臺灣博碩士論文加值系統

由於金屬有機支架具有較高的比表面積且方便修飾等特性，所以近年來廣受眾人研究；由於大部分的金屬有機支架無法長時間於水中保持穩定的結構，唯有特定某些金屬有機支架例外，其中鋯金屬有機支架( UiO-66)是個很好的例子。砷離子除了本身對於某些氧化金屬表面具有較佳的鍵結能力之外，對於含氨基修飾之化合物也有相當不錯的靜電作用力，因此本研究以含有氨基官能基的鋯金屬有機支架( UiO-66-NH2)作為吸附水中砷離子的吸附劑，希望能提升原有的鋯金屬有機支架( UiO-66)吸附砷離子的能力。首先藉由DLS、SEM與氮氣吸脫附裝置來確定哪一種合成條件合成出來的樣品構型較適合作為吸附砷的吸附劑，當DMF/Zr的莫耳比為350時，其結構呈現1微米左右球狀結晶，此結果比其他條件合成出來樣品的粒徑較大且無大孔的形成；接著再以XRD、FTIR、NMR與TGA來確認鋯金屬有機支架( UiO-66-NH2)的合成產物是否含有不純物，並將產物進行純化 。當確認鋯金屬有機支架( UiO-66-NH2)成功合成出來後，藉由杯瓶實驗測試鋯金屬有機支架( UiO-66-NH2)相較於UiO-66是否有較佳吸附砷離子的結果。由實驗結果得知，鋯金屬有機支架( UiO-66-NH2)在酸化6小時後，在pH 7條件下做吸附實驗，發現其具有與鋯金屬有機支架( UiO-66)差不多的最大砷離子吸附量147mg/g；由酸化時間與砷離子吸附量的趨勢來看，鋯金屬有機支架( UiO-66-NH2)的最大砷離子吸附量有可能可以超越鋯金屬有機支架( UiO-66)。

Recently, metal organic framework is popular research topic for scientist because it possesses high specific surface area and easy to modify. However, most of them are not stable when they are in aqueous solution for a long period except for UiO-66, one of metal organic framework, they can stay stable in aqueous solution. So compare to other MOFs, it can be applied in many ways. Besides, arsenate possess not only high affinity with some metal oxide surface but some electrostatic interaction with amine functional group. Hence, UiO-66-NH2 may possess higher maximum adsorption capacity for arsenate uptake than UiO-66. In this study, First, we would find out which kind of morphology of UiO-66-NH2 is suitable being adsorbent by DLS, SEM, nitrogen adsorption desorption isotherm. When the molar ratio of DMF and zirconium tetrachloride is 350, the size of product is about 1 micrometer and possess denser structure than other synthesis condition. Then, using XRD, FTIR, NMR and TGA to investigate whether the synthesis process for UiO-66-NH3+ can successfully synthesize it or not. Finally, measurement the adsorption capacity of UiO-66-NH2 by batch adsorption experiment. From the result, the maximum adsorption capacity of UiO-66-NH2 with 1M hydrochloride acid treatment for 6 hours is about 147mg/g. it is similar to result of UiO-66 which is 149mg/g. Moreover, the trend of the time for acid treatment and maximum adsorption capacity of UiO-66-NH3+ is in proportion. Hence, maximum adsorption capacity of UiO-66-NH3+ with longer period for acid treatment may higher than result of UiO-66.

中文摘要 iii
ABSTRACT iv
CONTENTS v
LIST OF FIGURES xi
LIST OF TABLES xiii
Chapter 1 Introduction 1
Chapter 2 Literature review 2
2.1 Arsenic 2
2.1.1 Introduction of arsenic 2
2.1.2 Adsorption technology for arsenate removal 5
2.2 Metal Organic Framework 8
2.2.1 UiO-66 10
Chapter 3 Material and Method 11
3.1 Chemicals 11
3.2 Synthesis process 12
3.2.1 Preparation of UiO-66 & UiO-66-NH2 12
3.2.2 UiO-66-NH2 hydrochloride acid treatment 13
3.3 Characterization and instrumentation 14
3.3.1 Powder X-Ray Diffraction 14
3.3.2 Fourier Transform Infrared Spectroscopy 14
3.3.3 Nuclear Magnetic Resonance 14
3.3.4 N2 adsorption and desorption isotherm 15
3.3.5 Field-Emission Transmission electron microscope 15
3.3.6 Field-Emission Scanning Electron Microscope 16
3.3.7 Dynamic light scattering 16
3.3.8 Zeta potential 16
3.3.9 pH meter 17
3.3.10 Inductively Coupled Plasma Mass Spectrometry 17
3.4 Adsorption experiments 18
3.4.1 Adsorption isotherm 18
3.4.2 Adsorption kinetic 19
Chapter 4 Result and discussion 20
4.1 The geometry structure of UiO-66-NH2 20
4.2 Characteristics of adsorbent 28
4.2.1 FTIR for UiO-66 & UiO-66-NH2 28
4.2.2 NMR for UiO-66 & UiO-66-NH2 31
4.2.3 X-ray Diffraction for UiO-66 & UiO-66-NH2 34
4.2.4 Thermogravimetric analysis for UiO-66-NH2 & UiO-66-NH3+ 37
4.3 Adsorption experiment 41
4.3.1 The pH effect for arsenate uptake 41
4.3.2 Adsorption kinetics 44
4.3.3 Adsorption isotherm 45
Chapter 5 Conclusion & future work 49
Chapter 6 Reference 50
Appendix A competitive adsorption 58

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