(725b) Synthesis of Uniform Silica Nanospheres In Liquid-Liquid Biphasic Systems Using Amines or Ammonia Catalyst and Their Controlled Self-Assembly | AIChE

(725b) Synthesis of Uniform Silica Nanospheres In Liquid-Liquid Biphasic Systems Using Amines or Ammonia Catalyst and Their Controlled Self-Assembly

Authors 

Wang, J. - Presenter, The University of Tokyo
Sugawara-Narutaki, A. - Presenter, The University of Tokyo
Fukao, M. - Presenter, The University of Tokyo
Shimojima, A. - Presenter, The University of Tokyo
Okubo, T. - Presenter, The University of Tokyo
Yokoi, T. - Presenter, Tokyo Institute of Technology


A significant progress has recently been made in the synthesis of uniform silica nanospheres (SNSs) less than 30 nm in diameter by using basic amino acids (e.g., lysine) as a base catalyst for hydrolysis of silicon alkoxide.1,2 Alternatively, this talk describes a more versatile and economical amino acid-free method to synthesize uniform SNSs with low polydispersity (<12%) in organic–aqueous biphasic systems containing tetraethoxysilane (TEOS), water, and primary amine (or ammonia) under precisely controlled pH conditions (pH 10.8–11.4).3 The diameter of the SNSs determined from scanning electron microscopy (SEM) can be tuned from ~12 to ~36 nm by simply changing the initial pH of the aqueous phase in the reaction mixtures. Moreover, the as-synthesized silica sol was taken as the starting material for studying the influences of the type of base catalysts on the solvent evaporation-induced three-dimensional (3D) self-assembly of SNSs. X-ray diffraction (XRD) and nitrogen adsorption–desorption were used to characterize the degree of packing of the resulting 3D SNSs arrays. The SNSs arrays that possess large interparticle mesopores with the diameter of ca. 8.1 nm and low packing fraction of ca. 66.1% are observed upon solvent evaporation of as-synthesized sol in the presence of primary amine. This indicates that SNSs are loosely packed, compared with the packing fraction of 74% for a face-centered cubic array of ideal hard spheres. In contrast, with the aid of an organic buffer or lysine as additives, the SNSs arrays having smaller mesopores (ca. 3.9 nm) and higher packing fraction of 70.5−71.5% are achieved. It is suggested that the chemical additives with the ability to maintain relatively strong repulsive interaction until the final stage of evaporation play a vital role in the fabrication of well-ordered SNSs arrays.

References

(1) Yokoi, T.; Sakamoto, Y.; Terasaki O.; Kubota, Y.; Okubo, T.; Tatsumi, T. J. Am. Chem. Soc. 2006, 128, 13664–13665.

(2) Yokoi, T.; Wakabayashi, J.; Otsuka, Y.; Fan, W.; Iwama, M.; Watanabe, R.; Aramaki, K.; Shimojima, A.; Tatsumi, T.; Okubo, T. Chem. Mater. 2009, 21, 3719–3729.

(3) Wang, J. Z.; Sugawara-Narutaki, A.; Fukao, M.; Yokoi, T.; Shimojima, A.; Okubo, T. ACS Appl. Mater. Interfaces, 2011, doi: 10.1021/am200104m.