Mechanism of Formation of Uniform-Sized Silica Nanospheres Catalyzed by Basic Amino Acids

• Published in: Chemistry of materials 2009-08, Vol.21 (15), p.3719-3729
• Main Authors: Yokoi, Toshiyuki, Wakabayashi, Junji, Otsuka, Yuki, Fan, Wei, Iwama, Marie, Watanabe, Ryota, Aramaki, Kenji, Shimojima, Atsushi, Tatsumi, Takashi, Okubo, Tatsuya
• Format: Article
• Language: English
• Subjects: Nanomaterials (Nanops, Nanotubes, etc.); Porous Materials (including Meso- and Micro-Porous Materials); Self-Assembly and Self-Assembled Materials
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/cm900993b

A liquid-phase method for preparing uniform-sized silica nanospheres (SNSs) 12 nm in size and their three-dimensionally ordered arrangement upon solvent evaporation have recently been pioneered by us. The SNSs are formed in the emulsion system containing Si(OEt)4 (TEOS), water, and basic amino acids under weakly basic conditions (pH 9−10). Here, we report the formation mechanism of the SNSs; the reasons for the uniform size and the ordered arrangement are described in detail. The formation process is monitored by FE-SEM, SAXS, and liquid-state NMR. The FE-SEM observations reveal that silica nanoparticles ca. 4 nm in size are formed in the water phase at the early stage (∼0.5 h) of the reaction. The SAXS measurements suggest that the number density of the particles remains unchanged when they are gradually grown. Liquid-state 1H NMR analyses suggest that TEOS are slowly hydrolyzed at the oil−water interface to continuously supply silicate species into the water phase. The silicate species are immediately consumed for the growth of the parent particles without forming new particles. The size of the SNSs can be tuned from 8 to 35 nm by varying the synthesis conditions and/or the amount of TEOS. The zeta potential and pH of the dispersion of SNSs throughout the solvent evaporation process are almost constant approximately at −40 mV and 9−10, respectively; the SNSs have been well-dispersed until the final stage of the evaporation process. The critical roles of basic amino acids in the formation and regular arrangement of SNSs are discussed based on the experimental results.