臺灣博碩士論文加值系統

本研究係以溶膠凝膠法來製備載氧化鋅光觸媒的碳纖維氈，與研究碳複合氧化鋅氈相關性能，利用碳纖維氈含浸在醋酸鋅溶膠凝膠溶液，烘乾後再經過高溫熱處理分別為200oC、300oC、400oC後，將碳纖維氈表面鋅離子還原成氧化鋅顆粒。製成碳複合氧化鋅氈後，以亞甲基藍為預設汙染物，根據氧化鋅的特性進行光降解實驗，驗證氧化鋅光催化之性能。
在材料分析方面，本研究利用冷場發射掃描式電子顯微鏡(FESEM)來觀察氧化鋅在碳纖維氈上的表面形態，並利用X光繞射儀(XRD)、能量散佈光譜儀(EDS)與化學分析電子光譜儀(XPS)來分析氧化鋅化學組成、晶型及其結構，並以感應耦和電漿光譜儀(ICP-OES)來定量碳纖維氈上氧化鋅的鋅濃度，配合比表面積分析儀(BET)來觀察碳纖維氈與氧化鋅的比表面積與光催化的關係，用光激發光螢光光譜儀(PL)來探討碳複合氧化鋅氈上的氧化鋅之光觸媒特性，配合紫外光降解亞甲基藍來驗證碳複合氧化鋅氈光觸媒效能。
實驗結果顯示0.1 M碳纖維複合氧化鋅氈熱處理200 oC後，其比表面積從碳纖維氈的0.01 m2/g增加到4.17 m2/g，有最大的比表面積，增加了417倍，但隨著熱處理溫度提高到300 oC與400 oC，可以發現氧化鋅顆粒變小，比表面積下降到2.05 m2/g與1.47 m2/g。在亞甲基藍(10 ppm)光降解實驗中，以200 oC熱處理0.1 M碳複合氧化鋅氈25平方公分大小，置於光降解反應器中，以100瓦高壓汞燈照射30分鐘後，亞甲基藍濃度從原來的100 %減少至5 %，有最好的光降解效率95%。
本研究發現光降解效能與碳纖維氈鍍上氧化鋅的比表面積成正比，且碳纖維氈含浸0.1 M氧化鋅sol-gel溶液，熱處理200oC後，有最佳的亞甲基藍的降解效能。


關鍵字: 碳纖維氈、氧化鋅、光觸媒、亞甲基藍。

Abstract
In this study, the sol-gel method was used to prepare ZnO / carbonfelt (ZnO/C) composite photocatalyst material. The process impregnated carbonfelt in zinc acetate sol-gel solution at different concentration (0.1 M, 0.01 M, 0.001 M). Then dried in oven 24 hr at 70oC, and then heated at different temperature (200oC, 300oC, 400oC) fot 1 to 30min. The zinc ions would reduced to zinc oxide particles in carbonfelt fiber surface after heated. The carbon composite zinc oxide felt would been test by photodegradation experiment. In this experiment, methylene blue was simulation as the default pollutants. The result will show carbon composite zinc oxide felt''s performance in photodegradation.
The ZnO particle''s dispersion and surface morphology in carbonfelt been observed by field emission scanning electron microscopy (FESEM). And used X-ray scattering techniques (XRD), energy dispersive spectroscopy (EDS) and X-ray Photoelectron Spectroscopy (XPS) to obtain ZnO crystal structure, weight percent and chemical composition. Used inductively coupled plasma spectrometers (ICP) to quantify the concentration of zinc ion of zinc oxide in carbonfelt. Photoluminescence (PL) would determination of photocatalytic performance and the specific surface area of carbonfelt and ZnO/C will measure by surface area and porosity analyzer to observe the surface area and photocatalytic properties. Finally, degradation of methylene blue to verify the photocatalyst performance of the carbon composite zinc oxide felt with ultraviolet light.
The experimental results showed that 0.1 M carbon fiber composite zinc oxide felt heat 200 oC''s specific surface area4.17 m2 / g was 417 times then carbonfelt 0.01 m2 / g. But heat to 300 oC and 400 oC have small surface area decreased to 2.05 m2 / g and 1.47 m2 / g.
Photodegradation experiments test was used methylene blue (10 ppm) and placed test sample size 25 cm2 in photodegradation reactor, then irradiation by 100W UV light for 30 minutes. Result show 0.1 M carbon composite zinc oxide felt to heat treatment of 200 °C have well photodegradation performance, the concentration of methylene blue from the original 100 % to 5 %, have the best photodegradation efficiency of 95 %.
This study found that carbonfelt coated with zinc oxide material''s photo- degradation performance was proportional to it''s specific surface area value.
The carbon fiber mat impregnated with 0.1 M oxidation of zinc by the sol-gel solution, and after heat treatment 200 oC, have the well degradation efficiency of methylene blue.


Key word : carbon fiber、ZnO、photocatalyst、methylene blue.

總目錄
中文摘要..................................................I
Abstract................................................III
致謝.....................................................VI
總目錄.................................................VIII
表 目 錄................................................XII
圖 目 錄...............................................XIII
第一章 緒論...............................................1
1.1 前言..................................................1
1.2 碳材料的演進與發展....................................3
1.3 碳材料的特性與應用....................................5
1.4 光觸媒材料介紹.......................................10
1.5 光觸媒材料應用.......................................12
第二章 文獻回顧與原理探討................................15
2.1 半導體光觸媒之光催化原理.............................15
2.2 半導體光觸媒之分類...................................19
2.2.1 可見光光觸媒.......................................20
2.2.2 紫外光光觸媒.......................................21
2.3 常見光觸媒介紹.......................................22
2.3.1 二氧化鈦(TiO2)光觸媒...............................22
2.3.2 氧化鋅(ZnO)光觸媒..................................23
2.4 半導體光觸媒之應用...................................26
2.5 半導體光觸媒之製備方法...............................28
2.6溶膠凝膠法 (SOL-GEL)法製備方式與原理概述..............31
2.6.1 溶膠凝膠製程之原理概述.............................31
第三章 實驗研究目的與動機................................36
3.1 研究目的.............................................36
3.2 研究內容.............................................37
第四章 實驗方式與步驟....................................39
4.1實驗藥品與材料........................................39
4.2實驗設備與分析儀器....................................39
4.3實驗流程..............................................41
4.4實驗方法..............................................43
4.4.1碳纖維氈之前處理....................................43
4.4.2氧化鋅溶膠凝膠(sol-gel)製備.........................43
4.4.3 碳複合氧化鋅氈製備.................................43
4.4.4 熱處理條件(High temperature strain)................44
4.5 碳複合氧化鋅之特性分析...............................45
4.5.1冷場發射掃描式電子顯微鏡及能量散佈光譜儀(FESEM).....45
4.5.2微波消化系統(Microwave Lab Station)與感應耦合電漿光譜(ICP-OES)................................................47
4.5.3 化學分析電子光譜儀(ESCA,Electron Spectroscopy Chemical Analysis)......................................48
4.5.4光激光譜儀(PL Spectroscopy).........................50
4.5.5 比表面積分析儀 (BET)...............................51
4.6 光催化實驗...........................................52
4.6.1實驗流程............................................52
4.6.2實驗裝置與方法......................................52
第五章 結果與討論........................................53
5.1、碳複合氧化鋅氈之物化性分析..........................54
5.1.1 碳纖維氈之透光性分析...............................54
5.1.2 碳纖維氈之表面型態分析.............................56
5.1.3 碳複合氧化鋅氈之表面形態...........................57
5.2 碳複合氧化鋅氈之材料分析............................62
5.2.1 X光繞射分析 (XRD).................................62
5.3 碳複合氧化鋅氈之元素分析............................65
5.3.1能量散佈光譜分析(EDS)..............................65
5.3.2化學分析電子光譜儀分析(XPS).........................67
5.3.3感應耦和電漿光譜儀(ICP).............................84
5.4 碳複合氧化鋅氈之比表面積分析 (BET)...................86
5.5碳複合氧化鋅氈之光激發螢光光譜(Photoluminescence)分析.91
5.6碳複合氧化鋅氈之光催化反應與UV-VIS分析圖譜............96
5.6.1光降解實驗..........................................98
第六章 結論.............................................104
參考文獻................................................106

參考文獻
【1】賴耿陽編著,「碳材料化學與工程」, (2001)
【2】Partrick J.W., Edward Arnold & Co.Ltd., 232 ,(1988)
【3】大谷杉郎,大谷朝男著,賴耿陽譯,「碳纖維材料入門」, p.35, (1983)
【4】Bansal, R. C. “ Active Carbon, ” New York, (1988).
【5】A. Shindo, Rep. Govn. md. Res. Osaka, No. 317 (1961).
【6】J.Hayashi,A.Kazehaya,K.Meroyama,A.P.Watkinson,Carbon,38,1873, (2000)
【7】M.A.Lillo-Rodenas,D Lozano-Castello,D.Cazorla-Amoros. A.Linares-Solano,Carbon,39,751, (2001)
【8】Savage,G.Carbon-Carbon Composites.1st ed.;Chapman &Hall:New York,(1993)
【9】Griffiths J.A. Marsh H.Carbon,18,59, (1980)
【10】R. Bacon, Chemistry and Physics of Carbon, Marccel Dekker, Vol. 9, p.1,(1973)
【11】S. N. Frank, A. J. Bard, J. Phys. Chem, 81, 1484-1486, (1977).
【12】S. N. Frank, A. J. Bard, “Photochemistry of colloidal semiconducting iron oxide polymorphs”, J. Phys. Chem, , 91, 5076-5083, (1987).
【13】M.C. Markham, M.C.Hannan, S.W.Evans, , J.Am. Chem.Soc., 76, 820,(1954);
M.C.Markham, M.C.Hanna, R.M..Paternostro and C.B.Rose, J.Am.Chem.Soc., 80,5394 ,(1958).
【14】Fujishima and Honda, 1972 A Fujishima, K Honda, Nature, 238, pp. 37–38, (1972)
【15】Frank S N , Bard A J.J. Phys . Chem , 81,1484~1486, (1977).
【16】高濂 鄭珊 張青紅著, 陳憲偉校訂, 奈米光觸媒,(2004)
【17】台灣大學化工系教授呂宗昕 著,圖解奈米科技與光觸媒,(2004)
【18】Hagfeldt, A. and Gratzel, M., Chem. Rev., 95, 49 ,(1995).
【19】Inoue et al, 1979; Linsebigler et al., 1995; 藤鳩昭等,(2000).
【20】Serpone N., J. Photochem. Photobio. A: Chem, 85, 247-255, (1995).
【21】台灣大學化工系教授呂宗昕 著,圖解奈米科技與光觸媒,p171,(2004)
【22】王志光,“以二氧化鈦為主的可見光觸媒發展與基本原理”, 工業材料雜誌,201,155-163 (2003)
【23】Ulrike D, Surf. Sci.Rep.48,53,(2003).
【24】Ü. Özgür, Y. I. Alivov, C. Liu, A. Teke, M. A. Reshchikov, S. Doğan,V.Avrutin, S. J. Cho, and H. Morkoç, J. Appl. Phys., 98 ,041301, (2005).
【25】S.J. Pearton, D.P. Norton, K. Ip, Y.W. Heo, T. Steiner,, Progress in Materials Science, 50 ,293–340 ,(2005)
【26】Serpone N.Solar Energy Materials and Solar Cells,38:369~379, (1995)
【27】Herrmann J.M,Guillard C ,Pichat P.Catalysis Today.,17:7~20, (1993)
【28】李曉平，徐寶琨，劉國範等。弁鄑鰹�,30:242~245,(1999)
【29】沈偉韌，趙文寬，賀飛等。化學進展。10:349~361, (1998)
【30】Khalil L.B,Mourad W E,Rophael M.W.Appl.Catal.B Environ.,17:267~273, (1998)
【31】Yamashita H,Ichihashi Y,Anpo M.et al.J.Phys.Chem.,100:16041~16044,(1996)
【32】Yamashita H,Ichihashi Y,Harada M.et.J.Catal.,158,97,(1996)
【33】Ebelmen, Annales de Chimie et de Physique, Ser. 3, Bd 57: 319-55,(1984)
【34】Geffcken, W. and Berger, E. Deutsches Reichspatent 736411, assigned to Jenaer Glaswerk Schott ＆Gen., Jena.(1939).
【35】D. M. Roy and Roy, Am. Mineralogist, 40, 147, (1995).
【36】83. H. Dislich, “New routes to multi-component oxide glasses”,
Angew Chem. Int. Ed. Engl., 10, 363,( 1971).
【37】陳慧瑛, 黃定加, 朱秦億, “溶膠凝膠法在薄膜製備上之應用”, 化工技術, 7 (11), 152-167, (1999).
【38】 D. M. Mattox, “Sol-gel derived, air-baked indium and tin oxide films,” Thin Solid Films, 204, pp.25-32, (1991)
【39】 Watt, W., Johnson, W., Pro. 3rd Conf. Ind. Carbon graphite, Soc.Chem. Ind., Lond., 431, (1971).
【40】 A. A. Koukin, Carbon Fibers and other heat-Resisting Fibrous Materials, Khimiya, Moscow, (1974).
【41】 S. B. Warner, L. H. Peebles Jr. and D. R. Uhlmann, J. Mater. Sci., 14, P.565, (1979).
【42】 Stephen Brunauer, P. H. Emmett, Edward Teller,J. Am. Chem. Soc., 60 (2), pp 309–319, (1938)
【43】 Houas, A.; Lachheb, H.; Ksibi, M.; Elaloui, E.; Guillard, C.; Herrmann,J. M., Appl. Catal. B-Environ. 31, 2, 145-157, (2001).