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    题名: 具高比例羧酸官能化之中孔洞材料於染料吸附及奈米金屬顆粒製備之應用;Direct Synthesis of Mesoporous Organosilicas Functionalized with Carboxylic Acid Groups: Study on Dye Adsorption and Fabrication of Metal (Ag, Pt) Nanoparticles
    作者: 張惟捷;Chang,Wei-chieh
    贡献者: 化學學系
    关键词: 中孔洞材料;亞甲基藍;奈米金屬;羧酸官能基;mesoporous;methylene blue;nanoparticles
    日期: 2013-07-22
    上传时间: 2013-08-22 11:40:39 (UTC+8)
    出版者: 國立中央大學
    摘要: 本篇論文主要合成兩種羧酸官能化之中孔洞材料,並分別探討羧酸官能化之中孔洞材料吸附染料亞甲基藍能力分析和吸附金屬離子加以還原成金屬奈米顆粒兩大部分。
    第一部分是利用非離子型界面活性劑F127做為模板,並利用1,3,5-trimethylbenzene (TMB)當作擴孔劑,再以tetraethyl orthosilicate (TEOS) 和carboxyethylsilanetriol sodium salt (CES)為共同矽源在酸性條件下合成孔洞大小約9-11 nm的具羧酸官能基中孔洞材料FTC-x;之後再利用該材料吸附亞甲基藍染料,最高可達 374 mg/g,並且在重覆使用上有很好的表現。
    第二部分是利用非離子型界面活性劑Brij 76為模板,利用1,2-bis(triethoxysilyl) ethane (BTEE) 和CES為共同矽源,合成具乙烷和羧酸官能基的雙官能基中孔洞材料EC-x,其中羧酸官能基含量最高可達85%;再利用該材料吸附銀、鉑兩種金屬離子,並利用熱還原法將金屬離子還原成金屬粒子,在製備金屬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有效控制金屬顆粒大小約3-4 nm鉑金屬與4-6 nm銀金屬。
    Here we report two projects,based one-pot synthesis of mesoporous organosilicas functionalized with carboxylic acid group. In the first project, well-order cubic mesoporous silicas FDU-12 functionalized with various contents of carboxylic acid groups were successfully synthesized via co-condensation of tetraethyl orthosilicate (TEOS) and carboxyethylsilanetriol sodium salt (CES) under acidic conditions using Pluronic F127 triblock copolymer as template, FTC-x (x refers to the [CES/(TEOS+CES)] molar ratio). The maximum loading of CES contents into the pore wall without degrading the Fm3m mesostructure was up to 50% (base on silicon).The cage size distrubutions 9-11 nm were obtained. In this study, a variefy of techniques was adopted to charaterize the FTC-x materials, including powder X-ray diffraction, nitrogen sorption measurement, 13C CP-MAS NMR, 29Si MAS NMR, fourier transform infrared spectrometer, thermogravimetric analyzer and transmission electron microscopy. And we used FTC-x to adsorp the dye, Methylene blue. The adsorption process was carefully studied with various systematic factors, including the loading amount of CES, the quanity of methylene blue, pH of adsorption system and the reuse ability. The aim of the second project was to synthesize high order ethane-briged periodic mesoporous organosilicas (PMOs) functionalized with carboxylic acid groups, up to 85%, EC-x (x refers to the [CES/(BTEE+CES)] molar ratio). In the study, many techniques were used to charaterize the EC-x materials just like FTC-x. Preparation of Ag and Pt nanoparticles is important application in EC-x. TEM was employed to observe the metal particles distrubution in EC-x, caculate the metal particles’s size from wide-angle XRD with Scherrer Formula and control the particles’s size by EC-x.
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