Facile synthesis and characterization of novel mesoporous and mesorelief oxides with gyroidal structures.
In this paper, we bring forward an effective strategy, solvothermal postsynthesis, to prepare ordered mesoporous silica materials with highly branched channels. Structural characterizations indicate that the titled mesoporous materials basically have the cubic double gyroidal (space group Ia-3d) structure with small fraction of distortions. The mesopore sizes and surface areas can be up to 8.8 nm and 540 m2/g, respectively, when microwave digestion is employed to remove the organic templates. A phase transition model is proposed, and possible explanations for the successful phase transition are elucidated. The results show that the flexible inorganic framework, high content of organic matrix, and nonpenetration of poly(ethylene oxide) segments may facilitate the structural evolution. This new synthetic strategy can also be extended to the preparation of other double gyroidal silica-based mesoporous materials, such as metal and nonmetal ions doped silica and organo-functionalized silica materials. The prepared 3D mesoporous silica can be further utilized to fabricate various ordered crystalline gyroidal metal oxide "negatives". The mesorelief "negatives" (Co3O4 and In2O3 are detailed here) prepared by impregnation and thermolysis procedures exhibit undisplaced, displaced, and uncoupled enantiomeric gyroidal subframeworks. It has been found that the amount of metal oxide precursors (hydrated metal nitrates) greatly influence the (sub)framework structure and single crystallinity of the mesorelief metal oxide particles. The single crystalline gyroidal metal oxides are ordered both at mesoscale and atomic scale. However, these orders are not commensurate with each other.
Tian
Bozhi
B
Molecular Catalysis and Innovative Materials Lab, Department of Chemistry, Fudan University, Shanghai 200433, PR China.
Liu
Xiaoying
X
Solovyov
Leonid A
LA
Liu
Zheng
Z
Yang
Haifeng
H
Zhang
Zhendong
Z
Xie
Songhai
S
Zhang
Fuqiang
F
Tu
Bo
B
Yu
Chengzhong
C
Terasaki
Osamu
O
Zhao
Dongyuan
D