具羧酸官能基之中孔洞材料於染料吸附 及製備奈米銀顆粒於催化之應用

Synthesis of Carboxylic Acid Functionalized Mesoporous Silica SBA-15 : Studies on Dye Adsorption and Fabrication of Silver Nanoparticles for Catalytic Reactions

黃亞揚(Ya-Yang Huang)

指導教授 ： 高憲明

國立中央大學/理學院/化學系/碩士(2015年)

摘要

本論文主要是利用非離子型界面活性劑P123作為模板，將具有羧酸官能基的矽源CES (Carboxyethylsilanetriol sodium salt) 和TEOS (Tetraethyl orthosilicate) 作為共同矽源在酸性條件下以直接共聚合成法進行合成，可得到二維六角柱狀之中孔洞材料，並分別探討羧酸官能基化之中孔洞材料對染料吸附應用和吸附金屬離子加以還原成金屬奈米顆粒及應用兩大部分。
第一部分是利用合成出之羧酸官能基化中孔洞材料，其簡稱STC-x，x = [CES/(CES+TEOS)] 應用在移除廢水中染料亞甲基藍及孔雀石綠。以STC-x (x = 0, 10, 30, 50) 探討對染料的吸附，發現pH值愈高與官能基含量提高皆有助於提高吸附量，並且將吸附數據代入吸附模型，Langmuir等溫吸附模式比 Freundlich等溫吸附模式更適合描述STC-x吸附染料之系統，並且比較此兩種染料的吸附情形，發現STC-x對亞甲基藍之吸附效果較佳。
第二部分則是利用合成出之STC-x，將其應用在吸附銀金屬離子，並利用熱還原法將金屬離子還原成金屬奈米粒子。在形成金屬奈米粒子的過程中因受到孔洞大小的空間限制及羧酸官能基的影響， 可以有效地將金屬顆粒尺寸最小控制在2-3 nm左右。並將其應用在還原4-Nitrophenol之催化反應。

關鍵字

中孔洞 ； 染料 ； 奈米金屬 ； 羧酸官能基

並列摘要

Mesoporous silicas SBA-15 functionalized with various contents of carboxylic acid groups were successfully synthesized via co-condensation of Tetraethyl orthosilicate (TEOS) and Carboxyethylsilanetriol sodium salt (CES) templated with a triblock polymer P123 at low HCl concentrations. All these materials have been characterized by powder X-ray diffraction (XRD), nitrogen sorption measurements, solid-state 13C and 29Si MAS NMR spectroscopy, thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and transmission electron
microscopy (TEM).
In the first project, the prepared mesoporous STC-x materials have been utilized as suitable adsorbent for methylene blue and malachite green. The adsorption process was carefully studied with varies systematic parameters, including the loading amount of CES, the quantity of dye, pH of adsorption system. The isotherm models and kinetic models were analyzed to describe the adsorption behavior of STC-x materials. As comparison, the adsorption capacity was also studied for methylene blue and malachite green. It shows that the adsorption capacity of STC-x for methylene blue is better than that of malachite green.
The aim of the second project was to prepare Ag nanoparticles within the uniform pore channels of STC-x. TEM images showed uniformly distributed nanoparticles inside the pore channels of STC-x. Synthesized Ag nanoparticles incorporated in STC-x were used as a good catalyst for the reduction of
4-nitrophenol to 4-aminophenol.

並列關鍵字

mesoporous ； dyes ； nanoparticles ； Carboxylic acid groups

參考文獻

(91) 潘育麒, 廖家秀, 高憲明, 固態核磁共振技術於孔洞材料之應用, 化學, 2004, 66, 209-219.

(90) 高憲明, 多核固態核磁共振於孔洞材料結構鑑定之應用, 化學, 2004, 62, 285-298.

(1) T. Maschmeyer, F. Rey, G. Sankar, J. M. Thomas, Heterogeneous catalysts obtained by grafting metallocene complexes onto mesoporous silica, Nature, 1995, 378, 159-162.

(2) I. S. Nielsen, E. Taarning, K. Egeblad, R. Madsen, C. H. Christensen, Direct aerobic oxidation of primary alcohols to methyl esters catalyzed by a heterogeneous gold catalyst, Catal. Lett., 2007, 116, 35-40.

(3) X. Zhung, Y. Wan, C. Feng; Y. Shen, D. Zhao, Highly efficient adsorption of bulky dye molecules in wastewater on ordered mesoporous carbons, Chem. Mater., 2009, 21, 706-716.