臺灣博碩士論文加值系統

合成鈀或銠金屬奈米粒子常用的方法大多為化學還原法，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，並且藉由界面活性劑來提升奈米粒子的分散程度。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。
製備鈀奈米粒子部分選用有機金屬化合物Pd(tfac)2作為前驅物，加入DTAB、MTAB、CTAB及OTAB等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、界面活性劑的種類以及反應溫度可以控制奈米粒子的大小。製備銠奈米粒子部分，選用Rh(acac)(CO)2為有機金屬前驅物，在有機溶劑中，加入不同的界面活性劑，利用加熱以及溶劑中的水份將前驅物分解還原成銠原子團簇，進而自組裝成奈米粒子。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 )、粉末繞射儀 ( XRD ) 等儀器鑑定奈米粒子的特性。

The common method for fabrications of palladium and rhodium nanoparticles is chemical reduction. Most of the fabrications are reduction of metal salts in aqueous solution. In order to promote the dispersion, surfactants usually were added to avoid aggregation of the particles .
A milder preparative method to reduce organometallic complexes to produce metal nanoparticles in organic phase was developed in this research. Furthermore, the sizes and the shapes of the nanoparticles were controlled by modulating several experimental parameters. For synthesizing palladium nanoparticles, organometallic palladium complexes, Pd(tfac)2 was 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 organic solvents. Thermal decomposition of the precursor and reduction of the precursor by water within the solvents produced palladium atomic clusters, these clusters further self-assembled to nanoparticles. The results demonstrated that the sizes of palladium nanoparticles could be controlled by modulating the concentration of the precursor in the solution, the kinds of the surfactants and temperature. For synthesizing rhodium nanoparticles, organometallic rhodium complexes, Rh(acac)(CO)2 were used as the precursors, and different kinds of surfactants were added in organic solvent. Thermal decomposition of the precursor and reduction of the precursor by water within the solvents produced rhodium atomic clusters, these clusters further self-assembled to nanoparticles. The characterizations of the palladium and rhodium nanoparticles were carried out by transmission electron microscopic (TEM), energy dispersive spectroscopic (EDS), electron diffraction (ED), and X-ray Powder Diffractometer .

總目錄
總目錄-----------------------------------------------------------------------------Ⅰ
中文摘要--------------------------------------------------------------------------Ⅳ
英文摘要--------------------------------------------------------------------------Ⅴ
表目錄-----------------------------------------------------------------------------Ⅶ
圖目錄-----------------------------------------------------------------------------Ⅸ
第一章 序論---------------------------------------------------------------------1
1.1 前言------------------------------------------------------------------1
1.2 奈米材料的簡介---------------------------------------------------3
1.3 奈米材料的發展史------------------------------------------------5
1.4 奈米材料的製備---------------------------------------------------7
1.5 奈米材料的應用與未來發展------------------------------------9
1.6 鈀金屬的簡介與其應用-----------------------------------------10
1.7 銠金屬的簡介與其應用-----------------------------------------12
1.8 研究動機-----------------------------------------------------------12
第二章 實驗部分--------------------------------------------------------------15
2.1 前驅物Pd(tfac)2之合成及鑑定--------------------------------15
2.1.1 實驗藥品及反應條件-------------------------------------------15
2.1.2 前驅物Pd(tfac)2的合成與鑑定-------------------------------16
2.2 製備鈀金屬奈米粒子--------------------------------------------17
2.2.1 實驗藥品及溶劑-------------------------------------------------17
2.2.2 實驗方法及流程-------------------------------------------------18
2.3 製備銠金屬奈米粒子--------------------------------------------19
2.3.1 實驗藥品及溶劑-------------------------------------------------19
2.3.2 實驗方法及流程-------------------------------------------------20
2.4 鑑定方法及儀器--------------------------------------------------21
2.4.1 樣品處理----------------------------------------------------------21
2.4.2 鑑定儀器----------------------------------------------------------22
第三章 結果與討論-----------------------------------------------------------24
3.1 前驅物Pd(tfac)2的合成-----------------------------------------24
3.2 製備鈀金屬奈米粒子--------------------------------------------24
3.2.1 製備鈀奈米粒子的探討¬----------------------------------------24
3.2.2 以Pd(tfac)2為前驅物製備鈀奈米粒子----------------------25
3.2.2.1 不同的界面活性劑下所得到的結果-------------------------26
3.2.2.2 不同溶劑下所得到的結果--------------------------------------27
3.2.2.3 調控溶劑量及前驅物與界面活性劑的莫爾數比----------28
3.2.2.4 溫度對生成奈米粒子的影響-----------------------------------32
3.2.2.5 除水與未除水系統的比較--------------------------------------33
3.2.3 以Pd(tfac)2為前驅物製備鈀金屬奈米粒子的鑑定-------34
3.2.4 鈀奈米粒子的應用----------------------------------------------36
3.2.5 總結----------------------------------------------------------------37
3.3 製備銠金屬奈米粒子--------------------------------------------37
3.3.1 製備銠奈米粒子反應時間的決定----------------------------37
3.3.2 以Rh(acac)(CO)2為前驅物製備銠奈米粒子---------------38
3.3.2.1 不同的界面活性劑下所得到的結果-------------------------38
3.3.2.2 不同溶劑下所得到的結果--------------------------------------38
3.3.2.3 調控溶劑量及前驅物與界面活性劑的莫爾數比----------39
3.3.2.4 溫度對生成奈米粒子的影響-----------------------------------39
3.3.2.5 除水與未除水系統的比較--------------------------------------40
3.3.3 以Rh(acac)(CO)2為前驅物製備銠奈米粒子的鑑定------40
3.3.4 總結----------------------------------------------------------------41
第四章 結論--------------------------------------------------------------------42
參考文獻------------------------------------------------------------------------101

1.Huang, S. H.; Liao, M. H.; Chen, D. H. Biotechnol. Prog., 2003, 19, 1095-1100.
2.Zeng, H.; Li, J.; Wang, Z. L.; Liu, J. P.; Sun, S. Nano Lett., 2004, 4, 187-190.

3.Enaam, H. R.; Fadhil, S. K.; John, F.; Jørn, B. C. Nano Lett., 2001, 1, 599-501.

4.Xiang, W.; Tao, P.; Xiaoqing, H.; Ross, A. W. Org. Lett., 2003, 5, 2699-2701.

5.Marino, A. C.; Qinhua, H.; Tuanli, Y.; Qingping, T.; Richard, C. L. J. Am. Chem. Soc., 2003, 125, 11506-11507.
6.Lakowicz, J. R.; Gryczynski, I.; Piszczek, G.; Murphy, C. J. J. Phys. Chem. B, 2002, 106, 5365-5370.
7.Wang, Y.; Meng, G.; Zhang, L.; Liang, C.; Zhang, J. Chem. Mater., 2002, 14, 1773-1777.
8.Patolsky, F.; Gill, R.; Weizmann, Y.; Mokari, T.; Banin, U.; Willner, I. J. Am. Chem. Soc., 2003, 125, 13918-13919.
9.Ramakrishna, G.; Das, A.; Ghosh, H. N. Langmuir, 2004, 20, 1430-1435.
10.Zhang, M.; Drechsler, M.; Muller, A. H. E. Chem. Mater., 2004, 16, 537-543.
11.Gu, H.; Ho, P. L ; Tsang, K. W. T.; Wang, L.; Xu, B. J. Am. Chem. Soc., 2003, 125, 15702-15703.
12.Qiu, H.; Rieger, J.; Gilbert, B.; Jerome, R.; Jerome, C. Chem. Mater., 2004, 16, 850-856.
13.Glynou K.; Ioannou, C.; Christopoulos, T. K.; Syriopoulou, V. Anal. Chem., 2003, 75, 4155-4160.
14.Prasad, B. L. V.; Savka, I. S.; Christopher, M. S.; Vladimir, Z.; Kenneth, J. K. J. Am. Chem. Soc., 2003, 125, 10488-10489.
15.Chen, S.; Pei, R.; Zhao, T.; Dyer, D. J. J. Phys. Chem. B, 2002, 106, 1903-1908.
16.Callegari, A.; Tonti, D.; Chergui, M. Nano Lett., 2003, 3, 1595-1598.
17.Gou, L.; Murphy, C. J. Nano Lett., 2003, 3, 231-234.
18.Hambrock, J.; Schroter, M. K.; Birkner, A.; Woll, C.; Fischer, R. A. Chem. Mater., 2003, 15, 4217-4222.

19.Xu, H. S.; Ning, B. W.; Chi, P. L.; Shuit, T. L.; Pil, S. G. K.; Tsun, K. S. Chem. Mater., 2004, 16, 1143-1152.

20.Ignacio, Q.; Mami, Y.; Kenya, K.; Jun, M.; Masato, K.; Hiroshi, N. Langmuir, 2002, 18, 1413-1418.

21.Marcos, A. G.; Alexandre, P. U.; Giovanna, M.; Ricardo, R. B. C.;
Wictor, C. M.; Jonder, M.; Gunter, E.; Jairton, D.; J. Am. Chem. Soc., 2005, 127, 4588-4589.
22.Okitsu, K.; Yue, A.; Tanabe, S.; Matsumoto, H. Chem. Mater., 2000, 12, 3006-3011.
23.Dhas, N. A.; Cohen, H.; Gedanken, A. J. Phys. Chem. B, 1997, 101, 6834-6838.
24.Zhu, M. Q.; Wang, L. Q.; Exarhos, G. J.; Li, A. D. Q. J. Am. Chem. Soc., 2004, 126, 2656-2657.
25.Matsui, J.; Akamatsu, K.; Nishiguchi, S.; Miyoshi, D.; Nawafune, H.; Tamaki, K.; Sugimoto, N. Anal. Chem., 2004, 76, 1310-1315.
26.Claudia, C. C.; Alexandre, P. U.; Giovanna, M.; Silvana, I. W.; Jairton, D.; J. Am. Chem. Soc., 2005, 127, 3298-3299

27.Yoshio, U.; Mamoru, M.; Naoki, O.; Katsuyuki, O. Organic Process Research & Development, 2003, 7, 191-195

28.Garcia, M. J. C.; Lezutekong, R.; Crooks, R. M.; J. Am. Chem. Soc., 2005, 127, 5097-5103.

29.Ramachandra, R. C. N.; Kulkarni, G. U.; Thomas, P. J.; Edwards, P. P. Chem. Soc. Rev., 2000, 29, 27–35

30.Seung, U. S.; Youngjin, J.; Jongnam, P.; Hyon, B. N.; Hyun, M. P.;
Hyung, J. Y.; Jouhahn, L.; Taeghwan, H. J. Am. Chem. Soc., 2004, 126, 5026-5027

31.Srikant, P.; Marcia, T. G.; Raymond, C. K.; Karine, M.; Surya, P. G. K.; George, A. O.; Mark, E. T. Chem. Mater. 2000, 12, 1985-1989

32.Kensuke, N.; Hideaki, I.; Yoshiki, C. Nano Lett., 2002, 2, 1183-1186

33.Teranishi,T.; Miyake, M. Chem. Mater. 1998, 10, 594-600

34.Kiyoharu, T.; Yoshinori, F.; Yoshitsugu, H.; Takeji, H.; Langmuir, 1999, 15, 5200-5203

35.Tetsu, Y.; Kuniko, I.; Nobuo, K. Langmuir, 2001, 17, 4701-4703
36.Wang, C. C.; Chen, D. H.; Huang, T. C. Colloids and Surface A: Physicochemical and Engineering Aspects, 2001, 189, 145–154.
37.Nikhil, R. J.; Wang, Z. L.; Tarasankar, P. Langmuir, 2000, 16, 2457-2463

38.David, E. C.; Francis, P. Z.; Stephen, M. G.; Royce, W. M. Langmuir, 2000, 16, 9699-9702

39.Chanel, K. Y.; Rainer, J.; Abraham, U.; Henry, W.; Alexander, K.; Miriam, R.; Jonathan, S. Langmuir, 1999, 15, 3486-3491

40.Daniela, T.; Orietta, M.; Andrea, C.; Claudio,B.; Francesco, V.; Simonetta, M.; Saverio, R. Macromolecules, 2003, 36, 4294-4301

41.Joaquin, C.; Robert, W. J. S.; Richard, M. C. J. Am. Chem. Soc., 2003, 125, 11190-11191

42.Francis, P. Z.; Stephen, M. G.; Royce, W. M.; Langmuir, 2001, 17, 481-488

43.Bera, D.; Kuiry, S. C.; Patil, S.; Seal, S. Appl. Phys. Lett., 2003, 82, 3089-3091.

44.Bera, D.; Kuiry, S. C.; Seal, S. J. Phys. Chem. B, 2004, 108, 556-562.
45.Aymonier, C.; Bortzmeyer, D.; Thomann, R.; lhaupt, R. M. Chem. Mater., 2003, 15, 4874-4878
46.Pei-Feng H. and Kai-Ming C. Nanotechnology, 2004, 15, 1059-1064
47.Kenji, O.; Hiroshi, B.; Yasuaki, M. Chem. Mater., 1996, 8, 315-317.
48.Gledison, S. F.; Alexandre, P. U.; Paulo, F. P. F.; Sergio, R. T.; Jairton D. Chem. Eur. J., 2003, 9, 3263-3269

49.Marcos, A. G.; Alexandre, P. U.; Giovanna, M.; Ricardo, R. B. C.; Wictor, C. M.; Jonder, M.; Gunter, E.; Jairton, D. J. Am. Chem. Soc., 2005, 127, 4588-4589.

50.Jürgen, W.; Shinya, W.; Wararat, B.; Shigeta, H. J. Phys. Chem. B, 2002, 106, 8547-8554

51.Zitoun, D.; Amiens, C.; Chaudret , B. J. Phys. Chem. B, 003, 107, 6997-7005.

52.Trevor, D. E.; Amandeep, K. S.; Brent, C. N.; Robert, E. C.; Chil, H. C.; Daniel, F. S.; Raymond, E. S. Chem. Mater., 2005, 17, 514-520.

53.Szilvia, P.; József, S.; Albert, O.; Imre, D. Chem. Mater., 2004, 16, 1674-1685.

54.James, D. H.; Krisztian, N.; Gabor, A. S.; Don, T. T. Nano Lett.,
2005, 5, 435-438
55.曠世偉著。以有機鈀金屬製備鈀奈米結構並探討其大小及形狀的控制，國立中正大學化學暨生物化學所碩士論文, 2004.
56.Siedle, A. R.; Newmark, R. A.; Pignolet, L. H. Inorg. Chem., 1983, 22, 2281-2286.
57.Manfred, T. R.; and Matthias, M. Adv. Mater., 1999, 11, 773-777.

58.Vincenzo, C.; Angelo, N.; Antonio, M.; Antonia, D.; Patrizia, I.; Organometallics 2003, 22, 4193-4197

59.André, H. M.; Jan, M. C. A.; John, H. M.; Huub J. W.; Johannes G.
Org. Lett., 2003, 5, 3285-3288.

60.Mingqi, Z.; Li, S.; Richard, M. C. J. Am. Chem. Soc. 1998, 120, 4877-4878.

61.Enaam, H. R.; Fadhil, S. K.; John, F.; Jørn B. C. Nano Lett., 2001, 1, 499-501.

62.Anand, M.; David, G. J. Y. Tetrahedron Letters, 2001, 42, 203–206.