銀鈀金屬奈米粒子的製備、鑑定 以及在催化反應的應用

Preparation, Characterization of AgPd Nanostructures and Application for Catalysis

林冠宇(Guan-Yu Lin)

指導教授 ： 吉凱明

國立中正大學/理學院/化學暨生物化學系/碩士(2015年)

摘要

本篇論文研究以有機金屬前驅物Palladium(II) acetylacetonate及(Trimethylphosphine)(hexafluoroacetylacetonato) silver(I) 於有機溶劑中進行熱裂解反應，並調控各實驗參數，如溶劑種類、濃度、反應溫度及前驅物與界面活性劑比例等。我們利用1-Octylamine、o-xylene、Decane及Dodecane等四種溶劑系統下，改變不同種類界面活性劑(如TOPO、SDS、C12-18TAB等)，發現在加入陽離子界面活性劑有顯著的形狀大小控制，可藉由調控界面活性劑與金屬前驅物的莫耳比例得到不同大小(~5、15 nm)之球形奈米粒子。所得之奈米粒子均為銀鈀原子均勻分佈之銀鈀合金，在溶劑自然揮發的環境下，銀鈀粒子由陽離子界面活性劑包覆並交疊，因此產生粒子間自組裝作用，形成一維線性、二維平面、三維堆疊的整齊排列。最後我們將以此奈米粒子做為Heck反應之催化劑，去探討不同尺寸銀鈀奈米粒子的催化活性。
鑑定方面，我們利用穿透式電子顯微鏡(TEM)觀察奈米粒子的粒徑大小及形狀，以X-ray粉末繞射儀(XRD)及選區電子繞射(SAED)鑑定其結構，並且利用能量分散光譜儀(EDS)、X-ray光電子能譜儀(XPS)及火焰原子吸收光譜儀(FAAS)檢測銀鈀奈米粒子的組成。

關鍵字：銀鈀粒子、奈米合金、自組裝

關鍵字

自組裝 ； 奈米合金 ； 銀鈀粒子

並列摘要

In this study, we have employed Pd(acac)2 and (hfac)Ag(PMe3) as precursors in various organic solvents to generate the Ag-Pd alloy nanoparticles by thermal decomposition method. Experimental factors such as solvents, concentration, reaction temperature and the mole ratio of precursor and surfactant were adjusted in this research. We varied the surfactants(TOPO, SDS, C12-18TAB et al.) and mole ratio of precursor and surfactant to obtain nanoparticles with different sizes(~5、15 nm) in 1-octylamine, o-xylene, decane and dodecane solvent systems. Especially, the cationic surfactants have significant effect on size control. The obtained Ag-Pd monodispersed nanoparticles have uniform distribution of silver and palladium atoms. In condition of solvent evaporation, the nanoparticles have induced self-assembly to the 1D line, 2D plane and 3D stack. This phenomenon is caused by size-controll and monodisperse. Finally, we have used Ag-Pd nanoparticles to investigate the catalytic activity of Heck reaction by differents of nanoparticle sizes.
The nanoparticles were characterized by transmission electron microscopy to observe the morphology. We analyze the structure of Ag-Pd nanostructures by X-ray diffraction(XRD) and selected area diffraction(SAED). The uniform composition is confirmed by the energy-dispersive X-ray spectroscopy(EDS), X-ray photoelectron spectroscopy(XPS) and flame atomic absorption spectrometry(FAAS).

Keywords： Ag-Pd nanostructures、Nanoalloy、Self-assembly

並列關鍵字

Nanoalloy ； Ag-Pd nanostructures ； Self-assembly

參考文獻

2. Haruta, M.; Kobayashi, T.; Sano, H.; Yamada, N. Chem. Lett. 1987, 16, 405-408.

3. Xia, Y. ; Xiong, Y.; Lim, B.; Skrabalak, S. E. Angew. Chem. Int. Ed. 2009, 48, 60-103.

5. Whitesides, G. M.; Grzybowski, B. Science, 2002, 295, 2418-2421.

6. Sánchez-Iglesias, A.; Grzelczak, M.; Pérez-Juste, J.; Liz-Marzán, L. M. Angew. Chem. Int. Ed. 2010, 49, 9985-9989.

11. Hirasawa, S.; Nakagawa, Y.; Tomishige, K. Catal. Sci. Technol. 2012, 2, 1150-1152.