脈衝火花放電綠色合成法製備奈米金膠體溶液之研究

Pulsed Spark-Discharge Assisted Green Synthesis for Colloidal Gold Nanoparticles

黃仁春(Jen-Chuen Huang)

指導教授 ： 曾國雄

國立臺北科技大學/電資學院/電機工程系所/博士(2011年)

摘要

本論文提出綠色合成-脈衝電火花放電法(Pulsed Spark-Discharge, PSD)製備奈米金膠體溶液(Colloidal Gold)。PSD是利用火花放電在去離子水(DI-water)或酒精(Ethanol)中製備奈米金膠體溶液。兩種奈米金膠體溶液被定性與定量包含：表面分析TEM/SEM、元素與化學成份分析EDX、結構分析XRD、以及Zeta表面電位、吸收光譜分析UV-Vis等。此外本論文採用FTIR 及GC/MS儀器探討奈米金表面的修飾物質，試圖解釋奈米金膠體溶液之懸浮機制。分析結果發現，火花放電會使介電液(水或酒精)因熱熔融、電漿等作用使其分解產生衍生物並修飾在奈米金之表面。例如：純水相金表面有經由火花放電時之純水所分解出之氫氧基所修飾，而酒精之衍生物較多，但其中只有具有去質子化能力之乙酸分子能產生出羧基，並經由配位作用(Coordination)修飾吸附於金顆粒上。
奈米金之應用非常廣泛，尤其是應用於人體上，但使用時需克服NaCl及pH酸鹼值的影響。本研究將定量NaCl加入PSD所製備之奈米金膠體溶液中以模擬人體環境研究其穩定性，另外並加入多種保護劑試圖找出最佳的奈米金保護劑，以提高在生物相容之各種應用之效價。此外本論文也比較四種不同的奈米金(傳統化學合成法、PSD法之介電液為純水、酒精、及純水酒精各半)，研究酸鹼環境變化對奈米顆粒懸浮特性之影響。以相互比較各種製備方式之奈米金樣品，在pH酸鹼值變化時對懸浮特性之影響。最後為了追求PSD製備法之可控制性及產物均勻度，探討製程參數中電氣參數之影響，以進一步獲得最佳製備參數。本研究同時也完成了PSD連續運轉模式之雛型系統，可作為將來量產及工業上之應用。

關鍵字

電火花放電法 ； 奈米金 ； 水相 ； 酒精相 ； FTIR ； GC/MS

並列摘要

A green method, using pulsed spark-discharge (PSD) to synthesize colloidal gold, is studied in this thesis. PSD uses spark discharge to synthesize gold nanoparticles (AuNPs) in deionized-water (DIW) and/or ethanol (EtOH). Qualitative and quantitative methods to analyze the two colloidal golds include: TEM/SEM to analyze surface properties, EDX to analyze chemical composition, XRD to analyze crystal structures, Zeta potential analysis and UV-Visible spectroscopy.
To investigate the suspension mechanism of colloidal gold, this thesis studies the modifications on the surface of PSD-AuNPs using FTIR and GC/MS. Our results show that spark discharge will oxidize dielectric fluids (water or ethanol) by hot melt or plasma and produce derivatives to add modifications to the surface of PSD-AuNPs. For example, aqueous gold will have hydroxyl groups as surface modifications. Ethanol has more derivatives, however among those only acetic acid can generate carboxylic group by deprotonation and then modify the surface of AuNPs by coordination.
While gold nanoparticles have widespread applications in many fields, especially for the human body, in use it must overcome the influence of NaCl and pH value; therefore, this study adds NaCl into PSD-AuNPs to simulate the human body to study its stability. Furthermore, a variety of protectants are added in an attempt to determine the best protectant for AuNPs and improve biologically compatible potency. In addition, this study also examined the effect of the change of pH value on the stability of suspension of the AuNPs samples by comparing four types of nanogold (fabricated by traditional chemical synthesis method, PSD method of using deionized water, ethanol, and half deionized water and half ethanol as the dielectric fluid). Finally, in order to achieve the controllability of PSD and uniformity of products, this thesis discusses the influence of electrical parameters to further obtain the best fabrication parameters. At the same time, a prototype system of continuous mode synthesis of PSD is devised for future mass production and industrial applications.

並列關鍵字

Pulse spark discharge method ； Colloidal gold ； FTIR ； GC/MS ； Production rate.

參考文獻

[2] E. L. Nagaev, "Equilibrium and quasiequilibrium properties of small particles," Physics Reports, vol. 222, no. 4-5, 1992, pp. 199-307.

[4] D. D. Awschalom, D. P. DiVincenzo and J. F. Smyth, "Macroscopic quantum effects in nanometer-scale magnets," Science, vol. 258, no. 5081, 1992, pp. 414-421

[5] L. Messori and G. Marcon, "Gold Complexes in the treatment of Rheumatoid Arthritis," Metal ions in Biological System, vol. 41, 2004, pp. 279–304.

[8] M. C. Roco, "Nanoparticles and Nanotechnology Research," Journal of Nanoparticle Research, vol. 1, no. 1, 1999, pp. 1-6.

[9] M. Reibold, P. Paufler, A. A. Levin, W. Kochmann, N. Patzke and D. C. Meyer, "Materials: Carbon nanotubes in an ancient Damascus saber," Nature, vol. 444, no. 7117, 2006, pp. 286.