title: Pore structures of ordered large cage-type mesoporous silica FDU-12s.
abstract: The pore variations of ordered cage-type mesoporous silica FDU-12s have been analyzed in detail by PXRD, SAXS, nitrogen sorption, and electron crystallography. FDU-12s with a cubic symmetry (space group, Fmm) were templated by amphiphilic triblock copolymer F127 with the addition of 1,3,5-trimethylbenzene and KCl under an acidic condition. Three typical samples with different unit cell sizes, pore cage diameters, and entrance sizes were obtained from different synthesis and hydrothermal treatment temperatures, as indicated by the differences in the PXRD and SAXS patterns. The pore structure changes in the three materials were observed by nitrogen adsorption/desorption and 3-D reconstruction of HRTEM images taken from different crystal orientations. The approximate pore structures of FDU-12s can be regarded as a face-centered cubic (fcc) close-packing of spherical cages, each connected to 12 nearest neighboring cages. However, the ideal spherical model is only valid for the FDU-12s prepared at a low temperature (L-FDU-12-100). The cage shape of the FDU-12s synthesized at a high temperature deviates from perfect spheres and is accompanied by an entrance enlargement. The temperature-dependent behavior of the PEO block is discussed with regard to its influence on the micelles and hence the cage configuration. The better understanding of the formation mechanism via the combined characterization techniques and modeling may lead to a more rational approach for tuning the pore cages and entrances of the mesoporous FDU-12 materials.
authors.affiliation: Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Advanced Materials Laboratory, Fudan University, Shanghai, 200433, P R China.
authors.forename: Ting
authors.initials: T
authors.lastname: Yu
authors.forename: Hong
authors.initials: H
authors.lastname: Zhang
authors.forename: Xuewu
authors.initials: X
authors.lastname: Yan
authors.forename: Zhengxia
authors.initials: Z
authors.lastname: Chen
authors.forename: Xiaodong
authors.initials: X
authors.lastname: Zou
authors.forename: Peter
authors.initials: P
authors.lastname: Oleynikov
authors.forename: Dongyuan
authors.initials: D
authors.lastname: Zhao