本論文中將探討鈀奈米粒子應用在化學鎳鍍浴之動力學與微構造對催化作用與其電化學之分析。線性掃描伏安法(linear sweep voltammetry, LSV)之分析結果證實，當鈀奈米粒子的使用量增加時，化學鍍浴中還原劑氧化反應電流峰也相對增強，此結果說明鈀奈米粒子具有極佳的催化能力，可應用於化學鎳鍍浴。此外，利用混合電位理論法(mixed potential theory, MPT)分析發現，鈀奈米粒子的使用量從2µl增加到5µl時，鎳沉積速率可從6.31×10-2 g/cm2.s 增加至9.11×10-2 g/cm2.s。但將等量奈米活化劑以電化學石英晶體微天平(electrochemical quartz crystal microgravimetry, EQCM)即時監控所測得的實際發生沉積速率，卻較混合電位理論法之理論值快，此結果說明當電位達到平衡時，在混合電位理論中不能忽略氫及磷的沉積有關之陰極電流。另外以場發射掃描式電子顯微鏡(field emission scanning electron microscope, FE-SEM)所獲得之資訊也證實，鎳晶體在以EQCM測量的前導時間後，才會連續沉積，並且所沉積鎳層晶粒的尺寸最窄分佈在大約在沉積時間開始後120秒時觀察到。此外，藉由較高濃度之鈀奈米粒子之催化，發現較高容量的磷沉積層存在於沉積層的微構造中。
再者，開發高活性之新奈米活化液也是本論文另一個研究項目，在本研究中，利用界面活性劑-硫酸十二酯鈉(sodium n-dodecyl sulfate, SDS)為奈米模板，並藉由加入氫離子來調整模板之靜電排斥力並調節聚合，已成功製備出利用模板自組裝行為之多孔性鈀奈米球，且透過控制加入之鈀鹽的濃度，可將自組裝之鈀奈米球直徑控制約為41.5nm至56.2nm的範圍。利用石英晶體微量天平(quartz crystal microbalance, QCM)與混合電位理論之分析結果證實，多孔性之鈀奈米球具有極佳之活性，可應用作為化學鍍鎳之活化液。另外，比較不同尺寸之鈀奈米球之活性，發現小尺寸之鈀奈米球對次磷酸鈉的氧化活性最大。

Active colloids responsible for charge transfer and electron transfer in electroless metal bath me investigated in this study. Herein, the electrochemical analysis for the catalytic effect of Pd nanoparticles on deposition kinetic and microstructure in the electroless nickel-phosphorous bath was studied. As supported by linear sweep voltammetry (LSV), the currents for oxidation peaks corresponding to Pd nanoparticles upon increasing amount are measured to be enhanced. The result shows that Pd nanoparticles have excellent catalytic power in electroless nickel-phosphorous depositions (ENpD) bath. In addition, the deposition rate, analyzed by mixed potential theory (MPT), was found to increas from 6.31×10-2 g/cm2.s to 9.11×10-2 g/cm2.s. However, based on the same quantity of nanocatalyst, the deposition rates, which are in-situely monitored by electrochemical quartz crystal microgravimetry (EQCM), are measured to be faster than theoretical value given by deduced from conclude MPT. The results that that the cathodic currents for depositing hydrogen and phosphorous in the mixed potential theory could not be neglected upon reaching the equilibrium potential. As for an additional information, supported by field emission scanning electron microscope (FE-SEM), the continuous growth of nickel crystal was found after the induction time measured by EQCM. The narrowest distribution of nanosize grain was obtained at 120 seconds. In addition, the deposited layer of P with higher content was found to exist in the deposited microstructure catalyzed by the Pd nanoparticles at high concentration.
Furthermore, mesoporous and self-assembled Pd nanopsheres have been prepared in the organized micellar template, sodium n-dodecyl sulfate (SDS), the electrostatic regulation of which was adjusted by adding H+ ions. The diameter of self-assembled nanospheres can be controlled from ~41.5nm to ~56.2 nm by the concentration of palladium ions added. As supported by the analysis of quartz crystal microgravimetry and mixed potential theory, the mesoporous nanospheres can be successfully used as activators and have the excellent activity for electroless nickel-phosphorous depositions. A comparison of deposition rate with a system of Pd nanospheres, the Pd nanosphere with small size was found to exhibit maximum activity toward oxidation of NaH2PO2, reducing agent of ENpD.

1.J. Colaruotolo, D. Tramontana, in: G. O. Mallory, J. B. Hajdu (Ed.), Electroless Plating: Fundamentals and Applications, American Electroplaters and Surface Finishers Society, Orlando (1990) Ch. 8
2.R. L. Zeller, Corrosion, 50 (1994) 457
3.T. M. Harris, Q. D. Dang, J. Electrochem. Soc., 140 (1993) 81
4.M. Bayes, I. Sinitskaya, K. Schell, R. House, Trans. Inst. Met. Finish., 69 (1991) 140
5.G. F. Cui, N. Li, D. Y. Li, M. Li, J. Electrochem. Soc., 152 (2005) C669
6.J. F. Hamilton, R. C. Baetzold, Science , 205 (1979) 1213
7.R. L. Cohen, K. W. West, Chem. Phys. Lett., 16 (1972) 128
8.H. Graham, R.W. Lindsay, H. J. Read, J. Electrochemical Soc., 112 (1965) 401
9.W. J. Tomlinson, M. W. Carroll, J. Mater. Sci., 25 (1990) 4972
10.陳俊翰，以銅離子為化學鍍鎳磷鍍液之穩定劑時其析鍍行為之探討，碩士論文，國立成功大學，中華民國 (2004)
11.楊聰仁，無電鍍鎳及其應用，國璋出版社 (1987)
12.G. O. Mallory, J. B. Hajdu, Electroless Plating: Fundamentals and Applications, AESF, Orlando, U.S.A. (1990)
13.李寧，化學鍍實用技術，化學工業出版社 (2004)
14.方景禮，電鍍添加劑理論與應用，國防工業出版社 (2006)
15.M. Froment, E. Queau, J. R. Martin, G. Stremsdoerfer, J. Electrochem. Soc., 142 (1995) 3373
16.鄭宗記，李昆峰，張憲彰，電化學石英晶體微天平之原理及應用，Chemistry，59 (2001) 219
17.A. J. Bard, L. R. Faulkner, Electrochemical Methods, John Wiley &Sons, New York (2001)
18.李建良，化學鍍活化液-鈀金屬奈米粒子，產業奈米技術應用資訊園地，10 (2004) 79
19.張立德，牟季美，奈米材料和奈米結構，滄海書局 (2002)
20.蘇品書，超微粒子材料技術，復漢出版社 (1998)
21.馬振基，奈米材料科技原理與應用，全華科技圖書股份有限公司 (2003)
22.郭清癸，黃俊傑，牟中原，物理雙月刊，23 (2001) 614
23.賴炤銘，李錫隆，奈米材料的特殊效應與應用，Chemistry，61 (2003) 585
24.曹恒光，連大成，淺談微乳液，物理雙月刊，23 (2001) 488
25.C. L. Lee, C. C. Wan, Y. Y. Wang, Adv. Funct. Mater., 11 (2001) 344
26.G. O. Mallory, in: G. O. Mallory, J. B. Hajdu (Ed.), Electroless Plating: Fundamentals and Applications, American Electroplaters and Surface Finishers Society, Orlando (1990) Ch. 1
27.Y. Sverdlov, V. Bogush, H. Einati, Y. Shacham-Diamand, J. Electrochem. Soc., 152 (2005) C631
28.W. Riedel, Electroless Nickel Plating, ASM International and Finishing Publication LTD., Ohio (1991) Ch. 3
29.M. Froment, E. Queau, J. R. Martin, G. Stremsdoerfer, J. Electrochem. Soc., 142 (1995) 3373
30.M. T. Reetz, W. Helbig, S. A. Quaiser, U. Simming, N. Breuer, R.Vogel, Science, 267 (1995) 367
31.K. Boal, F. Iihan, J. E. DeRouchey, T. Thun-Albrecht, R. P. Russell, V. M. Rotello, Nature, 404 (2000) 746
32.M. J. Hostetler, S. J. Green, J. J. Stokes, R. W. Murray, J. Am. Chem. Soc., 118 (1996) 4212
33.R. P. Andres J. D. Bielefeld, J. I. Henderson, D. B. Janes, V. R. Kolagunta, C. P. Kubiak, W. J. Mahoney, R. G. Osifchin, Science, 273 (1996) 1690
34.C. P. Collier, R, J. Sakally, J. J. Shiang, S.E. Henrichs, J. R. Heath, Science, 277 (1997) 1978
35.C. Petit, A. Taleb, M.P. Pileni, Adv. Mater., 10 (1998) 259
36.Rahman, J. Appl. Polym. Sci., 28 (1983) 1331
37.J.F. Mulder, W.F. Stickle, P.E. Sobol, K.D. Bomben, J.Chastain, Handbook of X-ray Photoelectron Spectroscopy, Perkin-Elmer Corporation, Minnesota, (1992)
38.M. José-Yacamán, M. Marín-Almazo, J. A. Ascencio, J. Mol. Catal., 173 (2001) 61
39.J. F. Hamilton, R. C. Baetzold, Science, 205 (1979) 1213