以多壁奈米碳管吸附水中雙酚A之特性研究

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余翊菱(Yi-lin Yu) 查詢紙本館藏

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環境工程研究所

論文名稱

以多壁奈米碳管吸附水中雙酚A之特性研究
(The research of the adsorption properties between multi-walled carbon nanotubes and bisphenol A)

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摘要(中)

由於奈米碳管多方面運用於各材料上的發展，必定會造成排放之問題，造成水體的汙染及生態環境上的變遷影響，故本研究為進一步了解其內部特性及吸附機制，挑選四種常見之化學氧化法(HNO3、piranha、NH4OH 25 %: H2O2 30 % = 50:50加熱迴流；KOH高溫氧化)作為碳管改質的方式，進行對於同樣被廣泛利用且被間接排入水體中的雙酚A之吸附實驗，探討其吸附行為與機制，有助於解決自然水體環境汙染問題。
研究發現經過氧化後之碳管其表面積、純度與官能基皆有增加之趨勢，動力吸附實驗方面，達吸附平衡時間由快至慢為A-MWCNTs(原始購得碳管)、N-MWCNTs(經HNO3氧化後碳管)、K-MWCNTs(經KOH氧化後碳管)，且其飽和吸附量各為0.3116、0.2039、0.5919 mmole/g，且皆較符合擬二階動力學模式。而在pH值之影響方面，發現主要受到雙酚A本體之解離作用影響，當雙酚A解離後帶負電與帶有負電官能基之奈米碳管表面定性正好相同，故雙酚A與碳管間形成靜電斥力，使得各種碳管之吸附環境pH值越高，有吸附量下降之趨勢。
等溫吸附實驗方面，主要影響吸附量多寡的原因為碳管的比表面積，尤其是K-MWCNTs，其氧化之強破壞力產生的高表面積而造成高吸附量，但吸附力仍受各氧化程序後產生之表面酸含氧官能基作用，而使吸附量下降，這也是A-MWCNTs之表面積雖高於N-MWCNTs，但相對吸附量卻相反之原因。在15、25、35℃下A-MWCNTs與N-MWCNTs皆符合Langmuir isotherm model，而K-MWCNTs則無法判定。且△Ho皆小於零，表示吸附過程為放熱反應，△Go亦皆小於零，可判定吸附反應為自發性。

摘要(英)

Due to various applications of carbon nanotubes, their discharge into natural water is expected and their adsorption phenomena should be studied to understand their fate and transport. In this study, four common chemical oxidation methods were chosen to modify multi-walled carbon nanotubes (MWCNTs), they are, HNO3, piranha, NH4OH 25 %: H2O2 30 % = 50:50, and KOH. Bispenol A (BPA) were adsorbed to investigate the influences of different oxidation methods of MWCNTs on the adsorption mechanisms.
It was found that, with proper oxidation parameters, nitric acid could introduce significant amount of oxygen-containing surface groups without altering the surface structure. Oxidation by KOH increased the surface area of MWCNTs dramatically and introduced oxygen-containing surface groups of the amount similar to that nitric-acid-treated MWCNTs. Thus the adsorption of BPA was only conducted by A-MWCNTs (as-purchased MWCNTs), N-MWCNTs (oxidized by HNO3), and K-MWCNTs (oxidized by KOH). The adsorption rates the fastest to the slowest were A-MWCNTs, N-MWCNTs, and K-MWCNTs and could be described by the pseudo-second order kinetic model. The adsorption capacities of A-MWCNTs, N-MWCNTs, and K-MWCNTs were 0.3116, 0.2039, and 0.5919 mmole/g, respectively. Comparison between the adsorption capacities of A-MWCNTs and N-MWCNTs showed that the oxygen-containing group hindered the π-π interactions and reduced the adsorption of BPA. The adsorption capacity was affected by solution pH, mainly due to the dissociation of BPA. Deprotonation of BPA leaded to electrostatic repulsions between BPA molecules and the surface of MWCNTs at high solution pH and, thus, reduction in the adsorption capacity.The enthalpy and free energy showed that adsorption of BPA on MWCNTs were exothermic and spontaneous.

關鍵字(中)

★ 奈米碳管
★ 雙酚A
★ 氧化
★ 吸附

關鍵字(英)

★ oxidation
★ bisphenol A
★ carbon nanotube
★ adsorption

論文目次

圖目錄 III
表目錄 V
第一章前言 1
1-1 研究緣起 1
1-2 研究目的 2
1-3 研究流程 3
第二章文獻回顧 4
2-1 奈米碳管簡介 4
2-1-1 基本特性 4
2-1-2 奈米碳管之合成與製備方法 6
2-2 奈米碳管之氧化方法 7
2-2-1 物理氧化法 8
2-2-2 化學氧化法 9
2-3 化學氧化法所造成碳管的改變 11
2-3-1 物理結構上之改變 11
2-3-2 化學特性上之改變 13
2-4 吸附理論 15
2-4-1 物理吸附與化學吸附 15
2-4-2 等溫吸附曲線 17
2-4-3 影響吸附有機物之因素 18
2-5 奈米碳管吸附汙染物之相關研究 20
2-5-1 無機汙染物之吸附 20
2-5-2 有機汙染物之吸附 21
2-6 雙酚A 24
2-6-1 雙酚A之特性及來源 24
2-6-2 雙酚A對人體的危害 26
2-6-3 雙酚A之吸附 27
第三章實驗方法 30
3-1 實驗設備與材料 30
3-1-1 實驗設備 30
3-1-2 實驗材料 33
3-2 實驗方法 34
3-2-1 奈米碳管之氧化程序 35
3-2-2 奈米碳管定性分析 38
3-2-3 雙酚A分析方法 40
3-2-4 實驗分析品保品管(QA/QC) 41
3-2-5動力吸附平衡實驗 42
3-2-6 等溫吸附平衡實驗 43
第四章結果與討論 46
4-1 奈米碳管的特性分析 46
4-1-1 奈米碳管之內部型態及表面孔隙分析 46
4-1-2 奈米碳管之官能基鑑定 54
4-1-3 奈米碳管之純度分析 56
4-2 碳管對BPA之吸附動力 59
4-3 不同改質奈米碳管對雙酚A之吸附及模式模擬 64
4-4 不同pH值下之吸附實驗 69
4-5 溫度之影響及吸附熱力學之分析 72
第五章結論與建議 80
5-1 結論 80
5-2 建議 82
參考文獻 83

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指導教授

秦靜如(Ching-Ju Monica Chin)

審核日期

2010-12-22

推文