本篇研究將探討奈米金顆粒沉積在銅鋅催化劑上進行甲醇重組反應。由研究顯示先利用共沉澱法合成銅鋅觸媒，經乾燥後再以沉積沉澱法在pH 7條件下將金沉積到銅鋅上，可有效減少金在合成過程中的流失，經鍛燒後可得到的較佳催化活性之金銅鋅觸媒。本篇研究以金重量百分比分別為0%，0.8%，3%，與4.3%，而銅含量保持為30%之催化劑進行特性鑑定並在固定反應床進行甲醇部分氧化反應，甲醇蒸氣重組反應與氧化性甲醇蒸氣重組反應之活性測試。
研究顯示金的添加能夠有效的降低反應中的一氧化碳濃度，且隨著金的添加量增加而減少。此外，在無氧的環境下（甲醇蒸氣重組反應），金的添加銅同樣能夠減少一氧化碳的形成。而利用較高濃度的氧氣進行反應並不能有效的降低甲醇部分氧化反應中一氧化碳的生成，反而造成嚴重的氫氣燃燒反應，並且在甲醇氧化蒸氣重組反應中，高濃度的氧反而導致更多的一氧化碳生成。
此外，我們也發現添加金能夠在較低的溫度啟動重組反應。藉由X光吸收光譜儀可以發現在150oC時只通甲醇且未預還原的情況下，Au4.3Cu30ZnO已經被還原成63%Cu0以及37%Cu+，而Cu30ZnO則維持在氧化銅的狀態，金的添加讓觸媒上的銅更容易的被甲醇還原。同時，在室溫下將甲醇通入還原後的Au4.3Cu30ZnO以及Cu30ZnO，發現Au4.3Cu30ZnO有較多的氧化亞銅以及氧化銅的形成，代表金的添加增加了更多的金銅介面，能夠吸附更多的甲醇。而在不同氧醇比的甲醇部分氧化反應中，Au3Cu30ZnO觸媒由0.1氧醇比的180oC 啟動溫度下降至0.7氧醇比的120oC，而Cu30ZnO只有10oC的差別，金對氧較佳的吸附能力改善了啟動溫度。
總結而言，金是一個用以降低反應啟動反應溫度與降低一氧化碳生成的理想添加劑。金的添加在未經過還原處理的情況下降低了啟動溫度，使得重組器能夠在更少的加熱模組與操作溫度下產生氫氣。

Nano gold particle supported on copper zinc catalyst to proceed methanol reforming was investigated in this study. A synthesis method was developed which utilized co-precipitation to produce copper zinc catalyst, gold was added at pH 7 by deposition precipitation method after copper zinc catalyst was precipitated and dried. This synthesis procedure avoids severe gold loss and preserves significant reactivity after calcination. Different gold content, 0%, 0.8%, 3% and 4.3%, on the 30%copper supported on zinc oxide catalyst synthesis by procedure mentioned above, were characterized and tested in a fixed bed reactor through partial oxidation of methanol (POM), steam reforming of methanol (SRM) and oxidative steam reforming of methanol (OSRM) reaction.
The addition of gold can suppress the carbon monoxide. In addition, with the increasing gold content, less CO is formed. Furthermore, in the absent of oxygen, addition of gold also decrease the CO formation in SRM reaction. Higher oxygen concentration in POM reaction did not decrease the CO formation significantly, but causing severe hydrogen combustion. Meanwhile, higher oxygen concentration in OSRM reaction leads to higher CO formation.
Besides, the addition of gold can lower the initiation temperature. In-situ XAS revealed that without pre-activation, there was no any CuO reduced by methanol on the Cu30ZnO. In contrast, 63% Cu0 and 37% Cu2O were observed on Cu30ZnO with 4.3% gold promoter. Meanwhile, methanol was passed through reduced Au4.3Cu30ZnO and Cu30ZnO at room temperature, Au4.3Cu30ZnO was found having more Cu2O and CuO species which represent more methanol was absorbed on the interface between copper and gold. Besides, we also discovered the initiation temperature of Au3Cu30ZnO was lower to 120oC when 0.7 O/M ration was used in POM reaction while Cu30ZnO was remain at 190oC. Better oxygen absorption ability of gold improved the initiation temperature.
Gold is an ideal additive to improve the initiation temperature and decrease CO formation. Lower initiation temperature without pre-activation allow simpler heating module and reduce cost for the reformer.

Abstracts ------------------------------------------------------------------------------------------ I
Abstracts in Chinese --------------------------------------------------------------------------- II
List of Tables ----------------------------------------------------------------------------------- VI
List of Figures --------------------------------------------------------------------------------- VII
Chapter 1 ------------------------------------------------------------------------------------------ 1
Background and Introduction ---------------------------------------------------------------- 1
1-1 Use of the energy 1
1-2 Fuel cells 2
1-3 Advantages and applications of fuel cells 3
1-4 Proton exchange membrane fuel cells (PEMFCs) 6
1-5 Hydrogen storage 10
1-6 Production of hydrogen from methanol 15
1-7 Paper review of product hydrogen from methanol reforming over Cu based catalyst 19
1-8 Promoter of Au 22
1-9 Motivation and approaches 23
1-10 References 25
Chapter 2 ------------------------------------- 32
Experimental Section -------------------------- 32
2-1 Chemicals and solutions 32
2-2 Catalyst preparation method 34
2-3 Induced coupled plasma-mass analyzer (ICP-Mass) 37
IV
2-4 Powder X-ray diffractometer (PXRD) 37
2-5 Transmission electron microscopy (TEM) 38
2-6 Temperature programmed reduction (TPR) 39
2-7 Temperature programmed oxidation (TPO) 40
2-8 N2O Chemisorption 41
2-9 X-ray Absorption Spectroscopy (XAS) 41
2-10 Catalytic activity 43
2-11 References 49
Chapter 3 ------------------------------- 50
The study of synthesis strategy for gold deposition on copper zinc oxide catalyst ------------------------ 50
3-1 Characterization of the catalysts 50
3-2 X-ray powder diffraction of the catalysts 53
3-3 H2-temperature programmed reduction 56
3-4 Transmission Electrons Microscopy 59
3-5 POM reaction over catalysts by different synthesis method 59
3-6 Conclusions 63
3-7 Reference 65
Chapter 4 --------------------------------------------- 67
The relationship between gold content and copper zinc catalyst in the methanol reforming process ------------ 67
4-1 Result of ICP-MS and Cu surface area of the catalysts 67
4-2 X-ray powder diffraction 70
V
4-3 Hydrogen temperature programmed reduction 71
4-4 Temperature programmed oxidation 74
4-5 POM reaction over gold promoted copper zinc catalyst 78
4-6 The effect of O/M ratio to POM reaction 82
4-7 SRM reaction over gold promoted copper zinc catalyst 85
4-8 The influence of water to reduced copper zinc catalyst by XAS study 89
4-9 The XANES study of DM and SRM reaction over copper zinc catalyst 91
4-10 OSRM reaction over gold promoted copper zinc catalyst 93
4-11 The effect of oxygen in OSRM reaction 94
4-12 Conclusions 98
4-13 References 100
Chapter 5 ------------------------------------- 104
The role of oxygen on the copper zinc catalyst with gold promoter ---------------104
5-1 The relationship of ignition temperature and gold content 105
5-2 Conclusions 115
5-3 References 117
Appendix---------------------------------------- 119
A new strategy for the catalyst activation ----- 119
A-1 Effect of bath pH 119
A-2 The effect of different alkaline agent 130
A-3Conclusions 136
A-4 References 137

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5-3 References:
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2. Iwasawa, Y., Liu, H., Kozlov, A. I., Kozlova, A. P., Shido, T., and Asakura, K., “Active Oxygen Species and Mechanism for Low-Temperature CO Oxidation Reaction on a TiO2-Supported Au Catalyst Prepared from Au(PPh3)(NO3) and As-Precipitated Titanium Hydroxide,” 1999, Journal of Catalysis, 185, 252-264
3. Caps, V., Quinet, E., Morfin, F., Diehl, F., Avenier, P., and Rousset, J-L., “Hydrogen effect on the preferential oxidation of carbon monoxide over alumina-supported gold nanoparticles,” 2008, Applied Catalysis B: Environmental, 80, 195–201
4. Metiu, H., Mills, G., and Gordon, M. S. “Oxygen adsorption on Au clusters and a rough Au.111. surface: The role of surface flatness, electron confinement, excess electrons, and band gap,” 2003, Journal Of Chemical Physics, 118, 4198-4205
5. Haruta, M., Tsubota, S., Kobayashi, T., Kageyama, H., Genet, M. J. and Delmon, B, “Low-Temperature Oxidation of CO over Gold Supported on TiO2, α-Fe2O3, and Co3O4,” 1993, Journal of Catalysis, 174, 1, 175-192
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A-4 References:
1. Schüth, F., and Wolf, A., “A systematic study of the synthesis conditions for the preparation of highly active gold catalysts,” 2002, Applied Catalysis A: General, 226, 1–13
2. Fierro, J.L.G., Lago, R.M., Peña, M.A., and Espinosa, L.A., “Mechanistic aspects of hydrogen production by partial oxidation of methanol over Cu/ZnO catalysts,” 2003, Topics in Catalysis, 22, 245-251
3. Fan, K-N., Cao, Y., Wu, G-S., Wang, L-C., Liu, Y-M., Dai, W-L., and He, H-Y., “Implication of the role of oxygen anions and oxygen vacancies for methanol decomposition over zirconia supported copper catalysts,” 2006, Applied Surface Science, 253, 974–982
4. Khassin, A. A., Pelipenko, V. V., Minyukova, T. P., Zaikovskii, V. I., Kochubey, D. I., and Yurieva, T. M., “Planar defect of the nano-structured zinc oxide as the site for stabilization of the copper active species in Cu/ZnO catalysts,” 2006, Catalysis Today, 112, 143–147
5. Boccuzzi, F., Manzoli, M., and Chiorino, A., “Decomposition and combined reforming of methanol to hydrogen: a FTIR and QMS study on Cu and Au catalysts supported on ZnO and TiO2,” 2004, Applied Catalysis B: Environmental, 57, 201-209
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