臺灣博碩士論文加值系統

合成金屬奈米粒子常用的方法有化學還原法、電解法、超音波震盪法等，其製備條件大多是在水相中以還原的方式將金屬鹽類還原成奈米粒子。
本論文試圖在有機相的環境中，以較溫和的加熱法將有機金屬化合物還原成奈米粒子，並且藉由調整各個實驗參數，來達到控制所生成奈米粒子的大小及形狀。實驗中選用有機鈀金屬化合物Pd(hfac)2、Pd(acac)2作為前驅物，加入 (C12H25)(CH3)3NBr、(C14H29)(CH3)3NBr、(C16H33)(CH3)3NBr、(C18H37)(CH3)3NBr 等含不同碳鏈長度的界面活性劑，在不同的有機溶劑中，利用加熱以及溶劑中的水份將前驅物分解還原成鈀原子團簇，而這些團簇更進一步自組裝成奈米粒子。研究發現，控制前驅物在溶液中的濃度以及界面活性劑的種類可以控制奈米粒子的大小，而改變前驅物與介面活性的比例，以及溶劑中的含水量，更可以得到不同大小以及形狀如六角形、方形、棒狀的鈀奈米粒子。這些實驗藉由穿透式電子顯微鏡 ( TEM )、能量分散光譜( EDS )、電子繞射 ( ED )、紫外光/可見光光譜儀 ( UV-vis ) 等儀器鑑定鈀奈米粒子的特性。

The commonly used methods for preparation of metal nanoparticles include chemical reduction, electrolysis, and ultrasonic cavitation. Most of the preparations mentioned above are reduction of metal salts in water phase.
I developed a milder preparative method to reduce organometallic complexes to palladium nanoparticles in organic phase. Furthermore, the sizes and the shapes of the nanoparticles were controlled by modulating several experimental parameters. In the experiments, organometallic palladium complexes, Pd(hfac)2 and Pd(acac)2 were used as the precursors and surfactants with various lengths of carbon chain including (C12H25)(CH3)3NBr, (C14H29)(CH3)3NBr, (C16H33)(CH3)3NBr, and (C18H37)(CH3)3NBr were added in different solvents. Thermal decomposition of the precursors and reduction of the precursors by water within the solvents produced palladium atomic clusters, these clusters further self-assembled to nanoparticles. The results demonstrated that the sizes of nanoparticles could be controlled by modulating the concentration of the precursors in the solution and the kinds of the surfactants. Palladium nanoparticles with different sizes and shapes such as hexagon, tetragon and rod can be obtained by varying the water content in the solvent and the mole ratio of precursor and surfactant. The characterizations of the palladium particles were carried out by transmission electron microscopic (TEM), energy dispersive spectroscopic (EDS), electron diffraction (ED), and ultraviolet-visible spectroscopic (UV-vis) analyses.

總目錄--------------------------------------------------------I
中文摘要----------------------------------------------------III
英文摘要-----------------------------------------------------IV
表目錄--------------------------------------------------------V
圖目錄-----------------------------------------------------VIII
第一章 序論--------------------------------------------------1
1.1 前言---------------------------------------------------1
1.2 奈米材料的簡介-----------------------------------------2
1.3 奈米材料的製備-----------------------------------------2
1.4 奈米材料的應用與未來發展-------------------------------4
1.5 鈀金屬的簡介及其奈米尺寸下的應用-----------------------5
1.6 研究動機-----------------------------------------------5
第二章 實驗部分----------------------------------------------8
2.1 製備前驅物所需的藥品及條件-----------------------------8
2.2 Pd(hfac)2的合成----------------------------------------8
2.3 Pd(acac)2的合成----------------------------------------9
2.4 製備鈀奈米粒子----------------------------------------10
2.4.1 實驗藥品---------------------------------------------10
2.4.2 實驗方法及流程---------------------------------------11
2.5 鑑定方法及儀器----------------------------------------13
第三章 結果與討論-------------------------------------------14
3.1 前驅物Pd(hfac)2 及Pd(acac)2的合成---------------------15
3.2 以Pd(hfac)2為前驅物製備Pd奈米粒子---------------------16
3.2.1 不同的溶劑所得到的結果-------------------------------16
3.2.2 不同的界面活性劑及前驅物濃度所得到的結果-------------16
3.2.3 不同加熱溫度及時間所得到的結果-----------------------20
3.2.4 在無水的o-xylene下所得到的結果--------------------------21
3.3 以Pd(acac)2為前驅物製備Pd奈米粒子--------------------24
3.3.1 不同的溶劑所得到的結果-------------------------------24
3.3.2 不同的界面活性劑及前驅物濃度所得到的結果-------------24
3.3.3 不同溫度下到的結果-----------------------------------28
3.3.4 在無水的o-xylene下所得到的結果-----------------------28
3.4 綜合鑑定分析-----------------------------------------29
第四章 結論-------------------------------------------------31
參考文獻----------------------------------------------------115

參考文獻
1.Lakowicz, J. R.; Gryczynski, I.; Piszczek, G.; Murphy, C. J.
J. Phys. Chem. B 2002, 106, 5365-5370.
2.Wang, Y.; Meng, G.; Zhang, L.; Liang, C.; Zhang, J. Chem.
Mater. 2002, 14, 1773-1777.
3.Patolsky, F.; Gill, R.; Weizmann, Y.; Mokari, T.; Banin, U.;
Willner, I. J. Am. Chem. Soc. 2003, 125, 13918-13919.
4.Ramakrishna, G.; Das, A.; Ghosh, H. N. Langmuir 2004, 20,
1430-1435.
5.Zhang, M.; Drechsler, M.; Muller, A. H. E. Chem. Mater.
2004, 16, 537-543.
6.Huang, S. H.; Liao, M. H.; Chen, D. H. Biotechnol. Prog.
2003, 19, 1095-1100.
7.Zeng, H.; Li, J.; Wang, Z. L.; Liu, J. P.; Sun, S. Nano
Lett. 2004, 4, 187-190.
8.Gu, H.; Ho, P. L ; Tsang, K. W. T.; Wang, L.; Xu, B. J. Am.
Chem. Soc. 2003, 125, 15702-15703.
9.Qiu, H.; Rieger, J.; Gilbert, B.; Jerome, R.; Jerome, C.
Chem. Mater. 2004, 16, 850-856.
10.Glynou, K.; Ioannou, C.; Christopoulos, T. K.; Syriopoulou,
V. Anal. Chem. 2003, 75, 4155-4160.
11.Yoo, J. W.; Hathcock, D.; El-Sayed, M. A. J. Phys. Chem. A
2002, 106, 2049-2054.
12.Maye, M. M.; Luo, J.; Lim, I. I. S.; Han, L.; Kariuki, N.
N.; Rabinovich, D.; Liu, T.; Zhong, C. J. J. Am. Chem. Soc.
2003, 125, 9906-9907.
13.Wang, X.; Yue, W.; He, M.; Liu, M.; Zhang, J.; Liu, Z.
Chem. Mater. 2004, 16, 799-805.
14.Choi, H. C.; Kim, W.; Wang, D.; Dai, H. J. Phys. Chem. B
2002, 106, 12361-12365.
15.Casula, M. F.; Corrias, A. Chem. Mater. 2003, 15, 2201-2207.
16.Yan, Y.; Liu, P.; Wen, J. G.; To, B.; Al-Jassim, M. M. J.
Phys. Chem. B 2003, 107, 9701-9704.
17.Wang, Y.; Tang, Z.; Correa-Duarte, M. A.; Liz-Marzan, L.
M.; Kotov, N. A. J. Am. Chem. Soc. 2003, 125, 2830-2831.
18.Chen, S.; Pei, R.; Zhao, T.; Dyer, D. J. J. Phys. Chem. B
2002, 106, 1903-1908.
19.Callegari, A.; Tonti, D.; Chergui, M. Nano Lett., 2003, 3,
1595-1598.
20.Gou, L.; Murphy, C. J. Nano Lett., 2003, 3, 231-234.
21.Hambrock, J.; Schroter, M. K.; Birkner, A.; Woll, C.;
Fischer, R. A. Chem. Mater. 2003, 15, 4217-4222.
22.Zhang, C.; OBrien, S.; Balogh, L. J. Phys. Chem. B 2002,
106, 10316-10321.
23.Yang, J.; Deivaraj, T. C.; Too, H. P.; Lee, J. Y. Langmuir
2004, 20, 4241-4245.
24.Hornebecq, V.; Antonietti, M.; Cardinal, T.; Treguer-
Delapierre, M. Chem. Mater. 2003, 15, 1993-1999.
25.He, J.; Ichinose, I.; Kunitake, T.; Nakao, A.; Shiraishi,
Y.; Toshima, N. J. Am. Chem. Soc. 2003, 125, 11034-11040.
26.Nelson, J. A.; Wagner, M. J. Chem. Mater. 2002, 14, 915-917.
27.Zhu, M. Q.; Wang, L. Q.; Exarhos, G. J.; Li, A. D. Q. J.
Am. Chem. Soc. 2004, 126, 2656-2657.
28.Matsui, J.; Akamatsu, K.; Nishiguchi, S.; Miyoshi, D.;
Nawafune, H.; Tamaki, K.; Sugimoto, N. Anal. Chem. 2004,
76, 1310-1315.
29.Gross, G. M.; Nelson, D. A.; Grate, J. W.; Synovec, R. E.
Anal. Chem. 2003, 75, 4558-4564.
30.Son, S. U.; Jang, Y.; Park, J.; Na, H. B.; Park, H. M.;
Yun, H. J.; Lee, J.; Hyeon, T. J. Am. Chem. Soc. 2004, 126,
5026-5027.
31.Wang, Y.; Herricks, T.; Xia, Y. Nano Lett., 2003, 3, 1163-
1166.
32.Esumi, K.; Tano, T.; Torigoe, K.; Meguro, K. Chem. Mater.
1990, 2, 564-567.
33.He, J.; Ichinose, I.; Kunitake, T.; Nakao, A.; Shiraishi,
Y.; Toshima, N. J. Am. Chem. Soc. 2003, 125, 11034-11040.
34.Naka, K.; Itoh, H.; Chujo, Y. Nano Lett., 2002, 2, 1183-
1186.
35.Harpeness, R.; Gedanken, A. Langmuir 2004, 20, 3431- 3434.
36.Wang, C. C.; Chen, D. H.; Huang, T. C. Colloids and Surface
A: Physicochemical and Engineering Aspects, 2001, 189, 145—
154.
37.Papp, S.; Szucs, A.; Dekany, I. Solid State Ionics, 2001,
141—142, 169—176.
38.Teranishi, T. Miyake, M. Chem. Mater, 1998, 10, 594-600.
39.Chen, S.; Huang, K.; Stearns, J. A. Chem. Mater, 2000, 12,
540-547.
40.Yonezawa, T.; Imamura, K.; Kimizuka, N. Langmuir 2001, 17,
4701-4703.
41.Bera, D.; Kuiry, S. C.; Seal, S. J. Phys. Chem. B. 2004,
108, 556-562.
42.Bera, D.; Kuiry, S. C.; Patil, S.; Seal, S. Appl. Phys.
Lett. 2003, 82, 3089-3091.
43.Carrey, J.; Bouzehouane, K.; George, J. M.; Ceneray, C.;
Blon, T.; Bibes, M.; Varue`s, A.; Fusil, S.; Kenane, S.;
Vila, L.; Piraux, L. Appl. Phys. Lett. 2002, 81, 760-762.
44.Cioffi, N.; Torsi, L.; Sabbatini, L.; Zambonin, P.G.; Bleve-
Zacheo, T. Journal of Electroanalytical Chemistry , 2000,
488 ,42—47.
45.Kenji, O.; Hiroshi, B.; Yasuaki, M. Chem. Mater. 1996, 8,
315-317.
46.Chen, W.; Cai, W.; Lei, Y.; Zhang, L. Materials Letters ,
2001, 50, 53—56.
47.Okitsu, K.; Yue, A.; Tanabe, S.; Matsumoto, H. Chem. Mater.
2000, 12, 3006-3011.
48.Dhas, N. A.; Cohen, H.; Gedanken, A. J. Phys. Chem. B,
1997, 101, 6834-6838.
49.Aymonier, C.; Bortzmeyer, D.; Thomann, R.; lhaupt, R. M.
Chem. Mater. 2003, 15, 4874-4878
50.Son, S. U.; Jang, Y.; Park, J.; Na, H. B.; Park, H. M.;
Yun, H. J.; Lee, J.; Hyeon, T. J. Am. Chem. Soc. 2004, 126,
5026-5027.
51.Esumi, K.; Tano, T.; Torigoe, K.; Meguro, K. Chem. Mater.
1990, 2, 564-567.
52.Siedle, A. R.; Newmark, R. A.; Pignolet, L. H. Inorg. Chem.
1983, 22, 2281-2286.
53.Lewis, F. D.; Salvi, G. D.; Kanis, D. R.; Ratner, M. A.
Inorg. Chem. 1993, 32, 1251-1258.