Mesoporous basic Mg-Al mixed metal oxides (MMOs) with a high surface area and large pore size have been prepared through the assembly of monodispersed layered double hydroxide nanoparticles (LDHNPs) with block copolymer templates. The particle sizes of the LDHNPs were mainly controlled by varying the concentration of tris(hydroxymethyl)aminomethane (THAM), which was used as a surface stabilizing agent. LDHNPs and micelles of a block copolymer (Pluronic F127) were assembled to form a composite. The composites were calcined to transform them into mesoporous MMOs and to remove the templates. The Brunauer-Emmett-Teller surface areas, mesopore sizes, and pore volumes increased as a result of using the templates. Moreover, the pore sizes of the mesoporous MMOs could be controlled by using LDHNPs of different sizes. The mesoporous MMOs prepared from the LDHNPs showed much higher catalytic activity than a conventional MMO catalyst for the Knövenagel condensation of ethyl cyanoacetate with benzaldehyde. The mesoporous MMO catalyst prepared using the smallest LDHNPs, about 12 nm in size, showed the highest activity. Therefore, the use of monodispersed LDHNPs and templates is effective for preparing highly active mesoporous solid base catalysts.

There has been significant interest in the crystallization of nanostructured silica into α-quartz because of its physicochemical properties. We demonstrate a single-crystalline mesoporous quartz superlattice, a silica polymorph with unprecedentedly ordered hierarchical structures on both the several tens of nanometers scale and the atomic one. The mesoporous quartz superlattice consists of periodically arranged α-quartz nanospheres whose crystalline axes are mostly oriented in an assembly. The superlattice is prepared by thermal crystallization of amorphous silica nanospheres constituting a colloidal crystal. We found that the deposition of a strong flux of Li(+) only on the surface of silica nanospheres is effective for crystallization.

Highly ordered mesoporous niobium-doped TiO2 with a single-crystalline framework was prepared by using silica colloidal crystals with ca. 30 nm in diameter as templates. The preparation of colloidal crystals composed of uniform silica nanoparticles is a key to obtain highly ordered mesoporous Nb-doped TiO2 . The XPS measurements of Nb-doped TiO2 showed the presence of Nb(5+) and correspondingly Ti(3+) . With the increase in the amount of doped Nb, the crystalline phase of the product was converted from rutile into anatase, and the lattice spacings of both rutile and anatase phases increased. Surprisingly, the increase in the amount of Nb led to the formation of plate-like TiO2 with dimpled surfaces on one side, which was directly replicated from the surfaces of the colloidal silica crystals.

Metal oxides are considered suitable candidates for thermoelectric materials owing to their high chemical stabilities. The formation of ordered nanopores within these materials, which decreases thermal conductivity (κ), has attracted significant interest. However, the electrical conductivity (σ) of reported nanoporous metal oxides is low, owing to electron scattering at the thin pore walls and many grain boundaries formed by small crystallites. Therefore, a novel synthesis method that can control pore walls while forming relatively large crystallites to reduce κ and retain σ is required. In this study, we used indium tin oxide (ITO), which is a typical example among metal oxides with high σ. Nanoporous ITOs with large crystallite sizes of several hundred nanometers and larger were successfully prepared using indium chloride as a source of indium. The pore sizes were varied using colloidal silica nanoparticles with different particle sizes as templates. The crystal phase and nanoporous structure of ITO were preserved after spark plasma sintering at 723 K and 80 MPa. The κ was significantly lower than that reported for bulk ITO due to the phonon scattering caused by the nanoporous structure and thin pore walls. There was a limited decrease in σ even with high porosity. These findings show that κ and σ are independently controllable through the precise control of the structure. The control of the thickness of the pore walls at tens of nanometers was effective for the selective scattering of phonons, while almost retaining electron mobility. The remarkable preservation of σ was attributed to the large crystallites that maintained paths for electron conduction and decreased electron scattering at the grain boundaries.

Organosiloxane-based mesoporous materials with periodically ordered pores (periodic mesoporous organosilicas, PMOs) have many applications due to their various organic functions, high surface areas, and large pore volumes. Conventional methods using...