Center for Surface Chemistry and Catalysis, Catholic University of Leuven, Kasteelpark Arenberg 23, B-3001 Leuven, Belgium.
J Am Chem Soc. 2011 Aug 31;133(34):13737-45. doi: 10.1021/ja205627t. Epub 2011 Aug 10.
Hexagonally ordered mesoporous silica coined COK-12 was synthesized in a continuous process by combining streams of sodium silicate and citric acid/sodium citrate buffered solution of (ethylene oxide)(20)-(propylene oxide)(70)-(ethylene oxide)(20) triblock copolymer (Pluronic P123) from separate reservoirs. COK-12 precipitated spontaneously upon combining both streams at nearly neutral pH and ambient temperature. Stable intermediates of the COK-12 formation process could be prepared by limiting sodium silicate addition. Investigation of these intermediates using small-angle X-ray scattering revealed COK-12 formed via an assembly process departing from spherical uncharged core-shell P123-silica micelles. The sterical stabilization of these micelles decreased upon accumulation of silicate oligomers in their shell. Aggregation of the spherical micelles led to cylindrical micelles, which aligned and adopted the final hexagonal organization. This unprecedentedly fast formation of P6m ordered mesoporous silica was caused by two factors in the synthesis medium: the neutral pH favoring uncharged silicate oligomers and the high salt concentration promoting hydrophobic interactions with surfactant micelles leading to silica accumulation in the PEO shell. The easy continuous synthesis process is convenient for large-scale production. The platelet particle morphology with short and identical internal channels will be advantageous for many applications such as pore replication, nanotube or fiber growth, catalytic functionalization, drug delivery, film and sensor development, and in nano dyes as well as for investigation of pore diffusion phenomena.
六方有序介孔硅 COK-12 通过将硅酸钠溶液和柠檬酸/柠檬酸钠缓冲溶液(聚氧乙烯(20)-聚氧丙烯(70)-聚氧乙烯(20)三嵌段共聚物(Pluronic P123))从单独的储液罐中连续流合并来合成。在接近中性 pH 值和环境温度下,将两种溶液合并时,COK-12 会自发沉淀。通过限制硅酸钠的添加,可以制备 COK-12 形成过程的稳定中间体。使用小角 X 射线散射研究这些中间体表明,COK-12 是通过一种组装过程形成的,该过程偏离了不带电的核壳 P123-二氧化硅胶束的球形。当硅酸盐齐聚物在其壳中积累时,这些胶束的空间位阻稳定性降低。球形胶束的聚集导致圆柱形胶束的形成,这些胶束排列并采用最终的六方组织。在合成介质中存在两个因素导致了 P6m 有序介孔硅的这种前所未有的快速形成:有利于不带电的硅酸盐齐聚物的中性 pH 值,以及促进与表面活性剂胶束的疏水相互作用的高盐浓度,导致二氧化硅在 PEO 壳中积累。这种易于连续合成的过程方便了大规模生产。具有短而相同的内部通道的血小板颗粒形态将有利于许多应用,例如孔复制、纳米管或纤维生长、催化功能化、药物输送、薄膜和传感器开发,以及纳米染料以及用于研究孔扩散现象。