萘基桥联有机-无机杂化介孔材料的合成及其光学性质

doi:10.3866/PKU.WHXB201212201

摘要/Abstract

摘要：

以短链阳离子三聚表面活性剂C₁₀H₂₁N⁺(CH₃)₂(CH₂)₂N⁺(CH₃)(C₁₀H₂₁)(CH₂)₂N⁺(CH₃)₂C₁₀H₂₁]·3Br^?为结构导向剂, 通过2,7-二(3-三乙氧硅基氨丙酯基)萘(NIS)和四乙氧基硅烷(TEOS)共缩聚, 制备了有序的萘基桥联的杂化周期性介孔有机硅(PMOs). 样品通过X射线衍射(XRD)、高分辨透射电镜(HRTEM)、氮气吸附-脱附、差示扫描量热/热重分析(DSC/TGA)表征. 结果表明, 当NIS占NIS和TEOS总量40% (摩尔分数)时, 可以形成具有结晶态孔壁的有序介孔杂化材料. 当NIS含量低于或高于40%时, 分别形成无定形孔壁的有序介孔杂化材料和无孔杂化材料. 随着孔壁中萘基基团的增加, 由于有机基团之间π-π堆积作用增强, 杂化介孔材料显示良好的热稳定性. 由于在二氧化硅骨架中嵌入荧光萘基基团, 杂化有机-无机有序介孔材料显示了激基缔合物的光学行为. 随萘基基团含量的增加, 杂化材料的紫外吸收峰发生蓝移, 形成H聚集体; 由于聚集引起的荧光淬灭, 杂化材料的荧光量子产率明显降低.

关键词: 有机-无机杂化材料, 2,7-二(3-三乙氧硅基氨丙酯基)萘, 三聚阳离子表面活性剂, 荧光, 桥联有机硅烷前驱体

Abstract:

Ordered naphthalene-bridged hybrid periodic mesoporous organosilicas (PMOs) were synthesized by co-condensation of 2,7-bis(3-triethoxysilylpropylaminocarbonyloxy) naphthalene (NIS) and tetraethoxy orthosilane (TEOS) using cationic trimeric surfactant C₁₀H₂₁N⁺(CH₃)₂(CH₂)₂N⁺(CH₃)(C₁₀H₂₁)(CH₂)₂N⁺(CH₃)₂C₁₀H₂₁]·3Br^? as a structure-directing agent. The resulting samples were characterized by powder X-ray diffraction, high resolution transmission electron microscopy, nitrogen adsorption-desorption, and differential scanning calorimetry/thermogravimetric analysis. Ordered mesoporous hybrid materials with a crystal-like pore wall formed when the molar ratio of NIS to the sum of NIS and TEOS was 40%. When this value is below or above 40%, ordered mesoporous hybrid materials with amorphous phase in the pore walls, and nonporous hybrid materials are obtained, respectively. As the number of naphthyl groups in the pore walls increases, the thermal stability of the hybrid materials is enhanced through the strong π-π interactions between organic groups. Because of the fluorescent naphthyl groups in the silica framework, the PMOs exhibit optical behavior consistent with excimer formation. Absorption spectra of the PMOs show blue shifts compared with that of the precursor (NIS), suggesting the formation of aggregates in the pore walls of the hybrid materials. As the molar ratio of NIS to the sum of NIS and TEOS increases, the fluorescence quantum yield of the PMOs decreases through fluorescence quenching caused by aggregation of naphthyl groups.

Key words: Organic-inorganic hybrid material, 2,7-Bis(3-triethoxysilylpropylaminocarbonyloxy) naphthalene, Cationic trimeric surfactant, Fluorescence, Bridged organosilane precursor

MSC2000:

O648

崔小燕, 韩书华, 孙元元, 王莎莎, 邱晓勇, 高萌. 萘基桥联有机-无机杂化介孔材料的合成及其光学性质[J]. 物理化学学报, 2013, 29(03): 639-645.

CUI Xiao-Yan, HAN Shu-Hua, SUN Yuan-Yuan, WANG Sha-Sha, QIU Xiao-Yong, GAO Meng. Synthesis and Optical Properties of Organic-Inorganic Hybrid Mesoporous Materials with Naphthalene Bridging Groups[J]. Acta Phys. -Chim. Sin., 2013, 29(03): 639-645.

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