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通过碱性共缩聚自组装实现具有1,2-双[3-(三乙氧基硅丙基)脲基]环己烷官能团的周期性介孔有机硅的骨架功能化。

Framework functionalization of periodic mesoporous organosilica with 1,2-bis[3-(triethoxysilylpropyl)ureido] cyclohexane function via basic co-condensation self-assembly.

作者信息

Abdul Wahab M, Kim I, Ha C S

机构信息

Department of Molecular and Performance Materials Cluster, Institute of Materials Research and Engineering (IMRE), 3 Research Link, Singapore 117602, Republic of Singapore.

出版信息

J Nanosci Nanotechnol. 2008 Jul;8(7):3532-8. doi: 10.1166/jnn.2008.110.

DOI:10.1166/jnn.2008.110
PMID:19051907
Abstract

The synthesized bis silylated long alkyl chain containing organosilicate precursor, 1,2-bis(3-(triethoxysilylpropyl)ureido)cyclohexane (BSPUCh) has been used as co-precursor with 1,2-bis (triethoxysilyl)ethane (BTSE) for the preparation of functional periodic mesoporous organosilicas (PMOs) via surfactant-mediated basic co-condensation self-assembly method. The various characterization techniques such as X-ray diffraction patterns (XRD), transmission electron microscope (TEM), N2 adsorption-desorption isotherms (BET), FT-IR, and 13C and 29Si CPMAS NMR spectroscopies were used to characterize the resulting structure of functionalized PMO mesostructures. Results obtained from XRD, TEM, and BET analysis clearly showed that the structural and pore arrangement of the functionalized PMOs were found to be dependent on the used concentration of BSPUCh. The functional PMOs showed well ordered mesophases when BSPUCh concentration was < or = 9 wt% in the initial mixtures, whereas higher concentration of the BSPUCh always produced disordered hierarchical mesostructures with bimodal pore size distributions. The incorporation of BSPUCh also reduces the surface area, pore volume, pore size, and pore wall thickness of the functionalized nanostructures, indicating that the BSPUCh is incorporated in the pore channels of the PMOs. The solid-state 13C and 29Si NMR spectra showed that the BSPUCh organosilicate with non-hydrolyzable bridging ligands propylureidocyclohexane has been successfully covalently linked in the framework of the resulting functional PMOs.

摘要

合成的含双硅烷基化长烷基链的有机硅酸盐前驱体1,2 - 双(3-(三乙氧基硅基丙基)脲基)环己烷(BSPUCh)已与1,2 - 双(三乙氧基硅基)乙烷(BTSE)作为共前驱体,通过表面活性剂介导的碱性共缩聚自组装方法制备功能化周期性介孔有机硅(PMO)。采用多种表征技术,如X射线衍射图谱(XRD)、透射电子显微镜(TEM)、N2吸附 - 脱附等温线(BET)、傅里叶变换红外光谱(FT - IR)以及13C和29Si交叉极化魔角旋转核磁共振光谱(CPMAS NMR)来表征所得功能化PMO介孔结构的结构。XRD、TEM和BET分析结果清楚地表明,功能化PMO的结构和孔排列取决于所使用的BSPUCh浓度。当初始混合物中BSPUCh浓度≤9 wt%时,功能化PMO呈现出有序的介相,而较高浓度的BSPUCh总是产生具有双峰孔径分布的无序分级介孔结构。BSPUCh的掺入还降低了功能化纳米结构的表面积、孔体积、孔径和孔壁厚度,这表明BSPUCh掺入到了PMO的孔道中。固态13C和29Si NMR光谱表明,带有不可水解桥连配体丙基脲基环己烷的BSPUCh有机硅酸盐已成功地共价连接到所得功能化PMO的骨架中。

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