臺灣博碩士論文加值系統

本研究開發Fe3O4@SiO2/Ag3PO4/GO可見光光觸媒材料。Ag3PO4能隙為2.45 eV可被可見光激發，且其有優良的光催化能力，故本研究以Ag3PO4為主體，結合磁性粒子以方便回收利用，最後加入氧化石墨烯，來提升材料的光催化速率。目前文獻上尚未有將Fe3O4@SiO2/Ag3PO4/GO四種材料做結合，其優點有：(1)可在可見光下激發、(2)具有磁性，方便回收利用、(3)製備方法簡易，所以未來在處理染料及汙染物上，是具有潛力的材料。首先Fe3O4奈米粒子以共沉澱法合成，再以逆微胞法加入四乙氧基矽烷，在Fe3O4奈米粒子外包覆SiO2。將AgNO3和Na2HPO4加入Fe3O4@SiO2懸浮液中，合成出Fe3O4@SiO2/Ag3PO4複合材料。固定Fe3O4@SiO2/Ag3PO4量分別與不同比例之GO做結合，找出其光催化速率最佳的最適比例。此光觸媒材料會以穿透式電子顯微鏡、X射線繞射鑑定，確認有成功合成出Fe3O4@SiO2/Ag3PO4/GO複合光觸媒材料。接下來會以Fe3O4@SiO2/Ag3PO4/GO在可見光下進行光催化實驗，降解甲基橙溶液，結果發現降解速率會優於Fe3O4@SiO2/Ag3PO4，主要原因為添加適量GO可有效的防止電子電洞對再結合。且此光觸媒材料有與磁性粒子做結合，所以在回收利用方面，可簡易的利用外加磁場將粒子回收。

Ag3PO4, with a band gap of 2.45 eV, shows excellent photocatalitc ability under visible light irradiation. Ag3PO4 was reported to integrate with magnetic materials for recycle use. Up to date, the combination of Fe3O4/ Ag3PO4 composite with graphene oxide (GO) was not found. Accordingly, a composite of Ag3PO4 and magnetic silica (Fe3O4@SiO2) was synthesized in this study, the resultant product Fe3O4@SiO2/Ag3PO4 was mixed with GO for investigating the photocatalytic activity of Fe3O4@SiO2/Ag3PO4/GO. First, the Fe3O4 nanoparticles prepared by co-precipitation method were dispersed a reverse microemulsion suspension containing tetraethyl orthosilicate (TEOS). Then, AgNO3 and Na2HPO4 were introduced into Fe3O4@SiO2 suspension for preparing Fe3O4@SiO2/Ag3PO4, followed by mixed with various amounts of GO. The as-prepared composites Fe3O4@SiO2/Ag3PO4/GO were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), confirming the magnetic Ag3PO4 were successfully combined with GO. The results indicate that the as-prepared composite exhibits higher visible-light photocatalytic activity toward methyl orange in aqueous solution compared with Fe3O4@SiO2/Ag3PO4, possible due to GO could suppress the recombination of electron-hole pairs. On the other hand, the magnetic photocatalyst Fe3O4@SiO2/Ag3PO4/GO could be easily collected from reaction mixture by a magnet. The magnetic composite Fe3O4@SiO2/Ag3PO4/GO is thought to be a potential photocatalyst for degrading dyes and pollutants under visible light.

摘要
Abstract
致謝
目錄
表目錄
圖目錄
第一章 緒論
1-1前言
1-2磷酸銀結構及應用
1-3磁性材料基本特性
1-4光催化反應原理
1-5磷酸銀複合材料文獻回顧
1-5-1磷酸銀結合磁性粒子
1-5-2磷酸銀結合氧化石墨烯
1-5-3磁性磷酸銀結合氧化石墨烯
1-6動機與目的
第二章 材料與方法
2-1實驗方法與分析儀器設備
2-1-1 化學藥品
2-1-2實驗設備
2-1-3分析儀器
2-2簡易實驗流程
2-3材料製備
2-3-1四氧化三鐵(Fe3O4)奈米粒子製備
2-3-2磁性二氧化矽(Fe3O4@SiO2)奈米粒子製備
2-3-3磁性磷酸銀(Fe3O4@SiO2@Ag3PO4)之製備
2-3-4漢默法製備氧化石墨烯
2-3-5 Fe3O4@SiO2/Ag3PO4/GO之製備
2-4材料鑑定
2-5光降解實驗
第三章 結果與討論
3-1 Fe3O4包覆SiO2對光觸媒材料的影響
3-2 Ag3PO4與磁性Ag3PO4複合材料之鑑定分析
3-3氧化石墨烯添加量對磁性Ag3PO4複合材料光催化效能之影響
3-4循環性測試
第四章 結論
參考文獻

[1]A. Fujishima, K. Honda, Electrochemical photolysis of water at a semiconductor electrode. Nature. 238, 37–38, (1972).

[2]V. Etacheri, M.K. Seery, S.J. Hinder, S.C. Pillai, Highly visible light active TiO2−xNx heterojunction photocatalysts. Chem. Mater. 22, 3843–3853 (2010).

[3]Z. Yi, J. Ye, N. Kikugawa, T. Kako, S. Ouyang, H. Yang, et al. An orthophosphate semiconductor with photooxidation properties under visible-light irradiation. Nat. Mater. 9, 559-564 (2010).

[4]X. Ma, B. Lu, D. Li, R. Shi, C. Pan, Y. Zhu, Origin of photocatalytic activation of silver orthophosphate from first- principles. J. Phys. Chem. 115, 4680-4687 (2011)

[5]J. Liu, H. Bai, Y. Wang, Z. Liu, X. Zhang, D.D. Sun, Self- assembling TiO2 nanorods on large graphene oxide sheets at a two-phase interface and their anti-recombination in photocatalytic applications. Adv. Funct. Mater. 20, 4175–4181 (2010).

[6]T. Xu, L. Zhang, H. Cheng, Y. Zhu, Significantly enhanced photocatalytic performance of ZnO via graphene hybridization and the mechanism study. Appl. Catal. B Environ. 101, 382–387 (2011).

[7]X. Chen, Y. Dai, X. Wang, Methods and mechanism for improvement of photocatalytic activity and stability of Ag3PO4: A review. J. Alloys Compd. 649, 910–932 (2015).

[8]余宣賦、程冠博 (2006)，磁性陶瓷粉末，科學發展408期，18-23。

[9]杜怡君、張毓娟等九人 (2008)，磁性基本特性及磁性材料應用，國立台灣大學化學系。

[10]鐘明芳 (2009)，摻混錳之氧化鋅奈米粒子的製備與特性分析，國立高雄應用科技大學化學工程與材料工程系碩士論文。

[11]Y.R. Yao, W.Z. Huang, H. Zhou, X. Cui, Y.F. Zheng, X.C. Song, Synthesis of core–shell nanostructured magnetic photocatalyst Fe3O4@SiO2@Ag3PO4 with excellent visible-light-responding photocatalytic activity. J. Nanoparticle Res. 16, (2014).


[12]G. Chen, M. Sun, Q. Wei, Y. Zhang, B. Zhu, B. Du, Ag3PO4/graphene-oxide composite with remarkably enhanced visible-light-driven photocatalytic activity toward dyes in water. J. Hazard. Mater. 244-245, 86–93 (2013).

[13]Q. Xiang, D. Lang, T. Shen, F. Liu, Graphene-modified nanosized Ag3PO4 photocatalysts for enhanced visible-light photocatalytic activity and stability. Appl. Catal. B Environ. 162, 196–203 (2015).

[14]C. Wang, M. Cao, P. Wang, Y. Ao, J. Hou, J. Qian, Preparation of a magnetic graphene oxide-Ag3PO4 composite photocatalyst with enhanced photocatalytic activity under visible light irradiation. J. Taiwan Inst. Chem. Eng. 45, 1080–1086 (2014).

[15]P. Wang, Y. Ao, C. Wang, J. Hou, J. Qian, Enhanced photoelectrocatalytic activity for dye degradation by graphene–titania composite film electrodes. J. Hazard. Mater. 223–224, 79–83 (2012).