Department of Applied Chemistry, Faculty of Science and Engineering, Waseda University, Ohkubo 3-4-1, Shinjuku-ku, Tokyo 169-8555, Japan.
Nanoscale. 2013 Jul 7;5(13):6145-53. doi: 10.1039/c3nr00334e. Epub 2013 Jun 3.
Particle size control of colloidal mesoporous silica nanoparticles (CMPS) in a very wide range is quite significant for the design of CMPS toward various applications, such as catalysis and drug delivery. Various types of CMPS and their precursors (colloidal mesostructured silica nanoparticles (CMSS)) with different particle sizes (ca. 20-700 nm) were newly prepared from tetraalkoxysilanes with different alkoxy groups (Si(OR)4, R = Me, Et, Pr, and Bu) in the presence of alcohols (R'OH, R' = Me, Et, Pr, and Bu) as additives. CMSS with larger particle size were obtained by using tetrabutoxysilane (TBOS) and by increasing the amount of BuOH, which is explained by both the difference in the hydrolysis rates of tetraalkoxysilanes themselves and the effect of added alcohols on the hydrolysis rates of tetraalkoxysilanes. Larger amounts of alcohols with longer alkyl chains decrease the hydrolysis rates of tetraalkoxysilanes and the subsequent formation rates of silica species. Thus, the preferential particle growth of CMSS to nucleation occurs, and larger CMSS are formed. Highly dispersed CMPS were prepared by the removal of surfactants of CMSS by dialysis which can lead to the preparation of CMPS without aggregation. Therefore, the particle size control through the tuning of the hydrolysis rate of tetraalkoxysilanes can be conducted by a one-pot and easy approach. Even larger CMPS (ca. 700 nm in size) show relatively high dispersibility. This dispersibility will surely contribute to the design of materials both retaining nanoscale characteristics and avoiding various nanorisks.
控制胶体介孔硅纳米粒子(CMPS)的粒径在很宽的范围内对于设计具有各种应用(如催化和药物传递)的 CMPS 非常重要。使用不同烷氧基(Si(OR)4,R = Me、Et、Pr 和 Bu)的四烷氧基硅烷,在醇(R'OH,R' = Me、Et、Pr 和 Bu)作为添加剂的存在下,制备了具有不同粒径(约 20-700nm)的各种类型的 CMPS 和其前体(胶体介孔有序硅纳米粒子(CMSS))。通过使用四丁氧基硅烷(TBOS)并增加 BuOH 的量,可以获得粒径更大的 CMSS,这可以通过四烷氧基硅烷本身的水解速率差异以及添加的醇对四烷氧基硅烷的水解速率的影响来解释。具有更长烷基链的醇的量越大,四烷氧基硅烷的水解速率越低,随后形成的硅物种的形成速率越低。因此,CMSS 优先进行成核的颗粒生长,从而形成更大的 CMSS。通过透析去除 CMSS 的表面活性剂,可以制备出高度分散的 CMPS,这可以导致没有聚集的 CMPS 的制备。因此,可以通过一种简单的一锅法来通过调节四烷氧基硅烷的水解速率来控制粒径。即使是粒径更大的 CMPS(约 700nm)也表现出相对较高的分散性。这种分散性肯定会有助于设计既保留纳米级特征又避免各种纳米风险的材料。