Template Synthesis Of Ordered Mesoporous Structure And Pore And Its Biological And Battery Applications

Porous solids are of scientific and technological interests because of their ability to interact with atoms, ions and molecules not only at their surfaces, but also throughout the bulk of the materials. Since the innovation of M41S mesoporous materials by the scientists at Mobil Research and Development Corporation, researchers around the world have prepared thousands of porous materials on mesoscale with different compositions, new pore systems and novel properties based on supermolecule assembly concept. At certain extent, mesoporous materials can be more or less synthesized/controlled at micro-, meso-, and macro-scale. Some ideas of structure-property-function relationships have been revealed. On the other hand, promising commercial utility is still lacking. To exploit the potential application of mesoporous/structured materials would be the main task in this field in the future.This thesis divides into two major parts. The first part, "soft-templating" synthesis of mesoporous silica is described, and in the second part, the materials structured on nano or meso-scale based on "hard-templating" concept is introduced. In each part, we also highlight the areas in which these novel nanoporous/structured materials' properties could be exploited."Soft" matters (e.g. proteins, surfactants and block copolyers) can be used as the templates for the synthesis of porous materials. In chapter 2, we describe the preparation of macroporous inorganic oxides (silica and titania) by using egg white as the templates. Their pore size can be tailored from 30 to 400 nm with the additive of surfactants. In chapter 3, a simple secondary hydrolysis process was used to synthesize highly ordered mesoporous silica templated by nonionic oligomeric surfactants with long hydrophilic chains. Mesoporous silica prepared by this process shows highly ordered hexagonal (p6mm) mesostructures and also improved hydrothermal stability compared with the materials synthesized from conventional route.In order to overcome the shortages of one-dimensional mesochannels of SBA-15 in mass transport, high-temperature (100 ~ 140 癈) hydrothermal treatment and introduction of TMB into embryo mesostructured SBA-15 was used to prepare a modified three-dimensional mesoporous SBA-15 (in chapter 4). Three-dimensional mesoporous SBA-15 has average mesostructure of hexagonal plane group symmetry p6mm. There aremany mesotunnels (2-8 nm) randomly distributed between their one-dimensional mesochannels, which generate three-dimensional large pore (up to 22 nm) networks.A cubic (f.c.c) mesoporous silica (denoted as FDU-12) is reported in chapter 5, which was prepared by using block copolymer as the templates in the presence of inorganic salts. Their entrance size can be adjusted in the range of 4 ~ 9 nm as confirmed by nitrogen sorption and the negative replicas of gold nanocrystals. It is revealed that the widen entrances facilitate the immobilization of enzymes and replication of a high ordered cubic (f.c.c) mesoporous carbon. In this chapter, we also introduce a highly ordered FDU-12 with ultra-large cells (44 nm) induced by low-temperature synthesis.In chapter 6, the applications of large pore mesoporous silica in enzyme immobilization and catalysis are demonstrated. 1) It is revealed that macrostructures of mesoporous silica have great influence on the bioimmobilization performance of mesoporous materials. Very rapid (< 10 min to reach the capacity of 200 mg/g) and high capacity (up to 533 mg/g) immobilization of enzymes within mesoporous silica has been achieved by finely tuning their morphology. 2) It showed that trypsin accommodated in mesoscopic confinement of mesoporous silica acted as more efficient biocatalysts and achieved far more rapid (10 min) and effective (58% protein sequence coverage) proteolysis compared to in-solution enzymatic digestion (overnight, 27% protein sequence coverage). The correlation between the macrostructure, surface characters and proteolysis efficiency has also been demonstrated. 3) With unique three-dimensional (3-D) cavity...