研究生: |
余宛樺 Wan-Hua Yu |
---|---|
論文名稱: |
製備重金屬感測器應用於批次及微流道偵測系統 Preparation of Electrochemistry Sensors for Heavy Metal Ions Detection in Batch and Microfluidic Systems |
指導教授: |
王孟菊
Meng-Jiy Wang |
口試委員: |
莊怡哲
Yi-Je Juang 陳克紹 Ko-Shao Chen 陳品銓 Pin-Chuan Chen 魏大欽 Ta-Chin Wei |
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: | 2016 |
畢業學年度: | 104 |
語文別: | 中文 |
論文頁數: | 126 |
中文關鍵詞: | 多層奈米碳管-聚苯胺 、重金屬 、溶出伏安法 、微流道 |
外文關鍵詞: | Multiwall carbon nanotube (MWCNTs), Stripping voltammetry |
相關次數: | 點閱:594 下載:0 |
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本論文研究目的為製備一次性重金屬感測器並固定多層奈米碳管-聚苯胺複合材料於電極表層以增加感測靈敏度,再以電鍍方式修飾鉍 (bismuth) 於修飾後電極的表層以降低析氫效應 (hydrogen evolution) 的產生,並將修飾後的電極 感測鋅、鎘、鉛及鎳並進行比較。
為了增加感測器靈敏度,本文的材料製備方面以化學合成方法將聚苯胺聚合於多層奈米碳管表面,並利用傅里葉轉換紅外線光譜 (FTIR)、X光繞射儀 (XRD)、場發射掃描式電子顯微鏡 (FE-SEM) 等儀器分析複合材料的官能基、結晶形態及表面形態。製備一次性重金屬感測器,修飾步驟為:利用氧氣電漿清潔電極表面及產生親水表面以利修飾多層奈米碳管-聚苯胺於電極表面時能均勻塗佈,再以電鍍法將鉍離子沉積於修飾後的電極表面,以降低在高電位下感測重金屬離子時會發生的析氫反應,而提高感測靈敏度。
本研究利用Bi/MWCNTs-PANI/SPE以方波陽極溶出伏安法 (square wave anodic stripping voltammetry) 感測單一鋅離子,感測靈敏度為9.05 μA ppb-1 cm-2 (5-50 ppb),高濃度時的感測靈敏度為1.91 μA ppb-1 cm-2 (50-200 ppb),實驗結果優於MWCNTs-PANI/GCE的感測靈敏度2.8 μA ppb-1 cm-2 (5-200 ppb),且以Bi/MWCNTs-PANI/SPE同時感測三種重金屬離子時鋅離子的感測靈敏度仍保有較感測單一鋅離子的81 %;本文亦利用MWCNTs-PANI/SPE以方波吸附陰極溶出伏安法 (square wave adsorptive cathodic stripping voltammetry) 感測鎳離子得到最好的感測靈敏度為0.751 μA ppb-1 cm-2。
為了符合市售產品化的需求,本論文最後一部分以三極式可拋棄碳電極結合微流道及注射式幫浦系統感測鎘離子,成功製備出重金屬感測器,感測線性範圍為50-1000 ppb,靈敏度為2.236 μA ppb-1 cm-2,偵測極限為15.2 ppb。
關鍵字:多層奈米碳管-聚苯胺、重金屬、溶出伏安法、微流道
In this study, electrochemical sensors were developed for the detection of heavy metal ions including zinc, cadmium, lead, and nickel in both batch and microfluidic systems. Two electrodes were applied for evaluating the electrochemical analyses: (i) glassy carbon electrode (GCE), and screen printed carbon electrode (SPE). In order to achieve higher sensitivity, the electrodes were modified with multi-wall carbon nanotubes (MWCNTs) mixed with polyaniline (PANI) (MWCNTs-PANI), or further integrating with bismuth (Bi/MWCNTs-PANI). The rationale of incorporating bismuth, facilitated by electrochemical deposition method, is to reduce the hydrogen evolution.
The functionalities, crystallinity, and morphology of MWCNTs-PANI were characterized by FTIR, XRD, and FE-SEM. To detect zinc, cadmium, and lead ions by square wave anodic stripping voltammetry (SWASV), the optimized conditions were obtained to be at the deposition potential of -1.5 V for GCE, -1.3 V for SPE. In addition, the deposition time was optimize to be 180 s in acetate buffer solution (0.1 M, pH 6.0).
The MWCNTs-PANI/GCE revealed the good sensitivity of 2.8 μA ppb-1 cm-2 for the detection of zinc ions with the linear range between 5 - 200 ppb, and the limit of detection (LOD) of 2.85 ppb. On the other hand, the Bi/MWCNTs-PANI/SPE was applied to detect Zn2+, Cd2+, and Pb2+ that two linear ranges were generally observed and the sensitivity was 7.367, 9.25, and 3.516 (μA ppb-1 cm-2) at lower concentration range. The linear range is 5-50 ppb for Zn2+ and Cd2+ and 30-80 ppb for Pb2+. For the detection at higher concentration, the second linear range was found to be 50-200 ppb for Zn2+ and Cd2+ and 80-200 ppb for Pb2+, that the sensitivity 1.913, 1.854, and 2.078 μA ppb-1, respectively.
On the other hand, the square wave adsorptive cathodic stripping voltammetry method was applied to detect nickel ions. The optimized parameters were at the deposition potential of 0.1 V and the deposition time for 180 s in ammonium buffer solution (at pH 9.0). The MWCNTs-PANI/SPE revealed the better sensitivity of 0.751 μA ppb-1 cm-2 with the linear range of 5 - 200 ppb for nickel ions detection.
Finally, the microfluidic system was applied for metal ions detection for the purpose of reducing sample consumption. The square wave anodic stripping voltammetry parameters were optimized, on line simultaneous determination of cadmium was performed and analytical curve were linearly acquired in the concentration range from 50-1000 ppb with the sensitivity 2.236 μA ppb-1 cm-2 and limit of detection was 15.2 ppb.
Keywords: Multiwall carbon nanotube (MWCNTs); Polyaniline; Composite; Stripping voltammetry; Heavy metal; Microfluidic.
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