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dc.contributorTsong-Jen Yangen_US
dc.contributorFu-Su Yenen_US
dc.contributor.advisorWenjea J. Tsengen_US
dc.contributor.authorFan, Jin-Weien_US
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dc.description.abstract本研究以C2Cl4為溶劑,AlCl3與PtH2Cl6為反應前驅物,有機微球為模板,於室溫下反應形成核殼結構微球,經高溫煅燒移除有機模板,獲得Pt/Al2O3的複合中空微球結構,將所製成之複合中空微球粉體,以場發射掃描式電子顯微鏡(SEM)與穿透式電子顯微鏡(TEM)觀察其殼層表面形貌與結構,以比表面積儀(BET)分析殼層結構,以感應耦合電漿質譜分析儀(ICP-MS)分析Pt金屬之負載量,並將其應用在氫化反應的還原製程上,並與自製實心觸媒做氫化效果的比較。 由TEM與SEM的結果證實,於室溫以AlCl3與PtH2Cl6改質之有機微球,經500℃高溫移除有機模板後,可得到尺寸均勻的Pt/Al2O3複合中空微球結構,由Al2O3構成中空球殼,Pt粒子則部分鑲埋在球殼內,部分團聚在Al2O3表面,其尺寸則在5nm左右。經過高溫煅燒後,附著在表面的Pt粒子會發生團聚現象,而只要Al2O3的球殼型態未崩解或轉換成α相結構,鑲埋在球殼內的Pt粒子即使經1100℃煅燒仍可安定且均勻分散於Al2O3球殼內。 由BET的結果發現,於室溫反應,經500℃煅燒後之Pt/Al2O3複合中空微球為以微孔洞為主之多孔結構,與同為室溫反應,經500℃煅燒所得純Al2O3中空微球結構比較,二者孔徑分布並無明顯差異,但Pt/Al2O3之比表面積值(BET=54.11 m2/g)明顯低於單純Al2O3(BET=70.39 m2/g)結構,推測是由於Pt取代多孔的Al2O3殼層所致。 比較吾人所合成的Pt/Al2O3中空觸媒,與含浸法製備的Pt/gamma-Al2O3實心觸媒(BET=9.31 m2/g)的氫化效果發現,在相同的Pt含量下,中空觸媒的轉化效果約為實心觸媒的三倍;經過氫化反應後回收的實心與中空觸媒,其上的Pt都有團聚的現象產生,但中空觸媒上的Pt團聚現象較不明顯,具有較佳的分散性,回收之後所失去的活性面積比例較低;回收後實心觸媒上的Pt粒子則團聚的非常嚴重,喪失的活性面積比例很高,就此觀察的結果預測,中空觸媒的回收再利用性是較佳的。zh_TW
dc.description.abstractMicrospheres are synthesized at room temperature by utilizing C2Cl4 as a solvent, AlCl3 and PtH2Cl6 as precursors, and organic microspheres as a template in this research work. The composite Pt/Al2O3 microspheres with a hollow structure have been fabricated by thermal removal of the organic template at elevated temperatures. Microstructures, morphology, and specific surface area of the hollow microsphere are examined by field emission scanning microscopy (FESEM), transmission electron microscopy (TEM), and Brunauer-Emmett-Teller (BET) analyses. The Pt loading is determined by inductively coupled plasma (ICP). In addition, hydrogenation catalysis has been carried out for the hollow Pt/Al2O3 microspheres, and is compared with the home-made solid Pt/Al2O3 catalyst. Evidenced by the TEM and SEM results, uniform composite hollow microspheres consisting of Al2O3 shell and partial Pt particles embedded in the shell with a size of about 5 nm are obtained by the implantation process. Some Pt aggregation has been found on the surface of Al2O3. The Pt particles tend to attach one another on the surface of Al2O3 to form aggregates upon isothermal holding at elevated temperatures. As long as the Al2O3 shell does not transform into α-Al2O3 structure, the Pt particles distribute uniformly and are stable within the shell even after calcination to 1100℃. The BET results show that Pt/Al2O3 composite hollow microspheres and pure Al2O3 hollow microsphere possess almost identical pore diameter. However, BET surface area of the Pt/Al2O3 was significantly lower than that of pure Al2O3, presumably due to the replacement of micropores by the Pt particles in composite case. For the hydrogenation ability, the conversion efficiency of the hollow catalyst is three times higher than that of the solid one. After the hydrogenation reaction, the recycled solid and hollow microspheres both show Pt aggregation, but the hollow one is less obvious. More importantly, the recycled hollow microspheres preserve much larger ratio of activated areas than that of the solid one, demonstrating that the hollow composite catalysts may present a better chance to become re-usable.en_US
dc.description.tableofcontents第一章 緒論 1 1.1 前言 1 1.2 研究動機 1 第二章 文獻回顧 2 2.1 合成中空結構方法 2 2.1.1硬質模板法 2層接層法(layer by layer) 3化學沉積法(chemical deposition) 5化學吸附法(chemical adsorption) 5奈米鑄型(nanocasting) 7 2.1.2犧牲模板法 8 Kirkendall effect 8 galvanic replacement 9 2.1.3軟質模板法 9乳膠微滴(emulsion droplets) 9囊泡(supramolecular micelles/vesicles) 10氣泡(gas bubbles) 11 2.1.4未使用模板法 12 2.1.5 本研究室所開發之合成方法 13 2.2催化作用(catalysis)[69] 15 2.2.1 觸媒(catalyst)[6] 15 2.2.2非均勻系催化作用(heterogeneous catalysis) 16 2.2.3觸媒的選擇[6; 69] 16 2.2.4 觸媒的擔體(support) 17 2.2.5 觸媒的衰退(deactivation) 17 2.2.6 觸媒反應系統 18 第三章 實驗流程與分析儀器介紹 21 3.1實驗藥品 21 3.2製程設備 21 3.3合成Pt/Al2O3複合中空微球的實驗流程 22 3.4合成實心Pt/gamma-Al2O3實驗流程 23 3.5分析儀器 24 3.5.1穿透式電子顯微鏡(Transmission electron microscopy,TEM) 24 3.5.2場發射掃描式電子顯微鏡(Field-Emission Scanning Electron Microscopy,FE-SEM) 24 3.5.3 X光繞射分析儀(X-ray Diffractometry,XRD) 24 3.5.4表面積分析儀(Brunauer, Emmett, and Teller,BET) 24 3.5.5感應耦合電漿質譜分析儀(Inductively Coupled Plasma-Mass Spectrometer,ICP-MS) 25 3.5.6氣相色層分析(Gas Chromatography,GC) 25 3.5.7氫化反應測試 25 第四章、結果與討論 27 4.1 室溫反應合成的Pt/Al2O3複合中空微球 27 4.1.1 SEM分析 27 4.1.2 TEM分析 30 4.1.3 比表面積分析(BET) 42 4.1.4 感應耦合電漿質譜分析(ICP-MS) 45 4.2 Pt/gamma-Al2O3實心觸媒 46 4.2.1 TEM分析 46 4.2.2 比表面積分析(BET) 48 4.2.3 感應耦合電漿質譜分析(ICP-MS) 49 4.3 氫催化反應 50 4.3.1 實心觸媒與空心觸媒催化效果比較 50 4.3.2 回收觸媒分析 53 TEM分析 53 第五章、結論 59 參考文獻 61zh_TW
dc.subjecthollow microsphereen_US
dc.subjectnanocomposite structureen_US
dc.titleMicrostructure and Hydrogenation Catalysis of Pt/Al2O3 Hollow Spheresen_US
dc.typeThesis and Dissertationzh_TW
item.openairetypeThesis and Dissertation-
item.fulltextno fulltext-
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