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標題: 前驅物植入方式合成中空ZnO暨中空Pt-Fe2O3複合殼層微球之研究
Synthesis of ZnO and Pt-Fe2O3 composite particles with hollow interiors by precursors implantation
作者: 郭旻鑫
Kuo, Min-Hsin
關鍵字: zinc oxide
iron oxide
hollow sphere
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,搭配金屬氯化物,對尺寸單一分散之有機模板進行表面改質,再以鍛燒移除模板,合成出中空微球。合成方式是將前驅物藉由植入硬質模板表層,形成核殼結構微球,有別於一般以披覆式合成中空球結構的方法。本研究中吾人將實驗分為兩個部份,首先合成ZnO中空球並探討金屬前驅體之植入機制,以及鍛燒溫度對球體結構之影響;第二部分則合成Pt/Fe2O3複合殼層微球,探討改變Pt前驅物濃度,Pt奈米顆粒於Fe2O3擔體殼層之佈植比例,與對球體微結構之影響。 在第一部份研究中,吾人將改質之有機模板(未鍛燒),以歐傑電子能譜儀(AES)進行縱深分析。結果顯示Zn前驅物是以植入之方式,與有機模板結合;以傅立葉轉換紅外線光譜儀(FTIR),對改質前與後之有機模板進行官能基分析,結果發現-CH=CH2、=CH2官能基之相對強度有所改變。吾人藉此推測前驅物與模板結合與植入過程之可能反應機制。最後分別利用熱重與熱差分析儀(TG/DSC)、場發射掃描式電子顯微鏡(FE-SEM)、穿透式電子顯微鏡(TEM),探討有機模板之熱裂解過程,並觀測在不同鍛燒溫度,對球體微結構之影響。觀測結果顯示,氧化鋅殼層於模板移除溫度前已生成,雖然高溫有助於模板移除以及殼層生成,但溫度過高,反而會造成球體崩塌。 在第二部份之Pt/Fe2O3複合殼層空心球的研究,吾人選用FeCl3以及H2PtCl6作為Fe2O3擔體殼層與活性金屬Pt之前驅物,並藉由改變Pt前驅物的含量,探討對其結構與組成的影響。首先以感應耦合電漿原子放射光譜儀(ICP-MS)對改質有機模板(未鍛燒),進行前驅物植入之元素含量分析。比較改質前驅物,與改質於模板上(Fe/Pt)莫爾比可發現,前驅物於合成反應過程中,存在著競爭植入的現象。接下來分別利用FE-SEM、TEM、BET對鍛燒處理後所得球體進行分析,結果顯示球體表面形貌、中空結構、孔徑分佈並不隨Pt佈植量的提高而有改變,但X光繞射分析儀(XRD)量測發現擔體晶粒尺寸與結晶度,隨Pt佈植量之提高而下降。最後將不同Pt佈植比例中空微球於交流電場施加環境,比較其熱性質之差異,結果發現Pt佈植量的提高,會導致釋放熱能效率下降。
A facile process has been developed to fabricate hollow spheres with nanoporous shell structure. The process used metal chloride as a precursor and polymeric hard template as the starting materials, together with tetrachloroethylene (C2Cl4) as a solvent. The hollow spheres were obtained after removal of the polymeric template by thermal pyrolysis. The process involves implantation of the precursor into the template surface to become a core-shell structure, different from those reported in the literature. In this work, the experiment was divided into two parts. First, we prepared ZnO hollow spheres, proposed a model to explain the implantation mechanism, and examined effect of calcinations temperature on hollow structure. Second, Pt/Fe2O3 composite hollow spheres were synthesized. Effect of Pt loading on microstructure of the composite particles was examined In the first part, ZnCl2 was used as the precursor. From ESCA/Auger depth analysis, Zn species penetrated to template surface for the implantation process. FTIR observed that -CH=CH2 absorption intensity becomes stronger but =CH2 absorption intensity gets weaker after the implantation. We inferred that the implantation maybe caused by tetrachloroethylene decomposition and Zn precursor recomposed to replace the original organic group on template surface. We also found that calcination temperature plays an important factor in synthesis of the hollow sphere shell. TG/DSC showed the template removal process. From SEM/TEM examination, the ZnO shell crystallized before the template had vanished, although high temperature seemed helpful to template core pyrolysis and formation of hollow spheres shell atructure. As temperature raised further to 700 oC would help the core removal, the spheres shell would collapse. In the second section, we chose FeCl3 and H2PtCl6 as the precursor for the synthesis of Pt/Fe2O3 composite hollow spheres. The H2PtCl6 concentration was adjusted in order to study the effect of Pt loading on shell structure of the composite hollow spheres. From ICP-MS analysis, we found out that the precursors would compete for the implantation. FE-SEM, TEM, BET were also used to analyze the different Pt loadings on the composite hollow spheres. XRD revealed that the Fe2O3 grain size and crystallinity decrease as the Pt loading increased. Finally, composite hollow spheres with different Pt loadings were prepared into electrorheological fluids and subjected to alternating magnetic field. Result revealed that heat transform efficiency descended when the composite hollow spheres with a higher Pt loading.
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