臺灣博碩士論文加值系統

　　本論文之內容可分成陽極觸媒和陰極觸媒兩個部分。由於乙醇不易在水溶液中進行氧化反應，因此許多觸媒材料被開發以降低其反應的過電位；而氧氣在生物體的新陳代謝中扮演一個重要的角色，它可被酵素還原成過氧化氫。故本研究的陽極觸媒主要探討修飾鎳電極催化乙醇氧化之電化學行為與其在感測器上的應用；陰極觸媒主要探討仿效素觸媒催化氧氣還原的電化學行為。以此搭配藉以了解有機與無機物質在無機與有機電極觸媒之氧化還原的行為。在陽極觸媒方面，本研究除了製備傳統大電極包括：氧化釕修飾鎳電極、電鍍alpha和beta態氫氧化鎳電極。也利用微製造技術製備微小電極包括：濺鍍奈米鎳電極、電鍍鎳硼電極。分別討論這些電極觸媒催化乙醇氧化行為與特性。並評估其對乙醇感測之靈敏度、反應時間、選擇性、穩定性。陰極部分乃在設計一個仿氧化酵素Laccase之觸媒，用以催化氧氣還原。以銅聚組織氨酸錯合物作為仿效素，探討此錯合物在水溶液中與其修飾在玻璃碳電極表面上的電化學行為。並將銅聚組織氨酸錯合物製備成微小陣列，改變不同銅對聚組織氨酸的莫耳組成，以掃瞄式電子顯微鏡(SECM)快速檢測其對氧氣還原的催化效果。

一、陽極觸媒
　　乙醇的定量廣泛的應用在醫學上、釀造業、化妝品業或是酒醉駕駛的防治。雖然傳統的液相層析儀或質譜儀可以精確量測乙醇含量，但這些儀器操作複雜、不易攜帶。本研究欲以修飾鎳觸媒催化乙醇氧化的觀點來設計一個攜帶方便、材料便宜、靈敏度高、反應時間快的乙醇感測器，並對不同的修飾鎳電極進行分析和評估。
氧化釕修飾鎳電極是以熱裂解的方式製備。經過修飾的鎳電極在水溶液的氧化電位較純鎳電極高，背景電流也比較大。注入乙醇後，氧化釕修飾鎳電極催化乙醇氧化的淨電流較純鎳電極高兩倍，顯示氧化釕修飾鎳電極能有效催化乙醇氧化反應。製備氧化釕修飾鎳電極的最佳條件為：氧化釕濃度2 M，重複浸泡氧化釕熱裂解次數6次，施加超音波功率150瓦。此條件下電極表面有最小的氧化釕顆粒（粒徑為120 nm），而釕和鎳之表面原子比為17。最佳條件所測得的靈敏度為4.92 µAppm-1cm-2，應答時間13秒，而乙醇濃度線性範圍在100與1000 ppm之間。
　　alpha態氫氧化鎳電極以定電流的方式製備，其電鍍時間和鍍液中硝酸鎳濃度的變化皆會影響膜表面的型態及特性，進而影響對乙醇的催化效果。將alpha態氫氧化鎳電極浸泡在高溫高濃度的氫氧化鉀溶液中，氫氧化鎳會從alpha態變成beta態。alpha態氫氧化鎳催化乙醇氧化的淨電流量較beta態氫氧化鎳高，但本文所製備的alpha態氫氧化鎳可逆性卻比bata態氫氧化鎳差。由BET測得以電鍍法製備出的氫氧化鎳膜具有多孔性，當alpha態氫氧化鎳超過一定的厚度時，會造成乙醇穿透氫氧化膜的阻力過大，會對乙醇完全無催化效果。alpha態氫氧化鎳電極對乙醇催化最佳的製備條件為：電流密度1 mAcm-2，硫酸鎳濃度：1 M，電鍍時間：15分鐘。此條件下，alpha態氫氧化鎳膜之厚度約為0.96 micro meter。
　　以微製造技術搭配濺鍍法所製備的奈米鎳電極具有高的比表面積，其對乙醇的催化效果較一般鎳電極佳。由AFM和SEM可觀測奈米鎳粒子的粒徑分佈在10到30 nm間。當濺鍍奈米鎳電極的厚度達到900 nm時，電極表面可感測乙醇的活性基已達飽和狀態，與�挹A氫氧化鎳薄膜有異曲同工之妙。奈米鎳電極對乙醇感測最佳的製備條件為：濺鍍時間45分鐘，濺鍍功率50瓦。此條件下測得的靈敏度為2.56 µAppm-1cm-2，而應答時間27秒，乙醇濃度線性範圍在100與600 ppm之間。此奈米鎳電極對乙醇溶液相較於乳酸、抗壞血酸、檸檬酸、蘋果酸、乙酸溶液，有極高的選擇性。但在含有醇基的環境下，其選擇性依序是甲醇＞乙醇＞丙醇＞丁醇。
　　鎳硼電極是以微製造技術搭配電鍍法所製備，所得到的活化膜具有高度結晶性。微小化的鎳硼電極比大電極對乙醇有較佳的催化效果。循環伏安圖顯示微小化鎳硼電極在乙醇加入後出現了另一個氧化峰，推測是三價鎳離子與乙醇反應速度和三價鎳離子還原成二價鎳離子速度不同導致。此電極感測乙醇的最佳製備條件為：電鍍溫度為80度，電鍍時間20分鐘。在此條件下所測得的靈敏度為6.1 µAppm-1cm-2，應答時間9秒，乙醇濃度線性範圍在100與600 ppm之間。當以酸類為干擾物測試時，鎳硼電極在對乙醇溶液有極高的選擇性。
綜合以上以鎳為主的陽極觸媒，相較於文獻上189-192催化乙醇氧化的觸媒材料可發現，鎳或修飾鎳觸媒有很高的靈敏度和很短的應答時間，但對於同類醇基的辨識率差。此外，由於氫氧化鎳( Ni(OH)2 )和過氧化鎳( NiOOH )有兩種型態存在，之間的轉換造成電極長期穩定性不佳，硼的加入可些微抑制靈敏度震盪的幅度。

二、陰極觸媒
　　氧氣還原反應廣泛的應用在燃料電池的陰極、染色處理、氧氣感測器等。鉑是目前最常用來催化氧氣還原的觸媒。然而，他的缺點包括容易被污染、價格昂貴。本研究欲以一個簡單的方式合成仿氧化酵素之觸媒來催化氧氣還原。利用聚組織氨酸為基質加入銅金屬離子形成錯合物來仿造Laccase的活性中心，分別在傳統三極式電化學反應器和掃瞄式電化學系統中作測試。在大電極的系統中可發現銅聚組織氨酸錯合物修飾玻璃碳電極相較於未修飾的玻璃碳電極，可降低氧氣還原的過電位並增進催化氧氣還原的電流。在掃瞄式電化學系統中，先以微噴射針筒製備不同比例組成的銅聚組織氨酸陣列當作基材，以直徑為25 micro meter的鉑微電極作為探針，利用「探針產生基材收集」的模式（tip generation substrate collection），在探針上產生氧氣，氧氣擴散到基材上還原的方式，快速檢測出具有最佳催化特性之觸媒組成。結果顯示催化氧氣還原的效果與銅離子對聚組織氨酸的莫耳百分比息息相關，銅離子對聚組織氨酸的莫耳濃度比在0.17時有最佳的催化氧氣還原的效果。

　　Ethanol quantification is important in medicine, brewing, fermentation and the control of drunken driving. Ethanol assays are also necessary for the quality control of ethanol based products in industry. Although liquid chromatograph and mass spectroscopy can determine with great precision ethanol concentrations, they are not suitable for ethanol analyses outside of the laboratory, due to the delicate and complicated instrumentation involved and the requirement for higher level operational skills. Therefore, we aimed to develop a convenient and simple ethanol sensor, with high a sensing performance, based on electrocatalytic technology using: RuO2-modified Ni; α-Ni(OH)2/Pt/Ti; sputtered Ni/Pt/Ti on an Al2O3 substrate; and electrodeposited Ni-B/Pt/Ti on Al2O3, as our electrodes.
　　The RuO2-modified Ni electrode was prepared by the thermal decomposition method. The anodic peak shifted to more anodic potentials when the background current was higher compared to a bare Ni electrode. Additionally, ethanol oxidation was more efficient with a RuO2-Ni electrode than with a bare nickel electrode. The sensing results were affected by the RuCl3 concentration, thermal decomposition numbers and ultrasonic irradiation used for preparing the working electrode. The optimal operating conditions for the RuO2-modified Ni electrode were 2 M Ru3+, 6 cycles of repeated thermal decomposition and 150 watts of ultrasonic irradiation. Under optimal sensing conditions, the best sensitivity and response times were 4.92 µAppm-1cm-2 and 13 s (90% response time), respectively.
　　Since the oxidation state of α-Ni(OH)2 is higher than beta- Ni(OH)2, we were interested in the factors influencing ethanol oxidation on the α-Ni(OH)2/Pt/Ti electrode. The α-Ni(OH)2 layer was formed on Pt in a nickel nitrate solution by cathodic deposition. Both electrode deposition time and the nickel nitrate concentration used for preparing the working electrode were found to affect the response current generated by ethanol oxidation. The results showed that the oxidation of ethanol significantly depended on the thickness and porosity of α-Ni(OH)2. A α-Ni(OH)2 film with a thickness of 0.96 μm was able to oxidize ethanol effectively. However, when the thickness of the α-Ni(OH)2 film was larger than 5.09 μm, there was no response current indicative of anodic oxidation. The optimal operating conditions for preparing a desired thickness of the α-Ni(OH)2/Pt/Ti electrode were 15 min at 1 mAcm-2 current density and 1 M Ni2+.
　　The film formed as a sputtered Ni/Pt/Ti layer on an Al2O3 substrate by a combination of micro-fabrication and sputtering techniques possess a high surface area. The particle size distribution is in the range from 10 to 30 nm as determined by both atomic force microscopy (AFM) and scanning electron microscopy (SEM). These results show the active site of NiOOH, which oxidizes ethanol reaches a saturation point while the thickness of sputtered Ni (900 nm) is in accordance with the α-Ni(OH)2/Pt/Ti electrode. Ethanol oxidation was more efficient on sputtered Ni/Pt/Ti formed on an Al2O3 substrate electrode than on a conventional nickel electrode. The optimal operating conditions used to generate the sputtered Ni/Pt/Ti on the Al2O3 substrate electrode were 45 min of Ni sputtering deposition time and 50 watts of Ni sputtering power. The response time of the prepared ethanol sensor is 27 s and the best sensitivity is 2.56 µAppm-1cm-2.
　　The electrodeposited Ni-B/Pt/Ti on Al2O3 substrate electrode was constructed using a thin-film technique. The sensing layers of Ni-B films prepared at constant cathodic current density have good crystallinity. The amperometric response of this miniaturized electrode was higher than that of traditional bulky electrodes. The micro-fabricated electrodeposited nickel-boron electrode exhibits good electrochemical performance in terms of response time (t(90%) = 9 s), linearity (100-600 ppm, r2 = 0.998), and sensitivity (6.1 µAppm-1cm-2). This sensor also shows a high selectivity to ethanol over mailc, citric, ascorbic, and acetic acids. The optimal operating conditions of these ethanol sensors were 80oC of electrodeposition temperature and 20 min of electrodeposition time.
　　The nickel based electrodes have high sensitivities and short response times compared to other electrocatalysts in cited in the literature186-192. The higher sensitivity of the RuO2 modified Ni and the electrodeposited Ni-B electrodes compared to the sputtered Ni electrode indicates that binary combinations of the electrocatalysts are superior to one component electrocatalysts. However, these electrodes have poor selectivity toward ethanol in the presence of other alcohols. They are also unstable, which precludes their use for long term measurements, due to the phase transformations between alpha and beta types although boron could slightly decrease the undulate sensitivity.
In the second part of this work a simple approach for the preparation and characterization of biomaterial-based electrocatalysts for oxygen reduction was carried out. Poly-L-histidine was used as a matrix and complexed by ligands with Cu2+ to mimic the active sites of laccases. A modified glassy carbon (GC) electrode with the Cu2+-poly-L-hisitidine complex was able to decrease the oxygen reduction overpotential as compared with a bare GC electrode. An array of Cu2+-poly-L-histidine spots with different compositions was deposited on a GC substrate and their catalytic activity with respect to oxygen reduction was evaluated by a SECM-based screening technique. The electrocatalytic activities of complexes for oxygen reduction depended strongly on the molar ratio of Cu2+ to poly-L-hisitidine and the applied potential of the substrate. The best composition of Cu2+-poly-L-hisitidine complex for oxygen reduction is at a molar ratio of 0.17 for Cu2+ to histidine residues.

Table of the Contents
Forward I
English abstract II
Chinese abstract V
Acknowledgements IX
Table of contents X
List of Figures XV
List of Tables XXIII
Frequent Abbreviations XXIV
Major Symbols XXV

Chapter 1 Introduction 1
1.1 Electrocatalysts 1
1.1.1 Electrochemical systems 1
1.1.2 Function of electrocatalysis 2
1.1.3 Electrocatalysts 3
1.2 Nickel as an electrocatalyst for alcohol oxidation 5
1.2.1 The structures of nickel oxide 5
1.2.2 The correlation between various phases of nickel oxide 8
1.2.3 Electrocatalytic oxidation of alcohol on nickel-based electrode 10
1.3 Other electrocatalysts for alcohol oxidation 12
1.3.1 Platinum based electrocatalysts 12
1.3.2 Ruthenium oxide and iridium oxide 14
1.3.3 Boron doped diamond based electrocatalysts 14
1.3.4 Other materials 15
1.4 Electrocatalysts for oxygen reduction reaction 15
1.4.1 Laccase and its reduction potential for oxygen reduction reaction 18
1.4.2 Cu2+-L-histidine complex 20
1.4.3 Cu2+-poly-L-histidine complex 25
1.5 Sensors 28
1.5.1 Historical development 28
1.5.2 Sensor definition and characteristics 28
1.5.3 Classification of chemical sensors 31
1.6 Ethanol sensors 40
1.6.1 Ethanol determination 40
1.6.2 Review of ethanol sensors 41
1.6.3 Microfabrication technology 48
1.7 Motivation of this study 52
Chapter 2 Principal 55
2.1 Scanning Electrochemical Microscopy 55
2.1.1 Ultramicroelectrodes as SECM probes 55
2.1.2 SECM mode of operation 56
2.1.3 Applications of SECM 58
2.2 The mechanism of electrodeposition of α-Ni(OH)2 60
2.3 Sputter deposition 61
Chapter 3. Experimental 62
3.1 Chemicals, materials, and instruments 62
3.2 Sensing electrodes preparation for ethanol oxidation 65
3.2.1 RuO2-modified Ni electrode 65
3.2.2 α-Ni(OH)2/Pt/Ti on titanium electrode 65
3.2.3 Nanostructured Ni/Pt/Ti on Al2O3 electrode 66
3.2.4 Electrodeposited Ni-B on Al2O3 electrode 68
3.3 Sensing electrodes preparation for oxidation reduction 68
3.3.1 Cu2+-poly-l-histidine modified glassy carbon electrodes 68
3.3.2 Tip electrode for SECM screening 69
3.3.3 Catalyst Spots on GC Substrate for SECM screening 69
3.4 Electrodes characterization and electrochemistry systems for ethanol oxidation 70
3.4.1 Electrodes characterization 70
3.4.2 Electrochemical measurements 72
3.4.3 Sensing procedure 72
3.5 Electrochemistry systems for oxidation reduction 73
3.5.1 Traditional three electrode analytical system 73
3.5.2 SECM analytical system 73
3.6 Instrumental analysis 75
3.6.1 X-ray diffratometer (XRD) 75
3.6.2 X-ray photoelectron spectroscopy (XPS) 76
3.6.3 Scanning electron microscopy (SEM) 76
3.6.4 Atomic force microscope (AFM) 76
Chapter 4. Nickel-based electrodes for the determination of ethanol 78
4.1 RuO2-modified Ni as working electrode 78
4.1.1 Structural characterization of the RuO2-modeified Ni electrode 78
4.1.2 The voltammetric behavior of the RuO2-modeified Ni electrode 78
4.1.2.1 Comparison of electrochemical properties for bare Ni and RuO2-Ni electrodes 78
4.1.2.2 Oxidation of ethanol at RuO2-modified Ni electrodes 81
4.1.3 Chronoamperometry 83
4.1.4 Optimal electrode composition and preparing conditions on the ethanol sensing 83
4.1.4.1 Effect of RuCl3 concentration 83
4.1.4.2 Effect of thermal decomposition numbers 87
4.1.4.3 Effect of ultrasonic irradiation 89
4.1.5 The stability of ethanol sensor 92
4.2 Effects of α-Ni(OH)2/Pt/Ti electrodes for ethanol anodic oxidation 94
4.2.1 Structural characterization of α-Ni(OH)2/Pt/Ti Electrode 94
4.2.2 Ethanol oxidation on α-Ni(OH)2/Pt/Ti and β-Ni(OH)2/Pt/Ti Electrodes 96
4.2.3 Optimal α-Ni(OH)2/Pt/Ti Electrode Conditions for Ethanol Oxidation 99
4.2.3.1 Effect of Electrode Deposition Time 99
4.2.3.2 Effect of Ni(NO3)2 Concentration 103
4.2.4 The interactive mechanism between the ethanol and α-Ni(OH)2 electrode surface 107
4.3 Sputtered Ni/Pt/Ti on Al2O3 substrate as working electrode 109
4.3.1 Film morphology imaged by atomic force microscopy 110
4.3.2 Comparison of electrochemical properties of Ni and sputtered Ni/Pt/Ti on Al2O3 substrate electrodes 110
4.3.3 Determination of potential window 113
4.3.4 Chronoamperometry 113
4.3.5 Effect of preparing conditions on ethanol sensing 116
4.3.5.1 Effect of electrode sputtering deposition time 116
4.3.5.2 Effect of electrode sputtering power 119
4.3.6 Interference studies 119
4.3.7 Reproducibility test 122
4.4 Electrodeposited Ni-B/Pt/Ti on Al2O3 substrate as working electrode 125
4.4.1 Characteristics of the electrodeposited Ni-B/Pt/Ti on Al2O3 substrate electrodes 125
4.4.2 Comparison of electrochemical behaviors of traditional bulky and miniaturized electrodes 127
4.4.3 Determination of potential window 131
4.4.4 Chronoamperometry 131
4.4.5 Effect of preparing conditions on ethanol sensing 133
4.4.5.1 Effect of electrodeposition temperature 133
4.4.5.2 Effect of electrodeposition time 137
4.4.6 Interference studies 138
4.4.7 Reproducibility test 138
Chapter 5. Biomimietic copper poly-L-histidine complexes for oxygen reduction 143
5.1 Ultraviolet-visible spectroscopic measurements 143
5.2 Cyclic votalmmetric behavior of Cu2+ in the aqueous solution in the absence and in the present of O2 at GC electrodes 143
5.3 Cyclic votalmmograms of Cu2+-L-histidine complexes in the aqueous solution in the absence and in the present of O2 at GC electrodes 146
5.4 Cyclic votalmmograms of Cu2+-poly-L-histidine complexes in the aqueous solution in the absence and in the present of O2 at GC electrodes 149
5.5 Electrocatalytic reduction of O2 at the Cu2+-poly-L-histidine complexes modified GC electrodes in PBS solution 156
5.6 Screening of Cu2+-poly-L-histidine complexes for oxygen reduction by SECM 160
Chapter 6. General discussion, conclusions and suggestions 169
6.1 General discussions 169
6.2 Conclusions 174
References 177

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