Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/10671
標題: 以植入法合成單一分散中空Al2O3暨Pt-Al2O3微球之研究
Synthesis of Monodispersed Al2O3 and Pt-Al2O3 Hollow Microspheres by Implantation of Precursor
作者: 李維特
Li, Wei-Te
關鍵字: Pt
Pt
Al2O3
organic microsphere
core-shell structure
Al2O3
有機微球
核殼結構
出版社: 材料科學與工程學系所
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摘要: 本研究以C2Cl4為反應溶劑,AlCl3為合成Al2O3之前驅物,有機微球為模板,藉由植入之方式使AlCl3前驅物存在於有機微球模板內,形成核殼結構微球,經由高溫煅燒移除有機模板,可得Al2O3中空微球。另外吾人採用AlCl3、H2PtCl6.nH2O作為合成Pt-Al2O3中空微球之前驅體,C2Cl4作為系統溶劑,採用兩種實驗製程,將獲得之改質有機微球經由空氣的氣氛煅燒,移除內部有機核,合成Pt-Al2O3中空複合微球。由ESCA縱深分析結果得知,含Pt或Al前驅物皆以植入方式存在於有機微球;改變AlCl3改質微球之反應溫度並改變煅燒溫度及持溫時間,將獲得之中空微球粉體,利用穿透式電子顯微鏡(TEM)觀察其殼層表面。此外並利用X光繞射分析儀(XRD)、拉曼分析儀(Raman)、場發射掃描式電子顯微鏡(FE-SEM)、穿透式電子顯微鏡(TEM)與比表面積分析儀(BET)等分析其表面微結構;以感應耦合電漿質譜分析儀(ICP-MS)分析Pt金屬之負載量。 由AlCl3改質有機微球的TEM分析得知,當合成反應溫度由25℃增加至75℃與95℃時,球殼厚度在高於25℃之合成溫度後有顯著增厚趨勢,從約30nm增加至約80nm;當反應溫度在75℃,隨著煅燒之持溫時間從2小時增加至24小時,微孔洞有逐漸減少趨勢,從約50nm減少至約10nm直至最後完全消失,猜測為α-Al2O3晶粒成長所造成。 由TEM及ICP結果顯示,經過1100℃煅燒後,製程I及製程II兩種製程皆可得到Pt-Al2O3複合微球,由製程I Pt/α-Al2O3發現,Pt負載量較低,Pt粒子粒徑小(約5nm)且較均勻,製程II Pt/α-Al2O3雖然Pt負載量較高,但Pt粒子粒徑較大(約40~180nm)且不均勻。由Raman結果顯示,經1000℃煅燒後,製程I Pt-Al2O3 即有Al2O3的α與θ相形成,並於1100℃煅燒後,結晶相完全轉變為α相,但製程II Pt-Al2O3在1000℃煅燒後只有θ相,於1100℃煅燒後,才形成α與θ相,要完全形成α相則需要1200℃。XRD結果顯示製程I與製程II Pt-Al2O3只發現會有α-Al2O3結晶相,但製程II Pt-Al2O3須在1100℃煅燒後方形成α相,而製程II Pt-Al2O3須在1200℃煅燒後形成α相,和XRD結果吻合。
This research uses C2Cl4 as a reactive solvent, AlCl3 as a precursor for Al2O3, and organic microspheres as a template in a way that the AlCl3 is implanted into surface of organic cores to form a core-shell structure. Al2O3 microspheres with hollow interiors are formed after thermal pyrolysis to remove the organic core. In addition, this research also uses C2Cl4 as a reactive solvent, AlCl3 and H2PtCl6.nH2O as precursors for synthesis of Pt-Al2O3 composite hollow particles. Two processes (processes I and II) have been used for the synthesis, and Pt-Al2O3 hollow microspheres are formed after thermal pyrolysis which removes the organic core. From the depth profile of ESCA analysis, the precursors used in the process are located beneath the surface of organic cores by an implantation of Al or Pt ions. The reaction temperature, calcination temperature and calcination time have been changed to examine the microstructure, phase transformation, and specific surface area of the hollow microspheres by TEM, FESEM, XRD, Raman and BET. The loading amount of Pt element is analyzed by ICP. From TEM analysis, the shell thickness of the Al2O3 hollow microspheres increases with the increasing reaction temperature. When the reaction temperature is held at 75oC, pores on the shell appear to decrease with the increasing calcination time, presumably caused by grain growth of α-Al2O3. From TEM and ICP results, at 1100oC, Pt loading is lower in the Process I Pt/α-Al2O3 and Pt particle size is smaller and disperses more uniform in alumina matrix. The Pt particle size is about 5nm. On the other hand, the Pt loading is higher for the Process II Pt/α-Al2O3, but the Pt particle size is larger (about 40~180nm). From Raman analyses, at 1000oC, αphase and θ phase Al2O3 are formed in the Process I Pt-Al2O3 and at 1100oC, the crystalline phase is completely transformed intoαphase. But after calcination at 1000oC, onlyαphase is formed in the Process II Pt-Al2O3. At 1100oC, the θphase is formed and theαphase is completely formed at 1200oC. From XRD results, only α-Al2O3 phase is found, but for the Process I Pt-Al2O3, the complete formation of α-Al2O3 phase occurs at 1100oC. On the other hand,αphase is formed at 1200oC for the Process II. Key word: Pt, Al2O3, organic microsphere, core-shell structure
URI: http://hdl.handle.net/11455/10671
Appears in Collections:材料科學與工程學系

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