臺灣博碩士論文加值系統

本研究製備出具有低成本且高電化學性能的觸媒-氧化銅觸媒應用於低耗能的電解甘油氧化。透過層析圖譜分析與拉曼光譜分析進而得出甘油氧化反應路徑。層析圖譜用於分析穩態系統中的產物分佈。在電解系統中，必須了解從反應物吸附、中間產物生成到產物脫附的反應步驟。原位拉曼光譜是檢測電極和電解質表面反應的方法。此外，通過控制電催化劑的性質以及電化學反應條件，可以調節電化學氧化以獲得高產品選擇性，然而，甘油分子中的羥基可以被選擇性地電氧化以形成醛（R-CHO）、酮（R-CO-R'）和羧基（R-COOH）基團。
氧化銅觸媒對於電解甘油氧化反應有較低的過電位(1.25 V vs. RHE)，在液相層析儀的定量產物分析中，主要檢測產物有二甲基丙酮(dihydroxyacetone, DHA)、甘油酸鹽 (glycerate) 、乙醇酸鹽 (glycolate) 、草酸鹽 (oxalate)、甲酸鹽 (formate)。在低電壓1.29 V vs. RHE計時安培測定中，產物分析顯示較高的C3產物選擇率，glycerate 26%、DHA 5%，然而，在高電壓下更容易使甘油C-C斷鍵，形成碳酸鹽 (carbonate)。原位拉曼光譜結合電化學反應系統進行反應機制探討，結合計時安培測定中，可觀測出甘油電解反應在氫氧化鈉水溶液中的反應路徑為甘油二級醇(DHA)的氧化進行，然而，DHA會自發性地轉換成GLAD。GLAD會持續氧化成glycerate，並接續向下的氧化反應。從C3產物的生成到C2、C1的偵測，得出氧化銅觸媒在NaOH水溶液下甘油氧化的反應路徑。除此之外，同時觀察到在電解質四硼酸鈉(Na2B4O7)添加甘油水溶液中(pH=9)，得出高於50%的DHA選擇率，證明在高OH基的環境下DHA較不易生存，且氧化銅觸媒顯示出對二級醇氧化的高選擇性。

Low-cost and high-efficient copper oxide, CuO, was used as an electrocatalyst for glycerol electro-oxidation reaction (GEOR). Copper oxide showed the onset potential of 1.25 V vs. RHE for GEOR in pH 13. High-performance liquid chromatography (HPLC), Raman spectroscopy and electrochemical method were used for analysis the products of GEOR. Considering that reactant adsorption, intermediate formation to product desorption are critical, HPLC was used for analyzing the product distribution in the bulk liquid while the in-situ Raman spectroscopy was employed to detect the surface reaction on the solid electrode. Accordingly, dihydroxyacetone (DHA), glycerate, glycolate, oxalate, and formate were detected quantitatively by HPLC. Interestingly, it was found that the product selectivity can be controlled by tuning the properties of the applied potential and solution pH. At the lower applied potential of 1.29 V vs. RHE in pH 13, three-carbon (C3) products have a higher selectivity, i.e. 26% for glycerate and 5% for DHA. However, C-C bond cleavage at higher potential was observed which lead to the formation of vast amount of formate and carbonate. From In-situ Raman spectroscopy, we found that the reaction pathway of GEOR in pH 13 by CuO catalyst started from the oxidation of secondary hydroxyl group, leading to the formation of DHA, and DHA spontaneously transferred to glyceraldehyde (GLAD). GLAD then oxidized to glycerate and continued the higher oxidation degree products. Lowering the pH to pH 9 can slow down the transformation of DHA to GLAD, thus, the ability of selective oxidation of glycerol to DHA (~60% selectivity) can be easily observed.

Abstract i
摘要 ii
Table of Content iii
Index of Figures v
Index of Table xii
Chapter 1 Introduction 1
Chapter 2 Literature Reviews 3
2.1 By-product of Biodiesel – Glycerol 3
2.2 Glycerol Oxidation 5
2.2.1 Glycerol Oxidation Products 7
2.2.2 Method of Glycerol Oxidation 10
2.2.3 Glycerol Electro-Oxidation Reaction (GEOR) 12
2.2.4 Metal Catalyst of GEOR 16
2.2.5 Metal Oxide Catalyst of GEOR 17
2.3 The pH Effect of Solution in Glycerol Oxidation 18
2.4 Method of GEOR Products Analysis 20
2.4.1 High Performance Liquid Chromatography, HPLC 21
2.4.2 In-situ Fourier Transform Infrared Spectroscopy, FTIR 22
2.4.3 In-situ Raman Spectroscopy 24
2.5 Electrocatalyst – Copper Oxide 28
Chapter 3 Experimental Method 29
3.1 Experimental Chemicals and Equipment 29
3.2 Synthesis of CuO Catalyst 31
3.3 Characterizations 31
Abstract i
摘要 ii
Table of Content iii
Index of Figures v
Index of Table xii
Chapter 1 Introduction 1
Chapter 2 Literature Reviews 3
2.1 By-product of Biodiesel – Glycerol 3
2.2 Glycerol Oxidation 5
2.2.1 Glycerol Oxidation Products 7
2.2.2 Method of Glycerol Oxidation 10
2.2.3 Glycerol Electro-Oxidation Reaction (GEOR) 12
2.2.4 Metal Catalyst of GEOR 16
2.2.5 Metal Oxide Catalyst of GEOR 17
2.3 The pH Effect of Solution in Glycerol Oxidation 18
2.4 Method of GEOR Products Analysis 20
2.4.1 High Performance Liquid Chromatography, HPLC 21
2.4.2 In-situ Fourier Transform Infrared Spectroscopy, FTIR 22
2.4.3 In-situ Raman Spectroscopy 24
2.5 Electrocatalyst – Copper Oxide 28
Chapter 3 Experimental Method 29
3.1 Experimental Chemicals and Equipment 29
3.2 Synthesis of CuO Catalyst 31
3.3 Characterizations 31
3.4 Electrocatalytic Oxidation of Glycerol and Products Analysis 32
3.5 Calculation of Products Distribution 34
3.6 Principle of Electrochemistry 35
3.6.1 Faraday’s Law of Electrolysis 36
3.6.2 Linear Sweep Voltammetry, LSV 37
3.6.3 Chronoamperometry 37
3.6.4 Electrochemical Impedance Spectroscopy, EIS 38
Chapter 4 Result and Discussion 40
4.1 Physical Characterization 40
4.2 Electrochemical Characterization 42
4.3 X-ray Photoelectron Spectroscopy (XPS) 45
4.4 Product Analysis of High-Performance Liquid Chromatography (HPLC) 47
4.4.1 Product Distribution 49
4.4.2 Carbon Balance 53
4.4.3 Oxidation Products Voltammograms 54
4.5 Product Analysis of Gas Chromatography (GC) 56
4.6 In-Situ Raman Spectrum 58
4.6.1 In-Situ Raman/ Chrono-amperometry 61
4.6.1 In-Situ Raman/ Cyclic Voltammetry 66
4.7 Reaction Pathway Study 68
4.8 Comparison of Different Electrolyte for GEOR 70
Chapter 5 Conclusion 78
References 80
Appendix 87

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