Direct cross-linking of silyl-functionalized cage siloxanes via nonhydrolytic siloxane bond formation for preparing nanoporous materials.

Bottom-up synthesis of siloxane-based nanoporous materials from siloxane oligomers is promising for constructing well-defined structures at a molecular level. Herein, we report the synthesis of nanoporous materials consisting of cage-type siloxanes through the nonhydrolytic siloxane bond formation reaction. Cage siloxanes with double-n-ring geometries (n = 4 or 6) modified with dimethylsilyl and dimethylethoxysilyl groups are synthesized and directly cross-linked using a B(C6F5)3 catalyst, resulting in the formation of porous networks composed of alternating cage siloxane nodes and tetramethyldisiloxane (-SiMe2OSiMe2-) linkers. Compared with conventional hydrolysis and polycondensation reactions of alkoxysilyl-modified cage siloxanes under acid conditions, the non-hydrolytic condensation reaction was found favorable for the formation of porous siloxane networks without unwanted cleavage of the siloxane bonds.

Hexagonal Prismatic Siloxanes Functionalized with Organosilyl Groups as Building Blocks of Nanoporous Materials.

Utilization of well-defined siloxane molecules allows for the construction of functional siloxane-based nanoporous materials based on the molecular design. Herein, a novel class of siloxane-based porous materials is synthesized via cross-linking of dimethylsilyl- and dimethylvinylsilyl-functionalized cage siloxanes with double-6-ring (D6R) geometry. Compared with the conventional double-4-ring cage siloxane, this study highlights the characteristics of D6R siloxanes as building blocks, demonstrating their high surface area and chemical stability. Furthermore, density functional theory calculations show their unique cation encapsulation ability.

Immobilization of isolated dimethyltin species on crystalline silicates through surface modification of layered octosilicate.

Single metal atoms supported on silica are attractive catalysts, and precise control of the local environment around the metal species is essential. Crystalline silica is useful as an efficient support for the incorporation of well-defined metal sites. Dimethyltin species were regularly grafted onto the layer surfaces of layered octosilicate, a type of two-dimensional (2D) crystalline silica. Dimethyltin dichlorides react with the surface silanol (SiOH) groups of the silicate layers. The formation of Si-O-Sn bonds was confirmed by 29Si magic-angle spinning (MAS) NMR. X-ray absorption fine structure (XAFS) analysis showed the four-coordinated Sn species. These results suggested the presence of well-defined dipodal dimethyltin species on the layer surfaces. The degree of modification of the silanol groups with the dimethyltin groups increased with increasing amounts of dimethyltin dichloride; however, the maximum degree of modification was approximately 50%. This value was interpreted as an alternate modification of the octosilicate reaction sites with dimethyltin groups. These results demonstrate the potential for developing highly active single metal catalysts with a high density of regularly arranged active sites on high surface area supports.

Integrated Extrinsic and Intrinsic Self-Healing of Polysiloxane Materials by Cleavable Molecular Cages Encapsulating Fluoride Ions.

Self-healing ability is crucial to increasing the lifetime and reliability of materials. In this study, spatiotemporal control of the healing of a polysiloxane material is achieved using a cleavable cage compound encapsulating a fluoride ion (F- ), which triggeres the dynamic rearrangement of the siloxane (Si-O-Si) networks. A self-healing siloxane-based elastomer is prepared by cross-linking polydimethylsiloxane (PDMS) with a F- -encapsulating cage-type germoxane (Ge-O-Ge) compound. This material can self-heal repeatedly under humid conditions. The F- released by hydrolytic cleavage of the cage framework contributes to rejoining of the cut pieces by promoting the local rearrangement of the siloxane networks. The use of a molecular cage encapsulating a catalyst for dynamic bond rearrangement provides a new concept for designing self-healing polysiloxane materials based on integrated extrinsic and intrinsic mechanisms.

Bridging the Gap between Zeolites and Dense Silica Polymorphs: Formation of All-Silica Zeolite with High Framework Density from Natural Layered Silicate Magadiite.

A silica zeolite (RWZ-1) with a very high framework density (FD) was synthesized from highly crystalline natural layered silicate magadiite, bridging the gap between the two research areas of zeolites and dense silica polymorphs. Magadiite was topotactically converted into a 3D framework through two-step heat treatment. The resulting structure had a 1D micropore system of channel-like cavities with an FD of 22.1 Si atoms/1000 Å3 . This value is higher than those of all other silica zeolites reported so far, approaching those of silica polymorphs (tridymite (22.6) and α-quartz (26.5)). RWZ-1 is a slight negative thermal expansion material with thermal properties approaching those of dense silica polymorphs. It contributes to the creation of a new field on microporous high-density silica/silicates. Synergistic interactions are expected between the micropores with molecular sieving properties and the dense layer-like building units with different topologies which provide thermal and mechanical stabilities.

Preparation of mesoporous nitrogen-doped titania comprising large crystallites with low thermal conductivity.

Reducing the thermal conductivity (κ) of mesoporous N-doped titania (TiO2) is crucial for the development of TiO2-based materials that exhibit excellent electronic, photochemical, and thermoelectric properties. Mesopores can contribute to the reduction of κ via phonon scattering, and the scattering effect due to the randomness of crystal interfaces should be significantly reduced to clarify the role of mesopores in reducing thermal conductivity. Highly ordered mesoporous N-doped TiO2 comprising large crystallites was prepared with silica colloidal crystals as a template into which a Ti source was introduced, followed by calcination with urea. N-doped samples comprising large crystallites exhibiting random mesopores were also prepared and used for the investigation of the effects of the shape and arrangement of the mesopore on phonon scattering. The mesostructures of the two separately prepared N-doped TiO2 samples were retained after sintering at 873 K and 80 MPa to fabricate pellets. Furthermore, the effective suppression of the long mean-free-path phonon conduction by the thin pore walls at a nanometer scale thickness significantly reduced the thermal conductivities of both samples. The presence of ordered mesopores further contributed to the reduction of κ, which was probably due to the enhanced contribution of the backscattering of phonons caused by ordered pore wall surfaces.

Preparation of new microporous europium silicate molecular sieve by selective leaching of alkali metal cations from europium silicate Eu-AV-9.

Acid treatment of crystalline silicates is a facile method of creating pores for the preparation of crystalline silica-based microporous materials, but its success depends on the acid treatment conditions and both the composition and crystallinity of the starting silicates. Here, europium silicate Eu-AV-9 containing Na+, K+, and Eu3+ ions was treated with acetic acid for 1 d or 14 d to synthesize microporous silicate with high Eu loading by the selective leaching of K+ and Na+ from the silicate. The acid-treated Eu-AV-9 had both crystallinity and microporosity capable of adsorbing CO2, while the adsorption of Ar was very low. In addition, the values of both micropore volume and BET area of acid-treated samples increased when the time of acid treatment was increased. This result was attributed to the formation of structural defects caused by eliminating Eu in Eu-AV-9 over time of acid treatment.

Anisotropic Crystal Growth of Layered Nickel Hydroxide along the Stacking Direction Using Amine Ligands.

Edge surfaces of two-dimensional crystals play crucial roles in their properties, such as intercalation behavior and catalytic activities; however, reports on the preparation of crystals with a high aspect ratio of thickness to lateral size, typically a prism-like crystal morphology composed of stacked layers, are scarce. We report the anisotropic crystal growth of ß-Ni(OH)2 along the stacking direction using bidentate amine ligands, which act as both the base and the reservoir of Ni2+ through the formation of Ni-diamine complexes. Various characterization results of the crystal structure, composition, and crystal orientation indicate the formation of hexagonal prisms of ß-Ni(OH)2 with an unusually high aspect ratio of the thickness to the lateral size higher than 1. A systematic investigation focusing on the molar ratio of amine ligands to Ni2+, the concentration of Ni-diamine complexes, and stability constants of the complexes revealed that anisotropic growth was promoted when the supersaturation was relatively high and was maintained constant for a long time. We clarified the role of amine ligands in controlling supersaturation through the controlled release of metal ions from stable complexes. ß-Co(OH)2 with a hexagonal prism shape was prepared using this protocol. This study provides valuable indications for developing synthetic chemistry for various layered compounds to achieve a controlled aspect ratio.

Variation of counter quaternary ammonium cations of anionic cage germanoxanes as building blocks of nanoporous materials.

Double-four ring (D4R)-type cage germanoxanes, having a fluoride anion in the cage, contain organic ammonium cations as counter cations outside the cage, and they are attractive as unique nano-building blocks of anionic porous materials. Although the variety of counter cations directly included in the cage germanoxane synthesis is limited, this study demonstrates that other tetraalkylammonium cations can be introduced by cation exchange in both discrete and cross-linked states. Tetraethylammonium (TEA) of a discrete cage germanoxane was replaced with tetrabutylammonium (TBA) in an organic solvent, which provides another starting material. TEA and TBA cations in cross-linked networks formed by hydrosilylation reactions of dimethylvinylsilylated cage germanoxanes with various oligosiloxanes as linkers were exchanged with tetramethylammonium (TMA) cations. The variation in the pore volume, which depends on the type of introduced counter cations and oligosiloxane linkers, is verified. In terms of bottom-up synthesis of nanoporous materials from cage-type germanoxanes, the selection of both the counter cation and cross-linker is important to vary the porosity.

Hydrolysis of Methoxylated Nickel Hydroxide Leading to Single-Layer Ni(OH)2 Nanosheets.

Various methods for the preparation of inorganic nanosheets have been established and they have contributed to the substantial development of the research on diverse two-dimensional materials. Covalent surface modification of layered metal hydroxides with alkoxy groups is known to effectively weaken the interactions between layers, although the modified ligands are irreversibly immobilized. This study proposes the use of methanol as a removable surface modifier forming monodentate alkoxy bonds to prepare nickel hydroxide nanosheets through hydrolysis. Methoxylated layered nickel hydroxide, consisting of randomly stacked nano-sized nickel hydroxide sheets (10-20 nm in size) having Ni-OCH3 groups on its surface, was synthesized in a powder form through the precipitation reaction of a nickel salt in methanol at room temperature. After dispersing the aggregated methoxylated nickel hydroxide in water, single-layer nickel hydroxide nanosheets with a thickness of 1.2 nm and a lateral size of 460 nm at maximum, which is larger than the size of original methoxylated nickel hydroxide were found in the suspension. The time-course experiments during hydrolysis suggested that two-dimensional crystal growth of exfoliated nickel hydroxide sheets proceeded, resulting in the formation of the nanosheets. Moreover, single-layer and nano-sized cobalt hydroxide was prepared through a similar manner. This work demonstrates that two-dimensional alkoxides consisting of polymeric M-O-M bonds are useful precursors for the design of metal-hydroxide-based nanomaterials.

Preparation of Ordered Nanoporous Indium Tin Oxides with Large Crystallites and Individual Control over Their Thermal and Electrical Conductivities.

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.

Direct bottom-up synthesis of size-controlled monodispersed single-layer magnesium hydroxide nanosheets modified with tripodal ligands.

Conventional top-down methods for preparing inorganic nanosheets possess fundamental challenges of morphological control. Herein, the direct synthesis of organically modified single-layer magnesium hydroxide nanosheets with narrow size distribution was achieved by the in situ modification of magnesium hydroxide with a tripodal ligand, tris(hydroxymethyl)aminomethane.

Synthesis of Cristobalite Containing Ordered Interstitial Mesopores using Crystallization of Silica Colloidal Crystals.

Cristobalite with ordered interstitial dual-sized mesopores was synthesized through the crystallization of silica colloidal crystals composed of monodispersed amorphous silica nanoparticles. An aqueous solution containing both a flux (Na2 O) and a carbon precursor (an aqueous low-molecular weight phenolic resin) was infiltrated into the interstices of silica colloidal crystals. The organic fraction in the nanocomposite was further polymerized and subsequently carbonized in an Ar flow at 750 °C to reinforce the colloidal crystal structure. The thermal treatment resulted in the crystallization of the colloidal crystals into cristobalite while retaining the porous structure. The cristobalite-carbon nanocomposite was calcined in air to remove the carbon and create interstitial ordered mesopores in the cristobalite. The surfaces of crystalline mesoporous silica are quite different from those of various ordered mesoporous silica with amorphous frameworks; thus, the present findings will be useful for a precise understanding and control of the interfaces between the mesopores and silica networks.

Preparation of Sub-50 nm Colloidal Monodispersed Hollow Siloxane-Based Nanoparticles with Controlled Shell Structures.

Hollow siloxane-based nanoparticles (HSNs) have attracted significant attention because of their promising unique properties for various applications. For advanced applications, especially in catalysis, drug delivery systems, and smart coatings, high dispersibility and monodispersity of HSNs with precisely controlled shell structures are important. In this study, we established a simple method for preparing colloidal HSNs with a uniform particle size below 50 nm by the reaction of colloidal silica nanoparticles with bridged organoalkoxysilane [1,2-bis(triethoxysilyl)ethylene: (EtO)3Si-C2H2-Si(OEt)3, BTEE] in the presence of a cationic surfactant. Upon the formation of organosiloxane shells by hydrolysis and polycondensation of BTEE, the core silica nanoparticles were spontaneously dissolved, and a part of the silicate species was incorporated into the organosiloxane shells. The size of the colloidal silica nanoparticles, the amount of BTEE added, and the pH of the reaction mixture greatly affected the formation of HSNs. Importantly, colloidal HSNs having micropores and mesopores in the shells were successfully prepared using silica nanoparticles (20, 30, and 40 nm in diameter) at pH values of 9 and 11, respectively. These HSNs are potentially important for applications in drug delivery systems and catalysis.

Preparation of periodic mesoporous organosilica with large mesopores using silica colloidal crystals as templates.

Organosiloxane-based mesoporous materials with periodically ordered pores (periodic mesoporous organosilica, PMO) have many applications due to their various organic functions, high surface areas, and large pore volumes. Conventional methods using surfactant templates (soft templates) are limited in terms of the diversity of organosilane precursors and precise control over the pore size in a relatively large mesopore region (10-50 nm). This paper demonstrates the preparation of PMOs with precisely controlled pore sizes (>10 nm in diameter) and various organosiloxane frameworks, using colloidal crystals of monodisperse silica nanospheres as a template. An inverse opal structure with interconnected spherical mesopores was obtained through polycondensation of hydrolyzed organoalkoxysilanes [(EtO)3Si-R-Si(OEt)3, R = C2H4, CH[double bond, length as m-dash]CH, and C6H4; PhSi(OEt)3], within the voids of silica colloidal crystals, followed by the preferential dissolution of silica under well-controlled basic conditions. The pore size varied depending on the size of the silica nanospheres. The versatility of this method will allow for the wide tuning of the physical and chemical properties of organosiloxane-based mesoporous materials.

Encapsulation of Cu nanoparticles in nanovoids of plate-like silica sodalite through interlayer condensation of Cu2+ ion-exchanged layered silicate RUB-15.

The interlayer condensation of layered silicates is a unique method for synthesizing zeolites and is effective for the introduction of metal species into platy zeolite frameworks. Layered silicate RUB-15 is a useful starting material because metal ions can be introduced between the layers and zeolite frameworks (all-silica SOD-type zeolite; silica sodalite) can be formed through interlayer condensation. In this study, Cu ions were intercalated into layered silicate RUB-15, and metal Cu nanoparticles were formed in the nanovoids of silica sodalite by a simple heat treatment in an inert atmosphere. Both interlayer condensation and the reduction of Cu2+ ions were confirmed by in situ XRD analysis performed during the heat treatment. The residual interlayer tetramethylammonium ions played two roles: the control of stacking sequence in the interlayer condensation and the reduction of Cu2+ ions. The formed Cu nanoparticles were stable in air atmosphere because of their confinement in the nanovoids of the sodalite frameworks.

Mesoporous Silica Nanoparticles with Dispersibility in Organic Solvents and Their Versatile Surface Modification.

Recently, colloidal mesoporous silica nanoparticles (MSNs) have attracted keen interest in scientific and technological fields. A significant issue regarding the effective use of colloidal MSNs is their dispersibility in various solvents, which is essential for their applications through surface modification. However, the dispersion media for colloidal MSNs have been extremely limited. Here, we report a new method for obtaining stable colloidal MSNs dispersed in various organic solvents through a gradual solvent exchange of colloidal MSNs from acidic water to an organic solvent by dialysis. This allows the colloidal MSNs to be dispersed as primary nanoparticles in organic solvents such as 1-butanol, 1-dodecanol, and tetrahydrofuran (THF), which are capable of hydrogen bonding with surface silanol groups. In addition, MSNs dispersed in THF can be modified with chlorosilanes while maintaining colloidal stability. Various organosilyl groups, such as trimethylsilyl and dimethylsilyl groups, can be densely grafted on the surfaces of MSNs. After trimethylsilylation, MSNs become dispersible even in a nonpolar and hydrophobic solvent like octane through the solvent exchange due to the preferential evaporation of THF. This method will offer a versatile approach to functionalizing colloidal MSNs toward a wide range of applications.

Selective Covalent Modification of Layered Double Hydroxide Nanoparticles with Tripodal Ligands on Outer and Interlayer Surfaces.

Layered double hydroxides (LDHs) have occupied an important place in the fields of catalysts, electrocatalysts, and fillers, and their applicability can be greatly enhanced by interlayer organic modifications. In contrast to general organic modification based on noncovalent modification using ionic organic species, this study has clarified in situ interlayer covalent modification of LDH nanoparticles (LDHNPs) with the tripodal ligand tris(hydroxymethyl)aminomethane (Tris-NH2). Interlayer-modified CoAl LDHNPs were obtained by a one-pot hydrothermal treatment of an aqueous solution containing metal salts and Tris-NH2 at 180 °C for 24 h. Tris-NH2 was covalently bonded on the interlayer surface of LDHNPs. Interlayer-modified NiAl LDHNPs were also similarly synthesized. Some comparative experiments under different conditions indicate that the important parameters for interlayer modification are the number of bonding sites per a modifier, the electronegativity of a constituent divalent metal element, and the concentration of a modifier; this is because these parameters affect the hydrolytic stability of alkoxy-metal bonds between a modifier and a layer of LDHNPs. The synthesis of interlayer-modified MgAl LDHNPs was achieved by adjusting these parameters. This achievement will enable new potential applications because modification of only the outer surface has been achieved until now. Interlayer-modified LDHNPs possessing CO32- in the interlayer space were delaminated into monolayers under ultrasonication in water. The proposed method provides a rational approach for interlayer modification and facile delamination of LDHNPs.

Alkoxy- and Silanol-Functionalized Cage-Type Oligosiloxanes as Molecular Building Blocks to Construct Nanoporous Materials.

Siloxane-based materials have a wide range of applications. Cage-type oligosiloxanes have attracted significant attention as molecular building blocks to construct novel siloxane-based nanoporous materials with promising applications such as in catalysis and adsorption. This paper reviews recent progress in the preparation of siloxane-based nanoporous materials using alkoxy- and silanol-functionalized cage siloxanes. The arrangement of cage siloxanes units is controlled by various methods, including amphiphilic self-assembly, hydrogen bonding of silanol groups, and regioselective functionalization, toward the preparation of ordered nanoporous siloxane-based materials.

Formation of silicate nanoscrolls through solvothermal treatment of layered octosilicate intercalated with organoammonium ions.

We report silicate nanoscrolls composed of only SiO4 tetrahedra with crystalline walls for the first time in this study. The procedure consists of the intercalation of layered octosilicate with dioctadecyldimethylammonium bromide ((C18)2DMABr) and the subsequent solvothermal treatment of the intercalated material in heptane. The walls of the obtained nanoscrolls are crystalline, which originates from layer crystallinity in the pristine silicate. The direction of rolling up is fixed at the a- or b-axis of the silicate based on the electron diffraction patterns of the nanoscrolls. Desorption of (C18)2DMABr, which is present in addition to (C18)2DMA cations, from the interlayer during solvothermal treatment is likely related to the nanoscrolling process. Although the yield of nanoscrolls is low, these findings will lead to the re-estimation of many layered silicates intercalated with long-chain alkylammonium compounds as precursors for silicate nanoscrolls with crystalline walls.