REQUIMTE/Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre, 4169-007 Porto, Portugal.
J Colloid Interface Sci. 2010 Apr 15;344(2):603-10. doi: 10.1016/j.jcis.2010.01.026. Epub 2010 Jan 18.
Silylation of several materials where the surface area arises from the internal pores (MCM-41 and FSM-16) or is essentially external (silica gel, and clays) was performed using three organosilanes: (3-aminopropyl)triethoxysilane (APTES), 4-(triethoxysilyl)aniline (TESA) and (3-mercaptopropyl)trimethoxysilane (MPTS). The materials were characterized by nitrogen adsorption-desorption at -196 degrees C, powder XRD, XPS, bulk chemical analysis, FTIR and (29)Si and (13)C MAS NMR. For MCM-41 and FSM-16 the highest amounts of organosilane are obtained for APTES, while for the remaining materials the highest amounts are for MPTS; TESA always anchored with the lowest percentage. In terms of surface chemical analysis, TESA anchored with the highest contents irrespectively of the material, and the opposite is registered for MPTS. Comparison of bulk vs surface contents indicate that TESA is mainly anchored at the material external surface. Moreover, with N or S (surface and bulk) contents expressed per unit of surface area, MCM-41 and FSM-16 (internal porosity) show the lowest amounts of silane; the highest amounts of silane per unit of surface area are obtained for the clays. Grafting of the organosilanes to the surface hydroxyl groups was corroborated by FTIR and (29)Si and (13)C MAS NMR. Furthermore, NMR data suggested that TESA and APTES grafted mostly through a bidentate approach, whereas MPTS grafted by a monodentate mechanism.
几种材料的硅烷化处理，其中表面积来自内部孔（MCM-41 和 FSM-16）或本质上是外部的（硅胶和粘土），使用三种有机硅烷进行：（3-氨丙基）三乙氧基硅烷（APTES）、4-（三乙氧基硅基）苯胺（TESA）和（3-巯丙基）三甲氧基硅烷（MPTS）。这些材料通过在-196°C 下的氮气吸附-解吸、粉末 XRD、XPS、体化学分析、FTIR 和（29）Si 和（13）C MAS NMR 进行了表征。对于 MCM-41 和 FSM-16，APTES 获得了最高量的有机硅烷，而对于其余材料，MPTS 获得了最高量的有机硅烷；TESA 总是以最低的百分比固定。就表面化学分析而言，TESA 无论材料如何，都以最高的含量固定，而 MPTS 则相反。比较体相和表面相含量表明，TESA 主要固定在材料的外表面。此外，用单位表面积上的 N 或 S（表面和体相）含量表示，MCM-41 和 FSM-16（内部孔隙率）显示出最低的硅烷含量；每单位表面积获得的硅烷量最高的是粘土。FTIR 和（29）Si 和（13）C MAS NMR 证实了有机硅烷接枝到表面羟基上。此外，NMR 数据表明，TESA 和 APTES 主要通过双齿方式接枝，而 MPTS 通过单齿机制接枝。
