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研究生:王鉦源
研究生(外文):Zhang-Yuan Wang
論文名稱:以化學還原法製備奈米級銀鈀微粉
論文名稱(外文):Preparation of Nanosize Silver-Palladium Particles by Chemical Reduction Method
指導教授:陳慧英陳慧英引用關係
指導教授(外文):Huey-Ing Chen
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系碩博士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:100
中文關鍵詞:奈米微粉核-殼
外文關鍵詞:silverpalladiumnanoparticlecore-shell
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本研究以硝酸銀、硝酸鈀為前驅鹽,甲醛為還原劑,PVP為保護劑,利用化學還原法製備銀鈀奈米微粉,文中探討反應液添加順序、反應時間、前驅鹽濃度、銀鈀比例、保護劑比例與還原劑比例等製備變因對銀鈀微粉之影響,並以TEM,XRD,UV/Vis及FT-IR等特性分析,探討統銀鈀微粉之生成機制。

實驗結果顯示,金屬前驅鹽、還原劑及PVP保護劑之濃度增加時,所得之微粉粒徑會有降低之趨勢。當銀鈀比例Ag/Pd <70/30時,所得為單佈性Pdcore-Agshell型奈米級微粉,且隨銀比例之增高,平均粒徑增大;但當Ag/Pd >70/30時,所得為雙佈性之銀鈀混合微粉。另外,當PVP/金屬比例為10時,所得微粉之粒徑為最小。

在銀鈀微粉之共還原機制方面,由於銀離子還原電位較鈀為小且鍵結能較高,因此在高銀鈀比例Ag/Pd >70/30時,鈀銀分別依序析出,且因銀易聚集成較大微粒,而形成雙佈性之微粉。當銀鈀比例Ag/Pd <70/30時,溶液中之銀離子便以先行析出之鈀奈米微粒為核種,包覆其上而生成核-殼型鈀銀奈米微粉。另外,以5.42 nm之鈀奈米微粒為核種,再加入硝酸銀等反應物,結果發現所得亦為雙佈性之微粉。因此,可印證鈀銀在高銀鈀比例時,係依序還原而出。
In this study, palladium-silver (Pd-Ag) nanoparticles were synthesized by the reduction of Pd(NO3)2 and AgNO3 with formaldehyde in the presence of polyvinylpyrrolidone (PVP). The effects of reactant addition, reaction time, Pd/Ag molar ratio, and HCHO/metal ratio on the properties of resultant Pd-Ag nanoparticles were investigated. Furthermore, the formation mechanism of Pd-Ag particles was also studied by means of TEM, XRD, UV/Vis, and FT-IR analyses.

Experimental results show that the Pd-Ag particle size is decreased with increasing the metal ion concentration, HCHO/metal ratio, and PVP/metal ratio. As the Ag/Pd ratio is less than 70/30, it is found that the resultant particles are nanosized dispersion with Pdcore – Agshell structure. Their particle sizes are increased with increasing the Ag/Pd ratio. As the Ag/Pd is larger than 70/30, the particles are suggested to be the mixture of Pd and Ag nanoparticles which exhibit bimodal size distribution. In addition, there exists a minimum size when the PVP/metal ratio is about 10.

For the formation of Pd/Ag nanoparticles at Ag/Pd>70/30, the Pd and Ag particles are sequentially obtained via homogeneous nucleation. However, the growth of big Ag particles caused by the large Ag-Ag bond energy leads to the bimodal particle size distribution. At Ag/Pd<70/30, Ag grains are deposited on the Pd particle surface via heterogeneous nucleation, which a Pdcore-Agshell structure is formed. Additionally, a bimodal size distribution is also obtained by reduction of AgNO3 with preseeding 5.42 nm Pd nuclei. This again confirms that the Pd/Ag nanoparticles are formed by the sequential reduction mechanism under high Ag/Pd ratio.
口試合格證明
誌謝
中文摘要 Ⅰ
英文摘要 Ⅱ
總目錄 Ⅳ
表目錄 Ⅶ
圖目錄 Ⅷ

第一章 緒論 1
1.1奈米科技發展 1
1.2奈米粒子簡介 2
1.3金屬奈米粒子簡介 3
1.3.1金屬奈米粒子之性質 3
1.3.2金屬奈米粒子之製備 5
1.3.3雙金屬奈米粒子 5
1.4銀鈀奈米粒子之應用 7
1.5研究目的 7

第二章 原理 14
2.1化學還原法簡介 14
2.2成核原理 15
2.3核-殼(core-shell)奈米粒子理論計算 19
第三章 實驗部分 25
3.1藥品 25
3.2分析儀器 25
3.2.1微粒特性分析 25
3.2.2濃度及轉化率分析 26
3.2.3一般儀器 26
3.3實驗方法及步驟 26
3.3.1共還原法製備純銀、純鈀與銀鈀奈米粒子 26
3.3.2以鈀為核種製備銀包覆鈀之核殼型奈米粒子 27
3.4分析方法 27
3.4.1晶態分析 28
3.4.2粒徑大小及分佈分析 28
3.4.3 UV/Vis分析 29
3.4.4熱重分析 29
3.4.5反應轉化率分析 29
3.4.6 FT-IR分析 29

第四章 結果與討論 34
4.1反應物添加順序之探討 34
4.2反應時間對粒子大小之影響 35
4.3金屬前驅鹽濃度之影響 36
4.4不同銀鈀比例之影響 37
4.5保護劑比例之影響 39
4.6保護劑機制之探討 41
4.7還原劑比例之影響 44
4.8以鈀為核種之銀鈀微粉製備探討 45
4.9微粉生成機制之推論 45

第五章 結論 93

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