本研究的主要目的是利用微波電漿氣相化學沉積法之技術自製導電鑽石薄膜電極，探討導電鑽石薄膜電極製程參數對電化學行為的影響，並且用電化學方法將奈米白金顆粒修飾導上電鑽石薄膜電極來偵測環境毒物-砷(III)。由於導電鑽石薄膜電極在電分析化學上比傳統電極有更多的優點包括耐久性、電導性、優良的化學惰性、較低的背景電流、較廣的偵測電位、抗熱、抗酸...等特性。所以發展導電鑽石薄膜電極來當做工作電極。
    導電鑽石薄膜電極製備在1500W微波功率、55torr氣體總壓、氫氣流速300sccm、甲烷流速50sccm、B(OCH3)3流速5sccm下，並施加-125V直流偏壓成核20分鐘、成長180分鐘即完成電極製備，此導電鑽石薄膜電極對1mM K3Fe(CN)6在循環伏安法的反應其標準偏差值為3.13% (n=8)。
電化學實驗選擇奈米白金修飾導電鑽石電極以計時安培法(Chronoamperomtric)進行環境毒物-砷(III)的偵測，利用循環伏安法在1.2～-0.2V電位區間以50 mV/sec的掃描條件下連續掃描20分鐘以修飾上奈米白金顆粒，偵測環境為0.1M pH4 醋酸緩衝溶液，偵測電位為0.8V (vs. Ag/AgCl)，前處理電位0.2V (vs. Ag/AgCl)，前處理時間15秒，偵測取樣時間為5秒。線性範圍0.1～100 (R=0.998)，靈敏度為273.25μA/mM，本系統的偵測極限(S/N=3)為16.7 nM，重複操作的相對標準偏差為1.013%(n=20)。

Conductive boron-doped diamond (BDD) electrode has attracted intensive attention recently. This prominent new material possess characteristics like its high electronic conductivity, excellent chemical inertness, a wide potential window, small residual current, as well as physical and chemical stability. This home-made BDD electrode, prepared by utilizing microwave plasma enhanced chemical vapor deposition (MPECVD) making electrode, is widely used for the detection environmental and biological samples.
A new scheme to measure Arsenic(III) with platinum nanoparticle modified boron doped diamond electrode was proposed by using chronoamperometry at the optimum conditions at buffer solution : 0.1M, pH4 acetate buffer; initial potential: 200mV(vs. Ag/AgCl) applied 20 seconds；detection potential: 800 mV(vs. Ag/AgCl);  sampling time: 5sec. The sampling time in chronoamperometry was sampling at the 5th second after the potential step. According to optimum operation conditions, the linear range of Arsenic(III) is obtained between 10 to 100 μM (R=0.998), and its sensitivity is 273.25 μA/mM with estimated detection limited about 16.7 nM (S/N=3). The relative standard deviation of twenty repetitive detections is 1.013%.

1-1 硼摻雜奈米鑽石電極薄膜在電化學分析上的應用………………1
1-1-1 簡介……………………………………………………………1
1-1-2 鑽石電極薄膜的特性…………………………………………2
1-1-3 鑽石薄膜及導電鑽石薄膜之合成及成長理論………………3
1-1-4 導電鑽石電極薄膜在電化學分析上的應用…………………5
     (1) 流動注射系統結合電化學偵測(FIA-EC)…………………5
     (2) 液相層析結合電化學偵測(HPLC-EC)……………………7
     (3) 毛細管電泳結合電化學偵測(CE-EC)及毛細管電泳晶片結合電化學偵測(CE-Chip-EC)…………………………………………9
     (4) 安培法(Amperometric)……………………………………10
     (5) 電位法(Potentiometric)…………………………………13
     (6) 其他電化學應用……………………………………………14
1-1-5  鑽石微電極……………………………………………………17
1-2砷……………………………………………………………………19
1-2-1 簡介……………………………………………………………19
1-2-2 砷在自然界中的分佈及其物種………………………………20
1-2-3 砷的毒理效應…………………………………………………21
1-2-4 砷、腐質酸與烏腳病…………………………………………23
1-2-5砷物種分析方法
(1)光譜法……………………………………………………………25
(2)高效能液相層析法………………………………………………25
(3)毛細管電泳法……………………………………………………26
(4)中子活化法………………………………………………………27
(5)電化學分析法……………………………………………………27
1-3化學修飾電極………………………………………………………28
1-3-1化學吸附法………………………………………………………29
1-3-2共價鍵結法………………………………………………………31
1-3-3高分子薄膜塗佈法………………………………………………33
1-3-4非均相材料混合塗佈法…………………………………………36
1-4修飾電極常見之特性及功能………………………………………39
 1-4-1 電催化…………………………………………………………39
 1-4-2 預濃縮…………………………………………………………40
 1-4-3薄膜阻隔………………………………………………………42
 1-4-4電釋放…………………………………………………………43
1-5本研究的目的………………………………………………………45

第二章	實驗部分

2-1 part I：硼摻雜鑽石薄膜電極製備條件與程序之探討
   2-1-1 儀器…………………………………………………………46
   2-1-2 藥品…………………………………………………………47
   2-1-3 鍍膜步驟……………………………………………………47
   2-1-4 硼摻雜鑽石電極製作條件之設計…………………………49
        (1) 摻雜源B(OCH3)3流速之探討…………………………49
        (2) 氣體CH4流速之探討……………………………………49
        (3) 直流偏壓之探討………………………………………49
        (4) 成長時間之探討………………………………………50
2-2 partII：奈米白金修飾硼摻雜鑽石薄膜電極電化學偵測砷(III)
   2-2-1 儀器…………………………………………………………50
   2-2-2 藥品…………………………………………………………50
   2-2-3白金修飾硼摻雜鑽石薄膜電極之製備……………………51
   2-2-4實驗條件之設計……………………………………………51
      2-2-4-1 反應機構之探討……………………………………51
      2-2-4-2 溶液酸鹼值之探討…………………………………51
      2-2-4-3 偵測電位之探討……………………………………51
      2-2-4-4 前處理電位之探討…………………………………51
      2-2-4-5 前處理時間之探討…………………………………52
      2-2-4-6 緩衝溶液種類之探討………………………………52
      2-2-4-7 緩衝溶液濃度之探討………………………………52
      2-2-4-8 分析特性之探討……………………………………52
第三章	結果與討論

3-1-1 硼摻雜導電鑽石電極製程參數之探討……………………53
           (1) 摻雜源B(OCH3)3流速之探討………………………53
           (2) 氣體CH4流速之探討………………………………54
           (3) 直流偏壓之探討……………………………………54
           (4) 成長時間之探討……………………………………55
           (5) 製程穩定性之探討…………………………………55
3-1-2 導電鑽石薄膜電極之分析……………………………………62
3-2-1 偵測機制及CV的探討…………………………………………64
3-2-2 奈米白金修飾導電鑽石薄膜電極製備法之探討……………65
3-2-3 分析最佳化的之探討…………………………………………71
          (1) 溶液酸鹼值之探討…………………………………71
          (2) 偵測電位之探討……………………………………71
          (3) 前處理電位之探討…………………………………75
          (4) 前處理時間之探討…………………………………75
          (5) 緩衝溶液種類之探討………………………………78
          (6) 緩衝溶液濃度之探討………………………………78
    3-2-4 分析特性之探討…………………………………………81
    3-3  結論………………………………………………………84

圖表目錄

圖(一) 硼流速之探討…………………………………………………56
圖(二) 甲烷流速之探討………………………………………………57
圖(三) 直流偏壓之探討………………………………………………58
圖(四) 導電鑽石薄膜電極之SEM圖…………………………………59
圖(五) 成長時間之探討………………………………………………60
圖(六) 導電鑽石薄膜鍍膜製程之相對標準偏差值…………………61
圖(七) 導電鑽石薄膜電極之拉曼光譜圖……………………………63
圖(八)循環伏安法圖譜500 μM As(III) 在0.1M硫酸溶液(a)空白導電鑽石薄膜電極 (b) 奈米白金修飾導電鑽石薄膜電極……………66
圖(九) 循環伏安法圖譜500 μM As(III)在0.1M硫酸溶液中，導電鑽石薄膜電極修飾白金顆粒在不同掃描範圍…………………………67
圖(十) 比較不同沉積時間奈米白金修飾導電鑽石電極之S/B值…68
圖(十一)比較奈米白金修飾導電鑽石電極及傳統白金電極之S/B值69
圖(十二) 奈米白金修飾導電鑽石薄膜電極之SEM圖………………70
圖(十三) 循環伏安法量測下，pH對氧化峰電位之探討……………72
圖(十四) 溶液之酸鹼值的探討………………………………………73
圖(十五) 偵測電位之探討……………………………………………74
圖(十六) 前處理電位之探討…………………………………………76
圖(十七) 前處理時間之探討…………………………………………77
圖(十八) 緩衝溶夜種類之探討………………………………………79
圖(十九) 緩衝溶夜濃度之探討………………………………………80
圖(二十) 本系統對於砷(III)分析的校正曲線……………………82
圖(二十一) 偵測砷(III)系統之穩定性……………………………83


表(一) 導電鑽石薄膜電極製作最佳化條件…………………………62
表(二) 實驗操作的最佳化條件………………………………………81
表(三) 砷(III)偵測系統之分析特性………………………………86
表(四) 砷(III)偵測方法比較………………………………………87

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