四種過渡金屬離子，包括銅（Cu），鎳（Ni），鎢（W）和鋅（Zn），用浸漬法浸漬在多孔TiO2-ZrO2（TZ）二元氧化物上，系統地研究和闡明了這些過渡金屬在表面酸性和氧化物的氨吸附中的作用。 TZ和浸漬粉末（TZM，其中M表示浸漬離子）保持多孔結構和高表面積（174-188m2/g）至600℃。雖然所有浸漬的離子都包含TZ基底的路易斯酸性，但由於四面體Cu和Zn物質與八面體Ti和Zr物質之間的結構不匹配，Cu和Zn物質另外增加了布朗斯台德酸度。具有高配位數的W和Ni的消耗消耗了表面OH基團，因此主要引入路易斯酸性。氨吸附容量為TZCu> TZZn> TZNi> TZW> TZ粉末。 Cu和Zn離子上的額外OH基團是TZCu和TZZn吸附劑的高氨吸附的主要貢獻者。在表面Cu /（Ti + Zr）原子比為6×10-3時，TZCu粉末的氨吸附容量最高，為1.81mmol / g。在該臨界Cu濃度下，Cu-OH基團之間的交叉縮合降低了吸附的活性位點。由於從Cu離子中消除OH基團，TZCu粉末在高溫解吸後的吸附容量降低了26.8％。然而，通過在環境空氣中暴露使用過的吸附劑，能夠回收吸附位點的損失。高氨吸附能力，寬範圍的酸度強度和良好的結構穩定性使浸漬的TZ粉末成為各種工業中有希望的氨去除吸附劑。

Four types of transition metal ions, including copper (Cu), nickel (Ni), tungsten (W), and zinc (Zn), were selected to be impregnated on the porous TiO2-ZrO2 (TZ) binary oxide with an impregnation method and the roles of those transition metals in the surface acidity and ammonia adsorption of the oxides were systematically examined and clarified. The TZ and the impregnated powders (TZM, where M means the impregnated ions) maintained the porous structure and high surface areas (174-188 m2/g) up to 600oC. While all the impregnated ions incrased the Lewis acidity of the TZ substrate, the Cu and Zn species additionally increased the Bronsted acidity as the result of structural mismatch between the tetrahedral Cu and Zn species and the octahedral Ti and Zr species. The W and Ni spcecies, which had high coordination numbers, consumed surface OH groups, thus introducing Lewis acidity primarily. The ammonia adsorption capacity was in the order of TZCu> TZZn> TZNi> TZW> TZ powders. The additional OH groups on the Cu and Zn ions were the major contributor to the high ammonia adsorption of the TZCu and TZZn adsorbents. The TZCu powder showed the highest ammonia adsorption capacity of 1.81 mmol/g at the surface Cu/(Ti+Zr) atomic ratio of 6 10-3. Over this critical Cu concentration, cross condensation between the Cu-OH groups decreased the active sites for the adsorption. The adsorption capacity of the TZCu powder decreased by 26.8% after high-temperatured desorption as the consequence of elimination of OH groups from the Cu ions. However, the loses of adsorption sites were able to be recovered by exposinig the used adsorbent in the ambient air. The high ammonia adsorption capacity, a wide range of acidity strength, and good structural stability enable the impregnated TZ powder to be a promising adsorbent for ammonia removal in variety of industries.

TABLE OF CONTENTS
摘要 i
Abstract ii
ACKNOWLEDGEMENT iii
TABLE OF CONTENTS iv
LIST OF TABLES vi
LIST OF FIGURES vii
CHAPTER 1 INTRODUCTION 1
1.1 Background and Motivation 1
1.2 Objectives 2
CHAPTER 2 LITERATURE REVIEW 4
2.1 Ammonia characteristic and removal methods 4
2.2 Adsorbents for ammonia removal 5
2.3 Surface acidity of binary oxides 9
2.4 Metal ion modification on surface acidity 10
CHAPTER 3 RESEARCH METHOD 13
3.1 Experimental design 13
3.2 Experiment materials 14
3.3 Solid acid synthesis 14
3.3.1 Solid acid substrate 14
3.3.2 Metal ion impregnation modification 15
3.4 Solid acid surface characterization 15
3.4.1 Ammonia Temperature Programmed Desorption (NH3-TPD) 15
3.4.2 N2 Adsorption-Desorption 16
3.4.3 X-ray Powder Diffraction (XRD) 16
3.4.4 X-ray Photoelectron Spectroscopy (XPS) 16
3.4.5 Energy Dispersive X-ray Spectroscopy with Scanning Electron Microscope (SEM-EDX) 17
3.4.6 Fourier-transform Infrared Spectroscopy with Pyridine Probe (Pyridine FTIR) 17
3.4.7 Thermogravimetric analysis (TGA) 17
CHAPTER 4 RESULT AND DISCUSSION 18
4.1 Microstructure 18
4.2 Chemical composition 22
4.3 Ammonia capacity 31
4.4 Adsorption sites 34
4.5 Optimization condition and regenerability 36
CHAPTER 5 CONCLUSION 41
REFERENCES 42
APPENDIX 46

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