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.

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.

The reduction of the diameter of Bi nanowires below 10 nm has been an important target because of the theoretical prediction with regard to significant enhancement in thermoelectric performance by size reduction. In this study, we have demonstrated the usefulness of mesoporous silica with tunable pore size as a template for the preparation of thin Bi nanowires with diameters below 10 nm. Bi was deposited within the templates through a liquid phase deposition using hexane and 1,1,3,3-tetramethyldisiloxane as a solvent and reducing agent, respectively. Bundles of thin Bi nanowires with non-crystalline frameworks were successfully obtained after the template removal. The diameter was precisely controlled between about 6 nm and 9 nm. The judicious choices of mesoporous silica and deposition conditions are critical for the successful preparation. The reliable formation of such thin Bi nanowires reported here opens up exciting new possibilities.

Mesoporous bimetallic Au–Pt with a phase-segregated heterostructure has been prepared by using mesoporous silica SBA-15 as a template. Au nanoparticles were prepared as a seed metal within the mesopores, and subsequently Pt was deposited, sandwiching the Au seeds. Energy-dispersive X-ray (EDX) spectral mapping showed that the framework of mesoporous bimetallic Au–Pt, prepared by removing the silica template with HF, was composed of Au nanoparticles joined with Pt nanowires. The Au/Pt ratio of the mesoporous bimetallic Au–Pt could be varied by controlling the number of Au deposition cycles. Pre-adsorbed CO (CO_ad) stripping voltammetry of the mesoporous bimetallic Au–Pt showed that the surfaces of the joined bimetallic structure were electrochemically active. This could be attributed to the open framework structure having a high ratio of exposed bimetallic mesopore surfaces. The described preparative approach, involving a mesoporous silica template and stepwise deposition within the mesopores, enables control of the nanostructure of the bimetallic material, which is greatly promising for the further development of synthetic methodologies for bimetallic structures.

The particle sizes of mesoporous silica nanoparticles most greatly affect their properties, including cellular uptake, cytotoxicity, and dispersity. The growth of colloidal mesostructured silica nanoparticles (CMSS) with particle sizes less than 100 nm was controlled by a modified seed-growth method by using alkoxysilanes (Si(OR)₄, R: Me, Et, Pr, and Bu) with different hydrolysis rates as additives. It was confirmed that the approximate matching of the hydrolysis rates of the added silanes with the consumption rates, determined by the total outer surface area of the seeds, is most important. CMSS with narrow particle-size distributions (e.g., 60 or 80 nm in size) were successfully prepared. Si(OPr)₄ was the most suitable additive, though Si(OEt)₄ was also useful for controlled growth. Si(OBu)₄ was usable but needed varied conditions for controlled growth. The mesostructures and the high dispersity of nanoparticles were retained, even after removal of the surfactants of the CMSS by dialysis. These findings should contribute to the more precise control of particle sizes of mesoporous silica nanoparticles and to the deeper understanding of their properties.

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 Nb⁵⁺ and correspondingly Ti³⁺. 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.

The design of siloxane-based nanoparticles is important for many applications. Here we show a novel approach to form core–shell silica nanoparticles of a few nanometers in size through the principle of “dispersion of ordered mesostructures into single nanocomponents”. Self-assembled siloxane–organic hybrids derived from amphiphilic alkyl-oligosiloxanes were postsynthetically dispersed in organic solvent to yield uniform nanoparticles consisting of dense lipophilic shells and hydrophilic siloxane cores. In situ encapsulation of fluorescent dyes into the nanoparticles demonstrated their ability to function as nanocarriers.

AST-type zeolite with a plate morphology can be synthesized by topotactic conversion of a layered silicate (β-helix-layered silicate; HLS) by using N,N-dimethylpropionamide (DPA) to control the layer stacking of silicate layers and the subsequent interlayer condensation. Treatment of HLS twice with 1) hydrochloric acid/ethanol and 2) dimethylsulfoxide (DMSO) are needed to remove interlayer hydrated Na ions and tetramethylammonium (TMA) ions in intralayer cup-like cavities (intracavity TMA ions), both of which are introduced during the preparation of HLS. The utilization of an amide molecule is effective for the control of the stacking sequence of silicate layers. This method could be applicable to various layered silicates that cannot be topotactically converted into three-dimensional networks by simple interlayer condensation by judicious choice of amide molecules.

Siloxane formation reactions of both the nonhydrolytic sol–gel process and Piers–Rubinsztajn reaction can be integrated as Lewis acid promoted siloxane syntheses without involving silanol groups. The former was developed in the field of inorganic materials chemistry and the latter was initiated in polymer chemistry. We have realized both reactions are quite similar, in terms of 1) the nonhydrolytic reaction, 2) the use of alkoxysilanes, 3) the group-exchange reactions competing with the siloxane formation, and 4) the proposed reaction mechanisms. This Minireview focuses on the above two reactions. The evolution of both reactions should realize a more sophisticated molecular design of siloxane compounds, which surely contributes to the development of advanced functional materials.

A repeating template method is presented for the synthesis of mesoporous metals with 2D hexagonal mesostructures. First, a silica replica (i.e., silica nanorods arranged periodically) is prepared by using 2D hexagonally ordered mesoporous carbon as the template. After that, the obtained silica replica is used as the second template for the preparation of mesoporous ruthenium. After the ruthenium species are introduced into the silica replica, the ruthenium species are then reduced by a vapor-infiltration method by using the reducing agent dimethylamine borane. After the ruthenium deposition, the silica is chemically removed. Analysis by transmission and scanning electron microscopies, a nitrogen-adsorption–desorption isotherm, and small-angle X-ray scattering revealed that the mesoporous ruthenium had a 2D hexagonal mesostructure, although the mesostructural ordering is decreased compared to that of the original mesoporous carbon template. This method is widely applicable to other metal systems. By changing the metal species introduced into the silica replica, several mesoporous metals (palladium and platinum) can be synthesized. Ordered mesoporous ruthenium and palladium, which are not easily attainable by the soft-templating methods, can be prepared. This study has overcome the composition variation limitations of the soft-templating method.

A spherosilicate dendrimer (DMS-1) with closely spaced reaction sites (SiH groups) on the dendrimer surface has been synthesized by stepwise silylation of double-four-ring silicate with chlorotriethoxysilane (ClSi(OEt)₃) and subsequently with chlorodimethylsilane (ClSiHMe₂). DMS-1 consists of a maximum of 40 Si atoms in the interior frameworks and 24 reactive SiH groups on the surface. Because DMS-1 is spherical and about 1.5 nm in diameter, it can be regarded as the smallest well-defined silica-based nanoparticle. DMS-1 also forms molecular crystals and is soluble in typical organic solvents. A molecularly ordered silica-based hybrid can be prepared by heating a cast film of DMS-1 at 180 °C for 5 days. The surface of DMS-1 can be modified by hydrosilylation with 1-hexadecene, triethoxyvinylsilane, and allylic-terminated tetraethylene glycol monomethyl ether. More than 20 SiH groups out of 24 react with these reagents. The solubilities of the products depend on the modification. DMS-1 is not only a building block for nanohybrids, but also the smallest and most precisely designed siloxane-based nanoparticle.

Here, the development of ordered mesoporous silica prepared by the reaction of layered silicates with organoammonium surfactants is reviewed. The specific features of mesoporous silica are discussed with relation to the probable formation mechanisms. The recent understanding of the unusual structural changes from the 2D structure to periodic 3D mesostructures is presented. The formation of mesophase silicates from layered silicates with single silicate sheets depends on combined factors including the reactivity of layered silicates, the presence of layered intermediates, the variation of the silicate sheets, and the assemblies of surfactant molecules in the interlayer spaces. FSM-16-type (p6mm) mesoporous silica is formed via layered intermediates composed of fragmented silicate sheets and alkyltrimethylammonium (C_nTMA) cations. KSW-2-type (c2mm) mesoporous silica can be prepared through the bending of the individual silicate sheets with intralayer and interlayer condensation. Although the structure of the silicate sheets changes during the reactions with C_nTMA cations in a complex manner, the structural units caused by kanemite in the frameworks are retained. Recent development of the structural design in the silicate framework is very important for obtaining KSW-2-based mesoporous silica with molecularly ordered frameworks. The structural units originating from layered silicates are chemically designed and structurally stabilized by direct silylation of as-synthesized KSW-2. Some proposed applications using these mesoporous silica are also summarized with some remarks on the uniqueness of the use of layered silicates by comparison with MCM-type mesoporous silica.