臺灣博碩士論文加值系統

本研究以陽極氧化蝕刻法製作二氧化鈦奈米管陣列電極(Titanium nanotube arrays，TNAs)，再利用綠色還原劑 - 茶和咖啡，還原氯化鈀成金屬鈀，再以微波水熱法合成摻附鈀的二氧化鈦奈米管陣列電極(Palladium Titanium Dioxide Nanotube Arrays, Pd/TNAs)。
對TNAs及Pd/TNAs材料進行物理特性分析，採用SEM、UV-vis、XRD、XPS等技術來鑑定TNAs表面結構、對光吸收度以及元素組成型態；在電化學方面以I-T、EIS、EPR等方法去測試TNAs光電流密度、電子阻抗能力、自由基種類。以光電化學(Photoelectrochemical, PEC)、電化學(Electrochemical, EC)、光催化化學(Photocatalytic, PC)與直接光照(Photolysis, P)等方式降解甲基橙。探討其脫色能力、總有機碳去除率以及產氫效率，結果顯示，以光電化學方式降解甲基橙去色度能力、總有機碳去除率以及產氫效率皆為最高。另外也比較了TNAs、Pd/TNAs、Pd/TNAs-C以及Pd/TNAs-G四種材料的電化學特性，在實驗結果顯示在1V電壓下(vs. Ag/AgCl) Pd/TNAs的光電流(4.0 mA/cm2)較未摻雜的TNAs(1.4 mA/cm2)高，顯示摻入Pd後能有效分離光生電子與電洞，提升光電化學氧化作用，研究結果證明，以光電化學方式催化降解污水中的有機汙染物具有良好的成效。

In this study, titanium dioxide nanotube arrays (TNAs) electrode was successfully synthesized by anodic oxidation etching method. As well as the use of green synthetic technology to add reducing agent tea or coffee to reduce metal palladium from palladium chloride. Synthesis of Palladium Titanium Dioxide Nanotube Arrays (Pd/TNAs) was conducted by Microwave Hydrothermal Method after the metal palladium was reduced。
In order to identify the surface structure, the light absorption and elemental composition, TNAs and Pd/TNAs were characterized by scanning electron microscopy (SEM), ultraviolet–visible spectroscopy (UV-vis), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). On the other hand, test the photocurrent density, electron resistance, and hydroxyl radicals by I-t plot, Electrochemistry Impedance Spectroscopy (EIS), and electron paramagnetic resonance (EPR) was investigated.
Four methods, Photoelectrochemical (PEC), Photocatalytic (PC), Electrochemical (EC), and Photolysis (P) were employed to test the methyl orange degradation efficiency, the total organic carbon (TOC) removal efficiency and hydrogen production efficiency. The results show that the Pd /TNAs-C performed the best efficiency.
The photocurrent (4.0 mA / cm2) of Pd /TNAs-C at 1 V (vs. Ag / AgCl) was higher than that of the uncoated TNAs (1.4 mA / cm2), indicating that Pd /TNAs-C can effectively separate photogenerated electrons and holes. Pd/TNAs is a material for promising for PEC degradation of organic pollutants
in wastewater.

摘要 I
Abstract II
目錄 III
表目錄 VII
圖目錄 VIII
第 一 章 緒論 1
1-1前言 1
1-2研究目的 3
第二章 文獻回顧 4
2-1 二氧化鈦簡介 4
2-1.1二氧化鈦 4
2-1.2二氧化鈦晶相 5
2-1.3二氧化鈦光催化機制 6
2-2二氧化鈦奈米管陣列 6
2-2.1二氧化鈦奈米管陣列介紹 6
2-2.2.1板模法 6
2-2.2.2陽極氧化蝕刻法 7
2-3綠色合成技術 8
2-3.1綠色合成技術-二氧化鈦奈米管陣列改質 9
2-4綠色合成技術-微波水熱法 9
2-4.1微波原理 9
2-4.2微波水熱法 10
2-5光電化學產氫 10
2-5.1燃料能源- 氫氣 10
2-5.2光電化學產氫機制 11
2-6偶氮染料 12
第 三 章 實驗步驟及方法 13
3-1實驗藥品與設備 13
3-2實驗步驟流程圖 15
3-3二氧化鈦奈米管陣列製備 16
3-3.1鈦片表面清洗 16
3-3.2鈦片陽極氧化蝕刻 16
3-3.2.1蝕刻液配製 16
3-3.2.2蝕刻鈦片 16
3-3.2.3鍛燒二氧化鈦奈米管 17
3-4摻雜氯化鈀二氧化鈦奈米管陣列電極製備 18
3-4.1綠色合成奈米鈀顆粒 18
3-4.1.1摻附鈀之二氧化鈦奈米管陣列(Pd/TNAs) 18
3-4.1.2使用咖啡摻附鈀之二氧化鈦奈米管陣列(Pd/TNAs-C) 18
3-4.1.3使用綠茶摻附鈀之二氧化鈦奈米管陣列(Pd/TNAs-G) 18
3-4.2微波水熱法 18
3-5材料物理化學特性分析 19
3-5.1紫外可見光分光光譜儀 (Ultraviolet–visible spectroscopy, UV-vis) 19
3-5.2掃描式電子顯微鏡 (Scanning Electron Microscopy, SEM) 20
3-5.3X光射線繞射分析儀 (X-ray diffraction, XRD) 21
3-5.4 X射線光電子能譜儀 (X-ray photoelectron spectroscopy, XPS) 21
3-6光電化學特性分析 22
3-6.1光電流測試 (I-t) 23
3-6.2電化學阻抗頻譜法 (Electrochemistry Impedance Spectroscopy, EIS) 23
3-7光電化學降解實驗 24
3-7.1模擬污染物-甲基橙配置 24
3-7.2甲基橙降解同時產氫 24
3-7.3總有機碳量 ( Total Organic Carbon, TOC ) 25
3-7.4電子順磁共振 (EPR) 25
3-7.4.1原理 25
3-7.4.2自旋捕捉技術 ( spin trapping ) 25
3-7.4.3DMPO溶液配製 26
第 四 章 實驗結果與討論 27
4-1材料物理化學特性分析結果 27
4-1.1掃描式電子顯微鏡(SEM) 27
4-1.2 X光繞射分析(XRD) 29
4-1.3 X光電子能譜分析(XPS) 31
4-1.4紫外-可見吸收光譜分析(UV-vis) 36
4-2光電化學特性分析 38
4-2.1光電流特性 38
4-2.2光電化學交流電阻抗能譜 40
4-2.2.1 電子壽命 43
4-3光電化學降解甲基橙 44
4-3.1比較光電化學、電化學、光催化與直接光照降解甲基橙 44
4-3.2比較各材料以光電化學、光催化、電化學降解甲基橙 46
4-3.3光電化學降解甲基橙並同時產氫 51
4-4光電化學降解總有機碳 (TOC) 56
4-4.1比較光電化學、電化學、光催化與直接光照降解甲基橙之TOC 56
4-5 Pd/TNAs光電極穩定性分析 59
4-6氫氧自由基機制與探討- EPR 61
第 五 章 結論與建議 63
5-1結論 63
5-2建議 64
參考文獻 65

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