臺灣博碩士論文加值系統

異質元素的奈米碳材摻雜可以改變許多例如光學、物理、化學及結構等特性。改善後的特性能更廣泛的應用在不同領域，像是電子元件、能量儲存或生物醫療等方面。此篇論文沿用本研究室先前發展出有效的方法，在大氣常壓下摻雜硼及氮元素於奈米碳管中，藉由調控溫度達到不同的氮摻雜水平，再結合金屬奈米粒子本身具備的高比表面積及高活性，形成奈米複合材料做為催化劑，應用在對硝基苯酚的還原反應，降低反應中的能量障礙，利用碳材及金屬間的協同作用，達到有效且快速解決環境、農業或工業廢水中酚類污染問題的目的。
此論文主要分為以下部分，第一章奈米複合材料以及對硝基苯酚還原反應的介紹及文獻回顧，包含實驗動機、合成方法的選擇、特性改善、對硝基本酚的動力學探討；第二章奈米複合材料的合成、酚類還原反應的實驗流程以及各種儀器包括穿透式電子顯微鏡、拉曼光譜X光光電子能譜、熱重分析/熱差分析等等的規格及分析條件；第三章奈米複合材料的分析結果，由各種儀器分析獲得形貌分析、尺寸分佈、導電性等特性，再由特性分析的結果延伸至第四章；討論複合材料對還原反應的活性表現以及改變反應物和還原劑對反應速率的影響；最後氮摻雜多壁奈米碳管應用在酚類還原反應的相關討論及參考文獻比較觸媒活性的結果將會呈現在第五章。

Heteroatom doping carbon materials can endow many properties. The improved features can be widely applied in different field. In this thesis, we follows our laboratory has previously developed an effective method to doping boron and nitrogen into the carbon nanotubes under atmospheric pressure, by controlling the temperature to achieve different levels of nitrogen content, and deposit the metal nanoparticles with high specific surface area and high activity on the tubes. The formation of nanocomposite as a catalyst to apply the reduction reaction of 4-nitrophenol(4-NP) to reduce the energy barrier of reaction. Because of synergy effect between the carbon materials and the metal nanoparticles can effectively and fast solve the problem of phenol pollution in waste water.
This thesis is divided into the following parts, the Chapter 1 introduction of nanocomposite materials and the introduction of 4-NP reduction reaction and literature review, including the motivation, the experimental set up, the choice of synthesis methods, the improvement of the properties, the kinetics of the 4-NP; Chapter 2 are synthesis of nanocomposites, experimental procedures for the 4-NP reduction, and various instruments. In the Chapter 3, the analysis results of nanocomposite were analyzed by various instruments to obtain features such as morphology, size distribution, conductivity, etc., and this parts were extended to the Chapter 4; the performance of the various catalyst for the 4-NP reduction reaction. And the effect of the concentration of reactants and reducing agents; the final discussion of the application of nanocomposite in the reduction of phenols and the comparison of activity with references will be presented in Chapter 5.

摘要 I
ABSTRACT II
ACKNOWLEDGEMENTS III
LIST OF FIGURE VI
LIST OF TABLES IX
LIST OF SCHEMES X
1. INTRODUCTION 1
1.1 INTRODUCTION OF MATERIALS OF CATALYST 1
1.1.1 Carbon nanotubes (CNTs) 1
1.1.2 Doped carbon nanotube 1
1.1.3 Platinum metal nanoparticles 5
1.2 INTRODUCTION OF 4-NITROPHENOL (4-NP) 7
1.2.1 4-Nitrophenol (4-NP) 7
1.2.2 4-NP reaction kinetics 10
1.2.3 4-NP reduction mechanism 16
2. EXPERIMENTAL METHODS 19
2.1 EXPERIMENTAL CHEMICALS 19
2.2 SYNTHESIS PROCESS 19
2.2.1 Doped carbon 19
2.2.2 Platinum nanoparticles deposition on carbon materials 20
2.3 CATALYTIC PROCESS 22
2.3.1 Catalytic reduction reaction of 4-NP 22
2.3.2 Change concentration of reactant (4-NP) 22
2.3.3 Change concentration of reduction agent (NaBH4) 23
2.4 CHARACTERIZATION 23
2.4.1 High temperature furnace 23
2.4.2 Transmission electron microscope (TEM) 23
2.4.3 Raman spectroscopy 24
2.4.4 X-ray diffraction (XRD) 24
2.4.5 X-ray photoelectron spectroscopy (XPS) 24
2.4.6 Thermogravimetric Analyzer (TGA) 25
2.4.7 Ultraviolet-visible spectroscopy (UV-Vis) 25
2.4.8 Four point probe 25
3. CHARACTERIZATION 27
3.1 ANALYSIS OF CARBON MATERIALS 27
3.1.1 Transmission electron microscope (TEM) 27
3.1.2 Raman spectroscopy 30
3.1.3 X-ray photoelectron spectroscopy (XPS) 32
3.1.4 Thermogravimetric analyzer (TGA) 34
3.1.5 Electrical conductivity measurement 35
3.2 ANALYSIS OF COMPOSITES 36
3.2.1 Transmission electron microscope (TEM) 36
3.2.2 Raman spectroscopy 39
3.2.3 X-ray diffraction (XRD) 39
3.2.4 Thermogravimetric analyzer (TGA) 40
4. RESULTS AND DISCUSSION 44
4.1 CATALYTIC PERFORMANCE OF CATALYST 44
4.1.1 Performance of multi-walled carbon nanotube (MWCNTs) 44
4.1.2 Performance of nitrogen doped carbon nanotubes (N-MWCNTs) 46
4.1.3 Performance of deposing Pt NPs on N-MWCNTs (Pt/N-MWNCTs) 50
4.2 CATALYTIC PERFORMANCE IN DIFFERENT CONDITION 52
4.2.1 Change concentration of reactant (4-NP) 52
4.2.2 Change concentration of reducing agent (NaBH4) 57
4.3 ACTIVATION ENERGY 69
4.4 COMPARE WITH REFERENCE 76
4.4.1 Normalized rate constant (kn) 76
4.4.2 Activation Energy (Ea) 77
5. CONCLUSION 78
6. REFERENCE 80

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