指導教授：駱尚廉臺灣大學：環境工程學研究所王南惠Wang, Nan-HuiNan-HuiWang2014-11-302018-06-282014-11-302018-06-282014http://ntur.lib.ntu.edu.tw//handle/246246/264204水鈉錳礦為一種層狀型錳氧化物，因具特殊含水層間結構使得離子易於在層間結構間進出。為增加其與有機污染物之親和性，可藉由將birnessite表面增加有機成分之改質來達成，本研究以水熱法將界面活性劑插層birnessite進行材料改質，合成CTMA-birnessite及birnessite，並應用於苯甲酸及甲基橙之去除。 合成之CTMA-birnessite及birnessite材料，以X射線繞射儀、穿透式電子顯微鏡、掃描式電子顯微鏡、傅立葉紅外線光譜儀、和X射線光電子能譜儀等儀器進行材料特性分析，結果顯示，合成之birnessite層間距為0.71 nm，而CTMA-birnessite之層間距增為3.28 nm；而合成之birnessite材料表面，Mn(II)、Mn(III)、及Mn(IV)之比例為22.1%、56.4%、及21.5%、CTMA-birnessite之材料表面則為9.5%、62.4%、及28.1%。 將合成材料用於吸附苯甲酸及甲基橙，結果CTMA-birnessite較birnessite高出37%之苯甲酸去除效能；CTMA-birnessite 在pH 3時對苯甲酸有較高的去除效率，而去除率會隨著pH增高而下降；CTMA-binessite吸附苯甲酸之反應速率較birnessite為高，無論CTMA-birnessite對苯甲酸或甲基橙之吸附動力曲線，均符合擬二階動力方程式；CTMA-birnessite對苯甲酸的等溫吸附曲線符合亨利方程式，對甲基橙的等溫吸附曲線則符合Freundlich等溫吸附模式。 由實驗結果顯示界面活性劑之插層改質後能提昇錳氧化物之吸附能力，且CTMA+插層至birnessite後，會提昇其對有機物質之吸附效率。本研究並提出苯甲酸或甲基橙分配在CTMA+上及吸附在birnessite表面上之作用機制。Birnessite is a layered manganese oxide mineral. The hydrated layer structure of birnessite allows for the cations transporting in the interlayer region. To enhance the sorption performance for the organic contaminants, birnessite needs to be first surface modified by organic moieties. Inserting hydrocarbon chain into layers can increase the interlayer distance and hydrophobic property, resulting in higher affinity toward organic substances. Cetyltrimethylammonium modified birnessite (CTMA-birnessite) is prepared by a simple hydrothermal method for removing benzoic acid and methyl orange. The synthetic birnessite materials are characterized by a number of characterization techniques, including powder X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM), Fourier transforminfrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The results indicate that the prepared birnessite has a basal spacing of 0.71 nm and CTMA-birnessite has a basal spacing up to 3.28 nm. The relative contents of Mn(II), Mn(III) and Mn(IV) on the sample surfaces are about 22.1%, 56.4% and 21.5% for birnessite, and 9.5%, 62.4% and 28.1% for CTMA-birnessite. The CTAB modified birnessite was used to remove benzoic acid and methyl orange in aqueous solution. CTMA-birnessite has a high removal efficiency of benzoic acid at pH 3, while the uptake of benzoic acid decreased with increasing pH values. The reaction rate of benzoic acid sorption increases with the incorporation of CTMA. The pseudo-second-order kinetic equation provides a good description of the benzoic acid and methyl orange sorption on CTMA-birnessite. Benzoic acid sorption on CTMA-birnessite was well interpreted by Henry isotherm model. Instead, methyl orange sorption on CTMA-birnessite was well interpreted by Freundlich isotherm model. The results show that the modification of birnessite by intercalation of the surfactant can enhance the sorption capacity of manganese oxides. The intercalation of CTMA+ to birnessite will enhance the efficiency on the sorption of organic substances. The mechanism of benzoic acid or methyl orange partition to CTMA+ and adsorption on the birnessite surface were also proposed in this study.目 錄 口試委員會審定書 i 誌謝 ii 中文摘要 iii 英文摘要 iv 目 錄 vi 圖 目 錄 ix 表 目 錄 xi 第 1 章 緒論 1 1.1 研究緣起 1 1.2 研究目的 3 第 2 章 文獻回顧 4 2.1 Birnessite型錳氧化物 4 2.1.1 錳氧化物之合成 9 2.1.2 Birnessite型錳氧化物對污染物之吸附應用 12 2.1.3 Birnessite型錳氧化物對污染物之吸附機制 15 2.1.4 錳氧化物之其他應用 23 2.2 陽離子界面活性劑 24 2.2.1 界面活性劑之性質 24 2.2.2 以CTAB改質去除污染物 27 2.3 苯甲酸及甲基橙 30 2.3.1 苯甲酸 30 2.3.2 甲基橙 34 第 3 章 實驗材料與方法 36 3.1 研究架構 36 3.2 實驗藥品及分析設備 38 3.2.1 實驗藥品 38 3.2.2 實驗分析設備 38 3.3 實驗方法 43 3.3.1 CTMA-birnessite及birnessite之製備 43 3.3.2 CTMA-birnessite及birnessite之固相表面特性測定 43 3.3.3 CTMA-birnessite之分子式計算 45 3.4 批式實驗 46 3.4.1 苯甲酸吸附/脫附實驗 46 3.4.2 甲基橙吸附實驗 48 3.4.3 CTMA插層機制鑑定 48 第 4 章 結果與討論 49 4.1 合成材料特性鑑定 49 4.2 XRD層間距分析 49 4.3 材料表面微結構鑑定 51 4.4 FT-IR材料官能基分析 54 4.5 XPS表面組成分析 59 4.6 界面活性劑插層機制探討 65 4.7 合成材料之分子式推算 69 4.8 苯甲酸之動態吸附行為 70 4.9 苯甲酸之等溫吸附線 74 4.10 pH值對污染物吸附之影響 76 4.11 插層界面活性劑對於吸附效能之影響 77 4.12 苯甲酸之吸附/脫附實驗 78 4.13 甲基橙之吸附 82 4.14 反應機制探討 87 第 5 章 結論與建議 92 5.1 結論 92 5.2 建議 94 參考文獻 953152140 bytesapplication/pdf論文使用權限：不同意授權吸附苯甲酸甲基橙界面活性劑水鈉錳礦thesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/264204/1/ntu-103-D96541004-1.pdf