1.1 實驗藥品 23 2.1.2 實驗器材 24 2.1.3 儀器設備 25 2.2 ZnTPyP 微米晶體及奈米結構溶液之製備 29 2.3 偵測器之製作過程 31 2.3.1 指叉電極規格及清洗 31 2.3.2 底座的製作 31 2.3.3 薄膜製作 34 2.4 氣體生成系統說明 36 2.4.1 吸附劑種類 38 2.5 LabVIEW程式之應用 39 2.5.1 LCR Meter 之數據紀錄 40 2.5.2 數據平滑功能 41 2.5.3 響應值之計算 43 2.5.4 電磁閥之轉向切換 44 2.6 有機氣體訊號處理 45 2.6.1 LCR Meter 參數設定 45 第三章 結果與討論 47 3.1 ZnTPyP 微米晶體及奈米結構之結構分析 47 3.1.1 SEM 及 TEM 47 3.1.2 XRD 49 3.1.3 UV-Vis 51 3.2 儀器測量之參數選擇 53 3.2.1 阻抗中電阻及電抗所佔之比例 55 3.2.2 電抗與電容換算 57 3.3 氣體選擇性 58 3.3.1 不同氣體下之響應值 58 3.3.2 有效氣體之檢量線 62 3.3.3 有效氣體之再現性與重複性 69 3.4 反應機制 73 3.4.1 氣體物理性質之討論 73 第四章 結論 78 參考文獻 79

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