具苯環及硫基官能基之中孔洞材料 SBA-1 的合成與鑑定;Synthesis and Characterization of Cubic Mesoporous Silicas SBA-1 with Phenyl and Thiol Functionalities

Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/6435

Title:	具苯環及硫基官能基之中孔洞材料 SBA-1 的合成與鑑定;Synthesis and Characterization of Cubic Mesoporous Silicas SBA-1 with Phenyl and Thiol Functionalities
Authors:	廖家秀;Chia-Hsiu Liao
Contributors:	化學研究所
Keywords:	SBA-1;中孔洞材料;硫醇;苯環;mesoporous;SBA-1;phenyl;thiol
Date:	2008-06-25
Issue Date:	2009-09-22 10:19:29 (UTC+8)
Publisher:	國立中央大學圖書館
Abstract:	本論文分為二個部份，第一部份是利用直接合成法，以PhTES (Phenyltriethoxysilane) 和 TEOS (Tetraethtyl orthosilicate) 為共同矽源，在酸性條件下合成具有苯環官能基的中孔洞材 SBA-1。研究發現苯環官能基化的中孔洞材料SBA-1，其PhTES含量最大可達33 mole % ，且結構仍相當良好。研究發現有效控制反應溫度、組成、界面活性劑總類對於合成具有規則立方排列、高表面積的中孔洞材料 Ph-SBA-1 是很重要的因素。利用固態核磁共振儀及其二維的 HETCOR、Exchange 技術來探測矽酸鹽類之間以及與界面活性劑在空間中的相對關係，由二維的13C{1H} HETCOR 和 1H-1H exchange 研究發現Ph-SBA-1 材料中的苯環官能基，和界面活性劑 CTMABr 的頭基部分 -N-(CH3)3 較鄰近，由二維的 29Si{1H} HETCOR 研究可得知植入於中孔洞材料中的苯環官能基分怖情形，是苯環官能基 (T group) 會和孔洞矽壁中的 Q4 group 較 Q3 group 鄰近。第二部份為中孔洞材料 SBA-1 的雙官能基化的研究，是利用直接合成法，以MPTMS ((3-Mercaptopropyl)trimethoxysilane) 和 BTEB (1,4-Bis(triethoxysilyl) benzene) 為共同矽源，合成具有苯環官能基和硫醇官能基的中孔洞材料 SH-BTEB-SBA-1。利用 XRD、等溫氮氣吸脫附及 13C 、29Si MAS NMR 來研究有機官能基對孔洞結構的影響。將 SH-BTEB-SBA-1 應用於吸附金屬上，發現對於汞、銅、銀離子都有相當良好的吸附效果，並發現吸附金屬後所測得的13C MAS NMR 光譜有明顯的變化，這提供了一種直接檢測固態樣品中金屬的方法。 The thesis is divided into two parts. In part one, well-ordered mesoporous silicas SBA-1 (cubic Pm3n symmetry) functionalized with phenyl groups have been synthesized via co-condensation of tetraethoxysilane (TEOS) and phenyltriethoxysilane (PhTES) under acidic conditions. The phenyl-containing units are incorporated quantitatively and reach a maximum PhTES loading up to 33 mol% without a significant degradation of the structural ordering of the Pm3n mesophase. The synthesis parameters such as temperature, type of surfactant, and synthesis composition have been systematically investigated as a function of PhTES contents. A combination of multinuclear (1H、13C、29Si) solid-state NMR and two-dimensional (2D) NMR correlation techniques such as 13C{1H} and 29Si{1H} HETCOR (heteronuclear correlation) and 1H-1H exchange NMR has been used to establish framework locations of phenyl functional groups that are incorporated in the mesoporous structure and their interactions with the surfactant molecules. 2D 13C{1H} HETCOR NMR experiments reveal that the phenyl moieties are in close spatial proximity to the trimethylammonium headgroups of the cationic surfactant species. 2D 29Si{1H} HETCOR NMR experiments reveal that the phenyl moieties are in close spatial proximity to the Q4 group than to the Q3 group. In part two, well-ordered mesoporous silicas SBA-1 (cubic Pm3n symmetry) bifunctionalized with phenyl and thiol groups have been synthesized via co-condensation of (1,4-Bis(triethoxysilyl) benzene) (BTEB) and ((3-Mercaptopropyl)trimethoxysilane) (MPTMS) under acidic conditions. The materials obtained were characterized by a variety of techniques including powder X-ray diffraction (XRD), nitrogen sorption measurements, 13C and 29Si magic angle spinning (MAS).The SH-BTEB-SBA-1 is a good candidate for being adsorbed metal ion (mercury ,copper ,and silver). Moreover, the 13C signal of the carbon atom adjacent to SH groups are senstitive to metal ion binding. We demonstrate that 13C CPMAS NMR is a good sensor for detecting the metal ion binding with SH groups.
Appears in Collections:	[Graduate Institute of Chemistry] Electronic Thesis & Dissertation

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