臺灣博碩士論文加值系統

本研究使用電化學電鍍法製備Ni-Pt薄膜，以電化學技術配合其他材料分析方法針對以下四個主題進行探討：(1)Ni-Pt之電化學式電流酒精感測器的效能；(2)Ni-Pt之酒精感測的反應動力行為；(3)Ni-Pt薄膜中Ni(OH)2/NiOOH相態轉變之電化學時效性質；(4)電化學氧化還原反應與酒精氧化反應過程中Ni-Pt薄膜電極之Ni(OH)2生成效率與內部結構的關係。經由實驗結果之觀察與數據分析可獲得各部分之主要結果，分別簡述如下。
在酒精感測效能方面，在鹼性溶液中於520 mV之感測電位下隨著Pt添加量的增加，平均靈敏度呈現下降而平均應答時間則縮短。Pt的添加有助於減緩靈敏度隨時間增加而下降的現象，改善穩定性之惡化，其中70 at %Pt含量的薄膜在63天之穩定性測試期間具有相對較好的穩定性。Ni-Pt薄膜對於甲醇、葡萄糖、維他命C的選擇性不佳，會產生極大的干擾訊號。
在酒精氧化動力學方面，Pt之添加雖然沒有增進酒精氧化反應速率，卻可提高Ni(OH)2/NiOOH電化學反應速率，可加快酒精感測速率，有助於縮短應答時間。當施加電位大於0.63 V時，Ni(OH)2/NiOOH在Ni-Pt薄膜之反應速率較在Ni薄膜上快速。添加Pt可有效抑制Ni(OH)2/NiOOH反應過程中氧化物之生成及薄膜電阻的增加，可減低薄膜的電化學反應電位隨著掃描速率的增加而提高的現象，有較好的可逆性。
在Ni(OH)2/NiOOH相態轉變方面，Ni(OH)2在Ni-Pt薄膜中隨著電化學掃描的進行持續成長並轉變成β-NiOH)2，而長時間電化學氧化還原掃描會加速α-Ni(OH)2轉變為β-NiOH)2。Pt之添加會減緩α-Ni(OH)2轉變為β-NiOH)2之速率；而厚度愈厚之Ni-Pt薄膜在電化學掃描過程中會產生較多比例的α-Ni(OH)2，阻礙薄膜中β-NiOH)2之轉變，有助穩定α-Ni(OH)2。置於KOH水溶液中之時效時間愈長，有助於Ni(OH)2成長轉變為β-NiOH)2。在潮濕的O2氣氛中，H2O與O2會在薄膜中與Ni形成額外的Ni(OH)2。經過長時間的酒精氧化過程之後，薄膜中的Ni(OH)2相態為β-NiOH)2，但仍含少數的α-Ni(OH)2。Ni-Pt薄膜中的β-NiOH)2相態可穩定保存於KOH水溶液中，有助穩定β-NiOH)2，但會因潮濕空氣中H2O與O2之插入而破壞β-NiOH)2的相態，並形成α-Ni(OH)2。
在Ni(OH)2生成效率與內部結構的關係上，隨著Pt的含量增加，造成Ni原子的分散及晶格結構的改變。可發現Ni(OH)2在不同Pt含量的薄膜電極中的形成速率互不相等，Ni-Pt薄膜電極中的Ni能夠有效率地形成Ni(OH)2；而純Ni薄膜的Ni(OH)2形成效率相對較差。

In this research, Ni-Pt thin films were prepared by the electrochemical deposition method. The experiment data were analyzed and presented by electrochemical method (ex: cyclic voltammetry and linear voltammetry), XRD, SEM, ICP-MS, EQCM, WDS, nano-AEM and XAS. The experiments are divided into four part of themes including: (1) the performance of electrochemically amperometric ethanol sensor with Ni-Pt thin films; (2) the electrochemistry and reaction kinetics of sensing ethanol on Ni-Pt thin films; (3) the electrochemical aging effect on the phase transformation of Ni(OH)2/NiOOH in the Ni-Pt thin films; (4) the rate of producing Ni(OH)2 on the Ni-Pt films and structure effect of Ni-Pt thin films. The results are summarized as follows briefly.
For the performance of ethanol sensor with Ni-Pt thin films, the sensitivity decreased with the increase of Pt content of the Ni-Pt thin film in KOH solution at the applied potential of 520 mV. The response time of sensing ethanol decreased with the increase of Pt content. The addition of Pt could reduce the decline of sensitivity with time and improved the stability of sensing ethanol. In addition, the Ni-Pt thin film which contained 70 at % Pt had best stability during 63 days. The Ni-Pt presented bad selectivity toward the interferences such as methanol, glucose and vitamins C.
For kinetics behavior of sensing ethanol on Ni-Pt thin films, although the addition of Pt in Ni-Pt thin films could not aid the rate of ethanol oxidation with NiOOH. It could promote the rate for electrochemical reaction of Ni(OH)2/NiOOH and accelerate the rate of sensing ethanol further. This could help to reduce response time. The rate of Ni(OH)2/NiOOH redox reaction would be faster than that on pure Ni film at the applied potential which is more than 0.63 V. Furthermore, the oxide which may increase the resistance of the Ni films could be restrained by the addition of Pt during Ni(OH)2/NiOOH redox reaction. This could reduce the increase of the potential of Ni(OH)2/NiOOH redox reaction with the increase of scan rate.
For the phase transformation of Ni(OH)2/NiOOH in the Ni-Pt thin films, Ni(OH)2 gradually grew and concerted to β-Ni(OH)2 in the Ni-Pt thin films during cyclic voltammetry. The rate of Ni(OH)2 converting to β-Ni(OH)2 could be accelerated with long-time cyclic voltammetry of Ni(OH)2/NiOOH. The addition of Pt could reduce the rate of Ni(OH)2 converting to β-Ni(OH)2 in Ni-Pt thin films. The thicker the Ni-Pt films were, the more the films contained the amount of α-Ni(OH)2. This fact also hindered the transformation of Ni(OH)2 to β-Ni(OH)2 in the Ni-Pt thin films. These are helpful to stabilize in α-Ni(OH)2. Aging in KOH solution for a long time could assist Ni(OH)2 in transforming to β-Ni(OH)2 in Ni-Pt films. Some H2O and O2 would enter into the Ni-Pt films to form extra amount of Ni(OH)2 while aging in a humid O2 environment. After long time of ethanol oxidation, the phase of most Ni(OH)2 in the Ni-Pt films was β-Ni(OH)2 although the films still contained a little number of α-Ni(OH)2. The phase of β-Ni(OH)2 in the Ni-Pt films could be stable in KOH solution rather than in a humid O2 environment where the structure of β-Ni(OH)2 may be destroyed by H2O an O2.
For rate of producing Ni(OH)2 and structure of the films, dispersion of nickel atom and structural change arose from the addition of Pt in the films. Various producing rates of Ni(OH)2 were found in the films of different content of Pt. Ni atoms were efficiently oxidized to Ni(OH)2 in the Ni-Pt films. However, Ni atoms were inefficiently formed to Ni(OH)2 during cyclic voltammetry.

摘要…………………………………………………………………………I
Abstract..........................................III
致謝…………………………………………………………………………VI
目錄…………………………………………………………………………IX
表目錄……………………………………………………………………..XIV
圖目錄……………………………………………………………………..XV
第一章 緒論…………………………………………………………………1
1.1 研究背景……………………………………………………………1
1.2 電化學式電流酒精感測器……………………………………………1
1.3 電化學觸媒之發展……………………………………………………4
1.4 鎳金屬於酒精氧化之研究發展………………………………………5
1.5 Ni(OH)2與NiOOH之研究回顧……………………………………….7
1.6 研究目的………………………………………………………………9
第二章 理論基礎…………………………………………………………...22
2.1 酒精感測器…………………………………………………………..22
2.1.1 電化學式電流酒精感測器之原理……………………………...22
2.1.2 感測器之特性…………………………………………………...23
2.1.3 酒精氧化之質傳控制模式……………………………………...26
2.2 酒精感測之反應動力行為…………………………………………..28
2.2.1 酒精氧化之反應機制…………………………………………...28
2.2.2 酒精氧化動力方程式之推導…………………………………...30
2.3 Ni(OH)2/NiOOH之相態轉換理論…………………………………...34
2.3.1 Ni(OH)2/NiOOH之轉換機制與質量變化………………………34
2.3.2電化學石英晶體微量天平之量測原理…………………………36
2.4 X光吸收光譜…………………………………………………………38
2.4.1 同步輻射光源…………………………………………………...38
2.4.2 X光吸收光譜之原理……………………………………………40
第三章 實驗方法與步驟…………………………………………………...67
3.1 藥品與儀器設備……………………………………………………..67
3.2 酒精感測實驗………………………………………………………..67
3.2.1 電極製備………………………………………………………...67
3.2.2 酒精感測系統與步驟…………………………………………...68
3.2.3 低掠角X光繞射分析…………………………………………..70
3.2.4 掃描式電子顯微鏡分析………………………………………...71
3.3 酒精氧化之反應動力行為分析……………………………………..72
3.3.1 旋轉電極製備…………………………………………………...72
3.3.2 電化學掃描分析………………………………………………...73
3.3.2.1 循環伏安法分析……………………………………………74
3.3.2.2 慢速線性伏安法分析………………………………………75
3.3.3 感應耦合電漿質譜儀…………………………………………...75
3.4 Ni(OH)2/NiOOH相態分析…………………………………………...76
3.4.1 石英晶片薄膜電極之製備……………………………………...76
3.4.2 EQCM實驗分析…………………………………………………77
3.4.2.1 長時間之循環伏安掃描分析………………………………77
3.4.2.2 不同條件之時效處理分析…………………………………79
3.4.3 X光波長散佈分析儀……………………………………………80
3.4.4 奈米級歐傑電子能譜儀………………………………………...81
3.5 X光吸收光譜分析……………………………………………………81
3.5.1 電極製備………………………………………………………...81
3.5.2 X光吸收光譜分析流程…………………………………………81
3.5.2.1 樣品前處理…………………………………………………82
3.5.2.2 X光吸收光譜……………………………………………….82
第四章 結果與討論………………………………………………………...94
4-1 Ni-Pt薄膜對於酒精的感測效能…………………………………….94
4-1-1 不同合金比例的Ni-Pt薄膜之晶格結構與表面形態…………94
4-1-2 Ni-Pt薄膜電極對於酒精氧化之極限電流區與電位窗………..97
4-1-3 Ni-Pt薄膜電極之酒精感測的靈敏度與應答時間……………..98
4-1-4 穩定性之測試…………………………………………………100
4-1-5 選擇性之測試…………………………………………………103
4-2 Ni-Pt薄膜電極對於酒精氧化之電化學特性………………………106
4-2-1 Ni/Au/Al2O3薄膜電極之循環伏安掃描………………………107
4-2-2 Ni-Pt/Au/Al2O3薄膜電極之循環伏安掃描……………………109
4-2-3 Ni與Ni-Pt旋轉電極於酒精氧化下之極化曲線……………..111
4-2-4 Ni及Ni-Pt電極之酒精感測的反應速率參數………………..115
4-2-4-1 Ni電極之反應速率參數的求取………………………….115
4-2-4-2 Ni-Pt電極之反應速率參數的求取……………………….117
4-2-4-3 Ni與Ni-Pt電極之反應動力行為的比較及Pt添加效果…117
4-3 Ni-Pt薄膜電極中Ni(OH)2/NiOOH之相態轉換…………………..120
4-3-1 長期電化學掃描下Ni(OH)2/NiOOH之相態變化……………121
4-3-2 不同合金比例下Ni(OH)2/NiOOH之相態變化………………127
4-3-3 不同沉積重量下Ni(OH)2/NiOOH之相態變化………………129
4-3-4 不同時效環境對於Ni(OH)2/NiOOH相態之影響……………130
4-3-4-1 Ni-Pt薄膜於KOH水溶液中之時效處理………………..130
4-3-4-2 Ni-Pt薄膜於潮濕的O2氣氛中之時效處理………………132
4-3-4-3 Ni-Pt薄膜於長時間酒精氧化之時效處理……………….133
4-3-4-4 Ni-Pt薄膜的β-Ni(OH)2/β-NiOOH之時效測試…………134
4-3-5 Ni-Pt薄膜中Ni(OH)2/NiOOH的相態變化對其酒精感測之穩定
性的影響……………………………………………………………...135
4-4 Ni-Pt薄膜電極的電子結構與原子排列情形………………………137
4-4-1 Ni-Pt薄膜電極之X光吸收近邊緣結構(XANES)……………137
4-4-2 Ni-Pt薄膜電極之延伸X光吸收精細結構(EXAFS)…………141
第五章 結論……………………………………………………………….190
未來工作…………………………………………………………………...192
參考文獻…………………………………………………………………...193

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