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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
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  •  上一筆

    • 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.

    目錄 致謝 v 摘要 i Abstract iii 目錄 vii 圖目錄 xi 表目錄 xxi 第一章 緒論 1 1-1 前言 1 1-2 研究動機 2 第二章 文獻回顧 3 2-1 感測重金屬的重要性 3 2-2 感測重金屬的整理與分類 4 2-3 火焰式原子吸收光譜分析方法 5 2-4 X光螢光光譜儀分析法 5 2-5 電化學感測重金屬 6 2-5-1 生物感測器 6 2-5-2 電化學直接感測重金屬 8 2-6 鉍應用於感測重金屬 15 2-7 聚苯胺應用於感測重金屬 17 2-8 多層奈米碳管-聚苯胺共聚物應用於感測重金屬 19 2-9 利用微流道系統感測重金屬 20 第三章 實驗方法 23 3-1 實驗藥品 23 3-2 實驗設備 25 3-3 實驗方法 25 3-3-1 製備多層奈米碳管-聚苯胺 25 3-3-2 製備重金屬感測器 26 3-3-3 微流道注射系統 28 3-4 分析儀器與方法 30 3-4-1 傅立葉轉換紅外線光譜儀 (FTIR) 30 3-4-2 場發射電子顯微鏡 (FE-SEM) 30 3-4-3 X光繞射分析 (XRD) 30 3-5 電化學分析原理 31 3-5-1 電化學裝置 31 3-5-2 循環伏安法 (cyclic voltammetry) 33 3-5-3 方波溶出伏安法 (square wave stripping voltammetry) 34 第四章 結果與討論 37 4-1 製備多層奈米碳管聚苯胺 38 4-1-1 多層奈米碳管聚苯胺表面形態 38 4-1-2 多層奈米碳管聚苯胺官能基分析 39 4-1-3 多層奈米碳管-聚苯胺結晶型態 41 4-1-4 多層奈米碳管-聚苯胺粒子電化學特性 42 4-2 以陽極溶出伏安法感測鋅離子 48 4-3 以陽極溶出伏安法同時感測鋅、鎘、鉛 67 4-4 比較於不同系統下感測鋅離子 69 4-5 本研究與其他文獻感測重金屬離子(鋅、鎘、鉛)之比較 70 4-6 利用陰極吸附剝離伏安法感測鎳離子 72 4-6-1 累積電壓對感測鎳離子的影響 72 4-6-2 以GCE感測鎳離子 73 4-6-3 以SPE感測鎳離子 75 4-6-4 以MWCNTs-PANI/SPE感測鎳離子 77 4-6-5 以Bi/MWCNTs-PANI/SPE感測鎳離子 79 4-7 微流道系統感測重金屬離子 81 4-7-1 流速對感測鎘離子的影響 81 4-7-2 沉積時間對感測鎘離子的影響 83 4-7-3 微流道系統感測鎘離子 84 第五章 結論與未來展望 87 5-1 結論 87 5-2 未來展望 88 第六章 參考文獻 89 第七章 問題與討論 99     圖目錄 Fig. 2-1 Schematic illustration of DNAzyme-based electrochemical sensor [39]. 6 Fig. 2-2 Amperometric current responses of HRP/PANI/Pt electrode to successive additions of 10 μL, 0.05 mM of hydrogen peroxide (curve r). After 2000 sec, 4.76 ppb cadmium ions was added (curve i) per 100 sec. At potential: -0.2 V; supporting electrolyte: 0.1 M PBS (pH 7.02) [43]. 7 Fig. 2-3 Metals and semi-metals that can be determined by stripping ananlysis (in italics are the species that are normally determined only after electrolytic accumulation, underlined are the species that are normally determined after non-electrolytic accumulation and in bold are the species that can be determined after either electrolytic or nonelectrolytic accumulation) [46]. 9 Fig. 2-4 Modes of accumulation in stripping ananlysis of metals. (A) Metal ions was electrolytic accumulation on the electrode. (B) Metal ions complex was adsorb on the electrode. (C) Metal ions accumulated on the electrode by chemically modified [46]. 10 Fig. 2-5 (A) The stripping curve and (B) the corresponding calibration curve of zinc, cadmium and lead detected by Hg-Bi/SWNTs/GCE at different concentrations (from a to h was 0, 10, 30, 50, 70, 90, 110, and 130 ppb, respectively) [45]. 11 Fig. 2-6 BIA-ASV measurements for the analysis of a fuel bioethanol sample before (a) and after addition of (b) 25; (c) 50; (d) 100 (e) 150; (f) 200 and (g) 250 ppb zinc by gold disk macroelectrode. Insert: respective calibration curve [48]. 12 Fig. 2-7 The adsorptive cathodic stripping voltammetry curve for detection of nickel ions by Bi-AuE in 0.1 M ammonia buffer solution (pH 9.0) containing 10 ppm Bi (III), 10-5 M DMG. Dash line was shown the blank stripping peak and the solid curve was shown the stripping peak of 50 ppb nickel ions at -0.96 V [44]. 13 Fig. 2-8 (A) The morphology of the screen-printed Bi nanoparticle porous C composite electrode. (B) Square wave anodic stripping voltammetry signals recorded in standard acetate buffer solutions containing 0, 10, 50 ppb of both Pb (II) and Cd (II) with SPEs without Bi nanoparticles (C-SPE) (a1 to a3), and Bi-C SPEs (b1 to b3). Electrodeposition was carried out at −1.7 V for 90 s and at −1.7 V for 300 s with Bi-C SPEs and C-SPEs, respectively [60]. 15 Fig. 2-9 Differential pulse stripping voltammetry of 30 mgL-1 each of Zn2+, Cd2+ and Pb2+ in 0.1 M acetate buffer (pH 4.0) at (c) MWCNTs/nafion/SPE, (b) nafion/Bi/SPE and (a) MWCNTs/nafion/Bi/SPE. Deposition potential: -1.35 V, deposition time: 120 s. Bismuth film plated in situ with the concentration 400 ppb [63]. 16 Fig. 2-10 The structure emeraldine salt form of PANI [66]. 17 Fig. 2-11 Sqare wave anodic stripping voltammetrys of 25 nM Cd2+ and 25 nM Pb2+ in solutions containing 20 mM H2SO4 and 30 mM KCl measured from: (a) bare GCE, (b) PANI/GCE prepared by cyclic voltammetry, (c) PANI/GCE prepared by multipulse potentiostatic method, and (d) Bi/PANI/GCE [56]. 18 Fig. 2-12 Voltammograms of different coatings for determination of Pb2+ (310.5 ppb) in 0.1 M acetate buffer solution. (a) bare GCE, (b) PANI was coated by electrochemistry methods (ECM) on GCE, (c) MWCNT-COOH was coated by ECM on GCE, (d) MWCNT-CO-PANI was coated by ECM on GCE, (e) MWCNT-CO-PANI was prepared and dropped on GCE [70]. 19 Fig. 2-13 Photograph of the three-electrode microchip [75]. 20 Fig. 2-14 (A) Stripping analysis and (B) standard addition plot for adding different concentrations of Cd2+ and Pb2+ to the seawater (R2=0.9996 and R2=0.9988 for Cd2+ and Pb2+, respectively). Standard solutions of Cd2+ and Pb2+ are added in 1.0, 2.0, 4.0, 6.0 and 8.0 ppm increments to the sample. The anodic stripping was performed using electrodeposition at -0.9 V for 10 s and subsequent scanning from -0.9 to 0.2 V at a scan rate of 0.1 V/s and a flow rate of 10.0 mL/min [75]. 20 Fig. 2-15 (a) Typical voltammograms and (b) calibration plots for the microfabricated three-electrode on-chip device in simultaneous detection of Cd2+ and Pb2+ ions (n=3) [74]. 21 Fig. 3-1 Schematic of synthesizing MWCNTs-PANI. Step 1 was made aniline monomer adsorp on (a) MWCNTs to become (b) aniline-MWCNTs. Aniline which on the MWCNTs was polymerized by adding APS to become (c) PANI-MWCNTs. 26 Fig. 3-2 The schemetic of (a) The disposable electrode SPE drop (b) the 10 wt% 1:33 MWCNTs-PANI composite 5 μL on electrode and (c) 200 ppb bismuth was deposited on MWCNTs-PANI/SPE by electroplating method. 27 Fig. 3-3 The disposable electrode 3-SPE (a) insert to microfluidic chip (b) and the solution flow rate would be adjust by syringing pump (c). 29 Fig. 3-4 The microfluidic chip. 29 Fig. 3-5 Schematic of Bragg's Law 31 Fig. 3-6 (a) Glassy carbon electrode (b) screen printed electrode 32 Fig. 3-7 Disposable screen printed three electrode 32 Fig. 3-8 Cyclic potential sweep. 33 Fig. 3-9 Resulting cyclic voltammogram 33 Fig. 3-10 The potential change of stripping voltammetry. 35 Fig. 3-11 The potential change by square wave anodic stripping voltammetry [2]. 35 Fig. 4-1 The morphology of synthesized MWCNTs-PANI with different rations between MWCNTs and PANI: (a) pure MWCNTs, (b) 1:4 MWCNTs:PANI, (c) 1:33 MWCNTs-PANI, (d) 1:50 MWCNTs-PANI, and (e) pure PANI. 38 Fig. 4-2 FTIR spectum of synthsized (a) PANI and the ration of MWCNTs and PANI was (b) 1:33 MWCNTs-PANI. 39 Fig. 4-3 The crystallinity of (a) pure MWCNTs, (b) 1:4 MWCNTs:PANI, (c) 1:33 MWCNTs:PANI, (d) 1:50 MWCNTs:PANI, and (e) pure PANI, analyzed by XRD. 41 Fig. 4-4 Cyclic voltammograms of 10 mM ferricyanide at (a) MWCNTs-PANI modified on O2 plasma pretreatment SPE, (b) MWCNTs-PANI modified on without O2 plasma pretreatment SPE, and (c) bare SPE. O2 plasma pretreatement under 40 W and 100 mtorr for 60 sec. 43 Fig. 4-5 (A) Cyclic voltammograms of 10 mM ferricyanide at MWCNTs-PANI/SPE under scan rate from 10 to 200 mV/s, and (B) Linearity of oxidation peak current verse square root scan rate. 45 Fig. 4-6 Cyclic voltammograms of 10 mM ferricyanide at (a) modified MWCNTs-PANI/SPE, (b) deposit 200 ppb bismuth on modified MWCNTs-PANI/SPE, and (c) bare SPE under scan rate 0.1 v/s 47 Fig. 4-7 Detection of zinc ions in 0.1 M ABS in pH 3 to 6 by square wave anodic stripping voltammetry (SWASV) method using GCE. Deposition potential: -1.5 V; deposition time: 120 s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV. 49 Fig. 4-8 The current response of 5 μM zinc ions in 0.1 M PBS in pH 6 and 7 compare to pH 6 acetate buffer solution by SWASV using GCE. Deposition potential: -1.5 V; deposition time: 120 s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV. 49 Fig. 4-9 The effects of deposition time for detection of 5 μM zinc ions by SWASV using GCE. Supporting electrolyte: 0.1 M acetate buffer solution, pH 6; deposition potential: -1.5 V; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV. 50 Fig. 4-10 The effects of deposition potential for detection of 5 μM zinc ions by SWASV using GCE. Supporting electrolyte: 0.1 M acetate buffer solution, pH 6; deposition time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV. .....................................................................................................................51 Fig. 4-11 (A) SWASV on bare GCE in solution containing 0 to 200 ppb zinc ions. (B) The calibration curves for determination of zinc ions of different concentrations. Supporting electrolyte: 0.1 M acetate buffer solution, pH 6; deposition potential: -1.5 V; deposition time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV; scan potential: -1.5 to -0.2 V 53 Fig. 4-12 (A) SWASV on PANI/GCE in solution containing 0 to 200 ppb zinc ions. (B) The calibration curves for determination of zinc ions of different concentrations. Supporting electrolyte: 0.1 M acetate buffer solution, pH 6; deposition potential: -1.5 V; deposition time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV; scan potential: -1.5 to -0.2 V 55 Fig. 4-13 (A) SWASV on MWCNTs-PANI/ GCE in solution containing 0 to 200 ppb zinc ions. (B) The calibration curves for determination of zinc ions of different concentrations. Supporting electrolyte: 0.1 M acetate buffer solution, pH 6; deposition potential: -1.5 V; deposition time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV; scan potential: -1.5 to -0.2 V 57 Fig. 4-14 The effects of deposition potential for detection of 200 ppb zinc ions by SWASV using SPE. Supporting electrolyte: 0.1 M acetate buffer solution, pH 6; deposition time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV. ……………………………………………………………………………58 Fig. 4-15 Effects of modified MWCNTs-PANI amount on SPE for detection of zinc ions by SWASV. Supporting electrolyte: 0.1 M acetate buffer solution, pH 6; deposition potential: -1.3 V; deposition time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV. 59 Fig. 4-16 Effects of the bismuth deposited concentration on MWCNTs-PANI/ SPE for detection of zinc ions by SWASV. Supporting electrolyte: 0.1 M acetate buffer solution, pH 6; deposition potential: -1.3 V; deposition time for detect zinc ions: 180 s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV. 60 Fig. 4-17 (A) Squre wave anodic stripping voltammetry on bare SPE in solution containing 0 to 200 ppb zinc ions. (B) The calibration curves for determination of zinc ions of different concentrations. Supporting electrolyte: 0.1 M acetate buffer solution, pH 6; deposition potential: -1.3 V; deposition time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV; scan potential: -1.3 to -0.2 V 62 Fig. 4-18 (A) Squre wave anodic stripping voltammetry on MWCNT-PANI/ SPE in solution containing 0 to 200 ppb zinc ions. (B) The calibration curves for determination of zinc ions of different concentrations. Supporting electrolyte: 0.1 M acetate buffer solution, pH 6; deposition potential: -1.3 V; deposition time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV; scan potential: -1.3 to -0.8 V. 64 Fig. 4-19 (A) Squre wave anodic stripping voltammetry on Bi/ MWCNTs-PANI/ SPE in solution containing 0 to 200 ppb zinc ions. (B) The calibration curves for determination of zinc ions of different concentrations. Supporting electrolyte: 0.1 M acetate buffer solution, pH 6; deposition potential: -1.3 V; deposition time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV; scan potential: -1.3 to -0.8 V. 66 Fig. 4-20 (A) Squre wave anodic stripping voltammetry on Bi/ MWCNTs-PANI/ SPE in solution containing 0 to 200 ppb zinc, cadmium, and lead ions. (B) The calibration curves for determination of zinc, cadmium, and lead ions of different concentrations. Supporting electrolyte: 0.1 M acetate buffer solution, pH 6; deposition potential: -1.3 V; deposition time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV; scan potential: -1.3 to -0.2 V. 68 Fig. 4-21 Comparison of different system detect zinc ions by SWASV. Supporting electrolyte: 0.1 M acetate buffer solution, pH 6; deposition potential: -1.3 V; deposition time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV. 69 Fig. 4-22 The current response of 100 ppb nickel ions and sensitivity affected by accumulation potential under 0.1 M ammonium buffer (pH: 9) which containing 1.25 × 10-4 M DMG by sqare wave adsorptive cathodic stripping voltammetry using GCE. Accumulation time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV. 72 Fig. 4-23 (A) Squre wave adsorptive cathodic stripping voltammetry (SWAdCSV) on bare GCE in solution containing 0 to 200 ppb nickel ions. (B) The calibration curve for determination of nickel ions of different concentrations. Supporting electrolyte: 0.1 M ammonium buffer solution containing 1.25 × 10-4 M DMG, pH 9; accumulation potential: 0.1 V; accumulation time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV; scan potential: 0.1 to -1.3 V. 74 Fig. 4-24 (A) SWAdCSV on bare SPE in solution containing 0 to 200 ppb nickel ions. (B) The calibration curve for determination of nickel ions of different concentrations. Supporting electrolyte: 0.1 M ammonium buffer solution containing 1.25 × 10-4 M DMG, pH 9; accumulation potential: 0.1 V; accumulation time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV; scan potential: 0.1 to -1.3 V. 76 Fig. 4-25 (A) SWAdCSV on MWCNTs-PANI/ SPE in solution containing 0 to 200 ppb nickel ions. (B) The calibration curve for determination of nickel ions of different concentrations. Supporting electrolyte: 0.1 M ammonium buffer solution containing 1.25 × 10-4 M DMG, pH 9; accumulation potential: 0.1 V; accumulation time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV; scan potential: 0.1 to -1.3 V. 78 Fig. 4-26 (A) SWAdCSV on Bi/MWCNTs-PANI/SPE in solution containing 0 to 200 ppb nickel ions. (B) The calibration curve for determination of nickel ions of different concentrations. Supporting electrolyte: 0.1 M ammonium buffer solution containing 1.25 × 10-4 M DMG, pH 9; accumulation potential: 0.1 V; accumulation time: 180s; fequency: 20 Hz; amplitude: 25 mV; step size: 5 mV; scan potential: 0.1 to -1.3 V. 80 Fig. 4-27 Detection of 500 ppb cadmium with flow rate from 0 to 300 μl/min by ASV using SPE under deposition time 600 s, deposition potential -1.3 V. Supporting electrolyte: 0.1 M acetate buffer solution, pH 6; frequency: 20 Hz; amplitude: 25 mV; step size: 5 mV; scan potential: -1.3 to -0.6 V. 82 Fig. 4-28 Effects of deposition time under 100, 500, 1000, 2000 ppb cadmium ions with the flow rate 250 μl min-1. Supporting electrolyte: 0.1 M ABS, pH 6; frequency: 20 Hz; amplitude: 25 mV. 83 Fig. 4-29 (A) SWASV for detection of cadmium by microfluidic system with the flow rate 250 μl min-1 and deposition time 600 s. (B) The calibration curve for detect cadmium by microfluidic system. Supporting electrolyte: 0.1 M ABS, pH 6; frequency: 20 Hz; amplitude: 25 mV; step size: 5 mV; scan potential: -1.3 to -0.2 V. 85     表目錄 Table 2-1 Comparison of different sensing heavy metal method 4 ppm (parts per million): 10-3 mg/L, ppb (parts per billion): 10-6 mg/L, ppt (parts per trillion): 10-9 mg/L 4 Table 2-2 Detection of heavy metal ions by anodic stripping voltammetry. 13 Table 2-3 Detection of heavy metal ions by Adsorptive cathodic stripping voltammetry. 14 Table 3-1 Experimental chemicals 23 Table 4-1 The functional group of synthesized PANI. 40 Table 4-2 The electroactive area of various electrodes. 43 Table 4-3 The electroactive area of various electrodes. 47 Table 4-4 Comparison for detection of heavy metal by ASV. 70

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