奈米碳管對硝基酚與銅混合溶液其吸附機制之探討

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研究生：	蘇建智 Jian-zhi Su
論文名稱：	奈米碳管對硝基酚與銅混合溶液其吸附機制之探討 Adsorption mechanism of nitrophenol and copper(II) from mixed liquor by mult-walled carbon nanotubes
指導教授：	秦靜如
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 環境工程研究所 Graduate Institute of Environmental Engineering
論文出版年：	2014
畢業學年度：	102
語文別：	中文
論文頁數：	117
中文關鍵詞：	協同效應、競爭吸附、循環伏安法
外文關鍵詞：	synergistic effect, competitive adsorption, cyclic voltammetry
相關次數：	點閱：15 下載：0
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本研究利用多壁奈米碳管吸附硝基酚異構物(2-NP 與 4-NP) 及Cu(II)
的混合溶液以探究其吸附機制，以及硝基酚與Cu(II) 之間的關係。利用批
次吸附實驗與電化學實驗這兩種實驗方法的結果來相互比較與解釋論述。
批次吸付實驗結果顯示，混合系統為酸性條件時，NPs 可能因苯環和含氧
官能基之間的作用力而不容易靠近碳管表面，Cu2+則較NPs 容易靠近碳管
表面。也可能是Cu2+可能與水形成水合作用，產生遮蔽效應，這些都將不
利於NPs 吸附於碳管表面，所以可以推測碳管對NPs 與Cu2+的吸附，可
能存在著相互競爭的關係。混合系統為鹼性條件時，碳管對於2-NP 與Cu2+
的吸附百分比均有明顯增加的現象，但對4-NP 的吸附百分比並沒有像
2-NP 的結果一樣顯著增加。結合循環伏安掃描結果可推測有三種可能的
吸附機制：(A) 2-NP 可能與銅離子形成新物質而吸附於碳管表面；(B) 碳
管可能是先吸附Cu2+而硝基酚負離子再藉由靜電吸引力吸附在Cu2+上；(C)
沉澱物之影響。至於當4-NP 與Cu2+的混合系統為鹼性條件時，推測其吸
附機制可能是碳管先吸附Cu2+而硝基酚負離子再藉由靜電吸引力吸附在
Cu2+上。此外，在電化學方面發現了後加入Cu2+的系統中，4-NP 的電流
值在加入Cu2+後有增加的趨勢，而Cu2+的電流值明顯小於4-NP 的電流值，
藉此可以做個推測，表示在此實驗中Cu2+會幫助4-NP 對於奈米碳管修飾
電極發生更佳的反應，而且4-NP 比Cu2+對於奈米碳管修飾電極具有更佳
的反應。

The objective of this thesis is to explorethe mechanismof baniry adsorption of Nitrophenol and Cu(II) by MWCNTs.Batch adsorption and cyclic voltammetry were conducted and compared. It is suggested that it would be difficult for NPs to get close to the surface of MWCNTs because of the interactions between the benzene ringof NPs and the oxygen-containing in acidic condition. It is also believed that the hydrationofCu2+limited the adsorption of NPs. In this case, it can be speculated that there is competition between NPs and Cu2+for the adsorption on fthe MWCNTs.On the other hand,
in alkaline solution, an apparent increase in theadsorption of 2-NP was found while such increase was not observed for 4-NP. Threeadsorption mechanisms may be possible: (A) 2-NP and Cu2+may form a new compounds,(B) MWCNT may adsorb Cu2+first, followed by the adsorption of dissociated nitrophenol ionsdue to the electrostatic attraction withCu2+, and (C) Surface precipitation of
Cu may decrease the negative charges of the MWCNTs surface.For 4-NP and copper are mixed in alkaline solution, Cu2+ may be adsorbed on the MWCNTs first followed by the adsorption of 4-NP.From CV, it was found that the current of 4-NP increased after Cu2+was added in the solution. Meanwhile, the current of Cu2+ became weaker than that of 4-NP. Therefore, it can be suggested that the presence of Cu2+may enhance the adosprtion of 4-NP onMWCNT.

摘要................................................................................................................................ I 
Abstract ......................................................................................................................... II 
誌謝.............................................................................................................................. III 
圖目錄........................................................................................................................ VII 
表目錄.......................................................................................................................... IX
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.........................................................................................................4
2-1-1 結構與基本特性..................................................................................4
2-1-2 奈米碳管之化性與改質.....................................................................6
2-2 吸附理論及特性............................................................................................9
2-2-1 物理吸附與化學吸附.........................................................................9
2-2-2 液相吸附擴散機制...........................................................................10
2-2-3 影響吸附之因素................................................................................11
2-3 銅及硝基苯酚異構物...................................................................................12
2-3-1 硝基苯酚異構物之特性與環境影響...............................................12
2-3-2 銅之特性及對環境影響...................................................................13
2-4 奈米碳管對汙染物的吸附行為與相關研究...............................................14
2-4-1 對有機污染物吸附機制....................................................................14
2-4-2 對重金屬之吸附................................................................................16
2-4-3 污染物間的競爭吸附.......................................................................18V
2-5 電化學分析...................................................................................................21
2-5-1 電化學反應原理與系統....................................................................21
2-5-2 循環伏安法........................................................................................23
2-5-3 奈米碳管之電化學分析...................................................................24
第三章實驗方法..........................................................................................................28
3-1 實驗材料與設備..........................................................................................28
3-1-1 實驗材料...........................................................................................28
3-1-2 實驗設備...........................................................................................29
3-2 實驗方法......................................................................................................31
3-2-1 奈米碳管之改質方法.......................................................................31
3-2-2 硝基苯酚異構物之定量分析...........................................................32
3-2-3 硫酸銅溶液配置及檢量線...............................................................33
3-2-4 批次吸附實驗...................................................................................33
3-2-5 電化學實驗-循環伏安法..................................................................35
第四章結果與討論......................................................................................................38
4-1 奈米碳管之定性分析..................................................................................38
4-1-1 奈米碳管的表面形態及孔隙分析...................................................39
4-1-2 奈米碳管之官能基分析....................................................................44
4-2 奈米碳管對硝基酚和銅的吸附能力..........................................................46
4-2-1 硝基酚的單一吸附系統...................................................................47
4-2-2 pH 值對 MWCNT 吸附硝基酚之影響...........................................49
4-2-3 pH 值對 MWCNT 吸附銅之影響...................................................51
4-3 奈米碳管對硝基酚與銅混合系統之吸附..................................................53
4-3-1 奈米碳管對 2-NP 與銅之吸附 ........................................................53
4-3-2 4-NP 與銅對奈米碳管之吸附 .......................................................60VI
4-4 奈米碳管修飾電極對硝基酚(NPs) 與 Cu(II) 之循環伏安法分析..........68
4-4-1 奈米碳管修飾電極(MWCNT/GCE)分析 2-NP 與 Cu(II)之反應 ...73
4-4-2 奈米碳管修飾電極(MWCNT/GCE)分析 4-NP 與 Cu(II)之反應 ...82
第五章結論與建議......................................................................................................97
5-1 結論..............................................................................................................97
5-2 建議..............................................................................................................99
參考文獻....................................................................................................................100
                                

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