臺灣博碩士論文加值系統

醋酸的多用途，除了常被當作化學用劑外，也是食醋與葡萄酒製品中重要的成份，因此能即時偵測醋酸濃度於排放廢棄物或食品品管中是相當重要的。然而目前被開發的醋酸感測器，多以生化酵素間接依耗氧量來推算醋酸濃度；或是以傳統方式來量測，其中包括酸鹼滴定法、氣相層析法、光聲光譜與近紅外線吸收光譜，用傳統方法偵測樣品的醋酸濃度不僅耗時，且需耗費額外的儀器操作。故能以電化學原理發展出一個能精確、價廉與應答快速的感測器，作為現場監控樣品中醋酸濃度是相當重要的。
本研究嘗試以常被運用在有機電化學合成中的氧化還原媒子來間接催化醋酸而得到應答電流。在初步工作電極選擇方面，是將電極置於感測系統環境，在溫度300K下含 0.005M的V2O5電解液，以循環伏安法測試該電極在原始溶液pH值(2.85)時是否有穩定的表現，如不與電解質起反應或電位窗向正方向偏移等，在測試白金、石墨、鉛與鎳等電極後，發現只有鎳電極能在該感測環境下，作為與電解液間穩定轉移電子的介面。
在靜置傳統三極式電極系統中，發現媒子濃度與電解液pH對於感測的影響是最直接的，而溫度與攪拌速率對於感測結果則會相互影響，實驗結果在300K下，pH值為2.85與0.005M的V2O5電解液，維持攪拌速率在600 rpm時有最好的感測表現，當施加電位在-1.1 V(vs. Ag/AgCl)，可得到應答電流與醋酸濃度的校正曲線i(uA)=-0.006359[HAc(ppm)]-0.482，靈敏度則為6.359 uA/ppm*cm2，線性係數0.992，偵測醋酸極限1800 ppm，應答時間33秒。
在電極微小化方面，以真空濺鍍方式製作濺鍍電極，並嘗試改變濺鍍因素來討論感測表現，結果發現真空度60 W、濺鍍功率 0.25torr及濺鍍時間20分鐘下，能得到均勻的濺鍍鎳層，而感測的結果也較好；相反的，高真空度、高濺鍍功率及短濺鍍時間下，會得到大鎳顆粒表面的薄膜或鍍層過薄，因此感測的結果也較差。
在靜置微小化電極系統中，在300K下pH值為2.85與0.005M的V2O5電解液，維持攪拌速率在60 rpm時能獲得最佳感測表現，即當施加電位在-1.8 V(vs. Ag/AgCl)，可得到應答電流與醋酸濃度的校正曲線i(uA)=-0.32[HAc(ppm)]-15.041，靈敏度則為1.28 uA/ppm*cm2，線性係數0.983，偵測醋酸極限600 ppm，應答時間7秒。
在反應控制系統中，對於鎳工作電極，由理論求得應答電流與醋酸濃度的關係式為:
r2=I2/nFA
=[k2K''1CV2O5*(CH+^2)/CH2O+K''1(CH+)^2]CHAc-(Ι-1)
其中，k2、K''1 、[V2O5] 、 [H2O]與 [H+]為常數，則應答電流與醋酸濃度成現性關係，因此理論與實際實驗結果幾乎相符；在擴散控制系統方面，由理論可推導出感測電流與醋酸濃度關係式。
i(t)=[nFA(Do^1/2)/(pi*t)^0.5]Co (Ι-2)
若上式中的n、F、A、Do與t均為常數，可由 i(t)與Co 一次方線性關係求得擴散係數Do。

Acetic acid is very useful, not only chemical agent but also the most important ingredient in vinegar and red wine. Hence, it is essential to detect acetic acid concentration immediately in discharged waste water or during quality control process in food industry. Up to now, the majority of the developed acetic acid sensors are enzyme-based. The enzyme-based sensors take advantage of indirect oxygen-consumed concentration to count acetic acid content un this study. The others are traditional methods including titration, gas chromatography, photoacoustic spectroscopy and near-infrared absorption spectroscopy. But the traditional methods are time-consuming and need extra expensive instruments. Therefore, it is very important to develop an exact, low-cost and fast-responding electrochemical sensor which can be in situ applied in the processes related to acetic acid concentration.
In this study, the concept of redox mediators is applied to catalyze acetic acid reduction indirectly. About initial choice of the working electrodes, the electrodes are set in a batch system as figure 3-3 shown. The sensing solution contained0.005MV2O5at 300K. During cyclic voltammogram test, nickel foil is much more stable interface for electron transference between sensing solution (pH=2.85) and electrode than platinum, carbon and lead.
In the three-electrode batch system, the optimal sensing conditions are as following: temperature at 300K, stirred rate at 600 rpm, pH 2.85 and0.005M V2O5 supporting electrolyte. When the applied potential set at -1.1V (vs. Ag/AgCl), the relationship between acetic acid concentration and response current was plotted resulting a straight line, i(uA)=-0.006359[HAc(ppm)]-0.482. The sensitivity of this system is 6.359 uA/ppm*cm2, the linear coefficient is 0.992, the detecting concentration range is from 0 to 1800ppm and the response time is 33 seconds.
The sputtered electrodes for sensing acetic acid were prepared at the conditions: degree of vacuum, sputtered power and sputtered time set at 0.25 torr, 60 W and 20 minutes, respectively. At this preparing condition, the optimal sensing conditions of a sputtered Ni electrode can be gained. As the optimal electrode test in a batch system was carried out resulting a straight line, i(uA)=-0.32[HAc(ppm)]-15.041. The sensitivity is 1.28 uA/ppm*cm2, the linear coefficient is 0.983, the detecting concentration range is from 0 to 600ppm and the response time is 7 seconds.
In kinetic control system, the relationship between response current and acetic acid concentration was derived theoretically as shown in equation (I-1) for Ni foil working electrode.
r2=I2/nFA
=[k2K''1CV2O5*(CH+^2)/CH2O+K''1(CH+)^2]CHAc-(Ι-1)
Where,k2 is, K''1is, [V2O5] is, [H2O] is, and [H+] is. Almost these parameters were constant. The relationship between response current and acetic acid concentration is linear. Experimental results are nearly fitting the theoretically analysis. In this case, when the diffusion was the rate determining step, the relationship between response current and acetic acid concentration was simplified to equation (I-2),
i(t)=[nFA(Do^1/2)/(pi*t)^0.5]Co (Ι-2)
Where, the constants, n is, F is, A is, Do is, and t is. Based on equation (I-2) and experimental data of a linear relationship between i(t) and the diffusion coefficient, Do, was obtained.

中文摘要………………………………………………………………I
英文摘要………………………………………………………………III
致謝……………………………………………………………………VI
目錄……………………………………………………………………VII
表目錄…………………………………………………………………XI
圖目錄…………………………………………………………………XII
符號說明………………………………………………………………XIV
第一章 緒論…………………………………………………………….1
1-1感測器之簡介及其主要特性…………………………………1
1-2常用感測器種類及原理………………………………………3
1-3 醋酸簡介……………………………………………………………6
1-3-1 醋酸之應用……………………………………………………6
1-3-2 醋酸進出口統計資料…………………………………………7
1-3-3 醋酸製程介紹…………………………………………………7
1-3-3-1 傳統製程…………………………………………………9
1-3-3-2 新穎的醋酸製程- Cativa Process……………………9
1-4 醋酸感測器之應用……………………………………………….11
1-4-1於廢水排放偵測之應用………………………………………11
1-4-1-1 半導體製程…………………………………………….11
1-4-1-2 內試鏡消毒…………………………………………….12
1-4-2食品工業上的應用……………………………………………14
1-5 醋酸分析方法之文獻回顧……………………………………….14
1-5-1 傳統醋酸分析方法………………………………………….14
1-5-1-1 酸鹼滴定法(Titration method) ……………………15
1-5-1-2 氣相層析法(Gas Chromatography) …………………15
1-5-1-3 光聲光譜法(Photoacoustic Spectroscopy) ………16
1-5-1-4 近紅外線吸收光譜法(Near-Infrared Absorption
Spectroscopy)…………………………………………16
1-5-2 感測器原理偵測醋酸……………………………………….18
1-5-2-1 固定酵素感測器(Immobilization Enzyme Sensor) 18
1-5-2-1-1 利用酵母菌酵素感測器………………………….18
1-5-2-1-2 利用激脢與氧化酵素感測器…………………….19
1-5-2-2 壓電式感測器(Piezoelectric Sensor)…………….20
1-5-2-3 電化學式感測器……………………………………….21
1-5-3 傳統醋酸偵測法與上述醋酸感測器缺點…………………….21
1-5-3-1 傳統醋酸偵測法缺點………………………………….22
1-5-3-2 上述醋酸感測器缺點………………………………….22
1-6 研究動機………………………………………………………….23
第二章 原理……………………………………………………………24
2-1 有機電化學簡介………………………………………………….24
2-1-1 電極材料的選擇…………………………………………….24
2-1-1-1鎳電極的簡介……………………………………………26
2-1-1-1-1 鎳於鹼性環境下………………………………….26
2-1-1-1-2 鎳於酸性環境下………………………………….27
2-1-2 電解液的選擇……………………………………………….27
2-1-2-1五氧化二釩(Vanadium pentoxide)簡介………………29
2-1-2-1-1 電極催化效應…………………………………….29
2-1-2-1-1-1 直接電極電解反應………………………….29
2-1-2-1-1-2 間接電極催化反應………………………….30
2-1-3 pH值的影響………………………………………………….31
2-1-4 攪拌速率與溫度的影響…………………………………….34
2-2 真空濺鍍之簡介………………………………………………….34
2-2-1 電漿………………………………………………………….34
2-2-2 濺鍍………………………………………………………….40
2-3 以氧化還原媒子間接催化醋酸動力分析……………………….43
2-3-1 醋酸與媒子間的反應機構………………………………….43
2-3-2 靜置系統中階梯濃度變化與反應極限電流關係………….51
第三章 實驗設備與步驟………………………………………………54
3-1 實驗藥品與儀器設備…………………………………………….54
3-1-1 實驗藥品…………………………………………………….54
3-1-2 實驗儀器…………………………………………………….56
3-2 實驗步驟………………………………………………………….58
3-2-1 液相系統(batch system)對醋酸的感測………………….58
3-2-1-1工作電極之製備…………………………………………58
3-2-1-1-1 鎳箔電極之製備………………………………….58
3-2-1-1-2 鉑電極之製備…………………………………….58
3-2-1-1-3 鉛箔電極之製備………………………………….58
3-2-1-1-4 電鍍鎳電極之製備……………………………….59
3-2-1-1-5 無電鍍鎳電極之製備…………………………….59
3-2-1-1-6 濺鍍鎳電極之製備……………………………….60
3-2-2 參考電極之製備…………………………………………….60
3-2-3 醋酸感測裝置……………………………………………….62
3-2-4 醋酸之感測分析…………………………………………….62
3-2-4-1 循環伏安法(Cyclic Voltammogram)求取電位窗……62
3-2-4-2 應答測試……………………………………………….65
3-2-4-3 靈敏度、應答時間之量測…………………………….65
3-2-4-4 產物測試……………………………………………….66
3-2-4-5 穩定性測試…………………………………………….66
3-2-4-6 電極表面分析………………………………………….66
3-2-4-6-1 掃描式電子顯微鏡分析(Scanning Electron
Microscope,SEM)…………………………………66
3-2-4-6-2 能譜儀分析(Energy-Dispersive Spectrometer,
EDS)……………………………………………….67
第四章 結果與討論……………………………………………………68
4-1 靜置系統中以金屬鎳電極感測醋酸結果……………………….68
4-1-1 工作電極材料的選擇……………………………………….68
4-1-2 極限電流測試……………………………………………….71
4-1-3鎳箔電極中實驗參數對醋酸感測的影響……………………73
4-1-3-1 電解質(媒子)濃度對感測的影響…………………….73
4-1-3-2 溫度對感測結果的影響……………………………….76
4-1-3-3 攪拌速率對感測結果的影響………………………….77
4-1-3-4 電解液的pH值對感測結果的影響…………………….80
4-1-3-5 應答曲線與濃度校正曲線…………………………….81
4-1-4 反應後的產物測試………………………………………….86
4-1-5 鎳箔電極之穩定性探討…………………………………….86
4-1-5-1 穩定電位飄移、靈敏度與線性關係的再現性……….89
4-1-5-2 工作電極感測前後SEM圖………………………………89
4-1-6 電鍍鎳與無電鍍鎳電極感測的結果……………………….92
4-1-6-1 電鍍鎳與無電鍍鎳電極的EDS分析……………………92
4-1-6-2 電鍍鎳與無電鍍鎳電極的極限電位窗……………….93
4-1-6-3 電鍍鎳與無電鍍鎳電極的感測結果………………….93
4-1-6-4 電鍍鎳與無電鍍鎳電極的SEM分析……………………94
4-2 靜置系統中以濺鍍鎳電極感測醋酸結果……………………….94
4-2-1 濺鍍參數對微小化電極感測的影響………………………101
4-2-1-1 真空度的影響…………………………………………101
4-2-1-2 濺鍍功率的影響………………………………………104
4-2-1-3 濺鍍時間與感測結果…………………………………109
4-2-2 實驗參數對微小化電極的影響……………………………114
4-2-2-1 電解液濃度對微小化電極的影響……………………114
4-2-2-2 溫度對微小化電極的影響……………………………115
4-2-2-3 攪拌速率對微小化電極的影響………………………115
4-3-1 綜合討論……………………………………………………123
4-3-1-1 三種不同鎳來源電極材料的綜合比較………………123
4-3-1-2 鎳箔電極與微小化電極之比較………………………123
4-3-1-3 實驗變數與感測結果…………………………………127
4-3-1-4 濺鍍參數與濺鍍鎳電極表面…………………………127
4-3-1-5 濺鍍鎳電極表面粒徑比較……………………………130
第五章 結論與建議………………………………………………….134
5-1 結論……………………………………………………………134
5-2 建議……………………………………………………………136
參考文獻………………………………………………………………137

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