Atsushi Shimojima

A Working Hypothesis for Broadening Framework Types of Zeolites in Seed-Assisted Synthesis without Organic Structure-Directing Agent

Recent research has demonstrated a new synthesis route to useful zeolites such as beta, RUB-13, and ZSM-12 via seed-assisted, organic structure-directing agent (OSDA)-free synthesis, although it had been believed that these zeolites could be essentially synthesized with OSDAs. These zeolites are obtained by adding seeds to the gels that otherwise yield other zeolites; however, the underlying crystallization mechanism has not been fully understood yet. Without any strategy, it is unavoidable to employ a trial-and-error procedure for broadening zeolite types by using this synthesis method. In this study, the effect of zeolite seeds with different framework structures is investigated to understand the crystallization mechanism of zeolites obtained by the seed-assisted, OSDA-free synthesis method. It has been found that the key factor in the successful synthesis of zeolites in the absence of OSDA is the common composite building unit contained both in the seeds and in the zeolite obtained from the gel after heating without seeds. A new working hypothesis for broadening zeolite types by the seed-assisted synthesis without OSDA is proposed on the basis of the findings of the common composite building units in zeolites. This hypothesis enables us to design the synthesis condition of target zeolites. The validity of the hypothesis is experimentally tested and verified by synthesizing several zeolites including ECR-18 in K-aluminosilicate system.

Formation of Hierarchically Organized Zeolites by Sequential Intergrowth

Hierarchically organized porous materials can provide multidimensional spatial networks on different length scales with improved characteristics relevant to molecular diffusion. Zeolites that are microporous crystalline materials having pores and channels at molecular dimensions are of great importance for industrial applications. However, the presence of only micropores in zeolite frameworks often limits the molecular diffusion and therefore, restricts the transport of bulky molecules. This problem can be resolved by shortening the effective diffusion path lengths, which has been achieved by miniaturizing zeolite crystals, delaminating or exfoliating layered zeolites, synthesizing zeolite nanosheets, and introducing mesopores into zeolite particles. Among these solutions, the fabrication of hierarchical zeolites with microand mesoporosity is of interest because it combines intrinsic micropores with bypass-interconnected mesopores, and therefore, enhances both the micropore accessibility and molecular traffic within zeolite particles. Hierarchical zeolites have been produced using several techniques, including top-down desilication by alkali postsynthetic treatment and bottom-up directed assembly by hard or soft templates. The hard-template method requires multistep procedures and is therefore unfavorable for large-scale production. Alternatively, the direct introduction of organic mesopore-generating agents (mesoporogens) during zeolite synthesis can create uniform mesopores. The use of such mesoporogens is currently one of the most promising methods for the single-step construction of hierarchical zeolites. Progress has been made using well-designed mesoporogens composed of long hydrophobic chains and hydrophilic zeolitic structure-directing groups to generate zeolites with tunable mesoporosity and to direct the hierarchical assembly of zeolite nanosheets, yielding mesoporous zeolites with house-of-cards-like structures. These hierarchical nanosheets showed excellent catalytic performance in several important reactions because the presence of thin layers with specific crystalline faces facilitates catalysis at the exteriors or pore mouths. Such mesoporogens are probably necessary for the direct, singlestep synthesis of hierarchical zeolites. Herein we report an alternative, mesoporogen-free approach for the construction of hierarchically organized MFI zeolites by sequential intergrowth using a simple organic structure-directing agent (OSDA). The selection of an appropriate OSDA and optimized synthesis conditions that can form plate-like zeolites with enhanced 908 rotational intergrowths seems to be a key to achieving a hierarchical structure with three classes of porosity in one structure: the intrinsic microporosity of the zeolite framework together with mesoporosity existing within the zeolite plates and macroporosity stemming from the complex intergrown structure. Epitaxial and rotational intergrowths are commonly observed in many zeolites. We have hypothesized that by engineering the zeolite intergrowths, hierarchically organized zeolites can be constructed without the need for mesoporogens. In particular, we have focused on the MFI zeolite because it is an excellent catalyst in many industrial processes and a promising material for membrane separation. MFI zeolite that contains sinusoidal channels along the a axis interconnected with straight channels along the b axis is often formed with 908 rotational intergrowths, in which substantial (h00) faces are epitaxially overgrown on the (0k0)

Extension of size of monodisperse silica nanospheres and their well-ordered assembly

A liquid-phase method for preparing uniform-sized silica nanospheres (SNSs) 12 nm in size and their three-dimensionally ordered arrangement upon solvent evaporation have recently been pioneered by us. Here we report the successful control of the sphere sizes in the wide range from 14 to 550 nm by the seed regrowth method. In this method, the dispersion of SNSs 14 nm in size as seeds was prepared in the emulsion system containing Si(OEt)(4) (TEOS), water and arginine under weakly basic conditions (pH 9-10). An appropriate portion of this dispersion is added to the solution containing water, ethanol and arginine, and then TEOS is added. The additional TEOS introduced into the regrowth system contributed only to the resumed growth of the seeds, not to the formation of new silica particles. The size of interparticle pores was finely tuned by changing the size of the spheres. The preparation of three-dimensionally ordered porous carbons by using the colloidal array of silica nanospheres as a template is also reported.

Porous Siloxane–Organic Hybrid with Ultrahigh Surface Area through Simultaneous Polymerization–Destruction of Functionalized Cubic Siloxane Cages

A novel hierarchically porous, hyper-cross-linked siloxane-organic hybrid (PSN-5) has been synthesized by Friedel-Crafts self-condensation of benzyl chloride-terminated double-four-ring cubic siloxane cages as a singular molecular precursor. Simultaneous polymerization of the organic functional groups and destruction of the siloxane cages during synthesis yielded PSN-5, which has an ultrahigh BET surface area (∼2500 m(2) g(-1)) and large pore volume (∼3.3 cm(3) g(-1)) that to our knowledge are the highest values reported for siloxane-based materials. PSN-5 also shows a high H(2) uptake of 1.25 wt % at 77 K and 760 Torr.

Silica sodalite without occluded organic matters by topotactic conversion of lamellar precursor.

Novel pure silica sodalite with hollow sodalite-cages has been synthesized for the first time by topotactic conversion of layered silicate (RUB-15) precursor. This success has been achieved by stepwise syntheses from silicate monomers, through clusters and layers, to microporous crystals. The pretreatment of layered silicate with small carboxylic acids before conversion is a crucial step. The obtained sodalite possesses accessible micropores, as confirmed by physical adsorption of hydrogen molecules. This plate-like silica sodalite would be very promising as fillers in mixed-matrix membranes for hydrogen separation.

Synthesis of Ordered Porous Graphitic-C3N4 and Regularly Arranged Ta3N5 Nanoparticles by Using Self-Assembled Silica Nanospheres as a Primary Template

Uniform-sized silica nanospheres (SNSs) assembled into close-packed structures were used as a primary template for ordered porous graphitic carbon nitride (g-C(3)N(4)), which was subsequently used as a hard template to generate regularly arranged Ta(3)N(5) nanoparticles of well-controlled size. Inverse opal g-C(3)N(4) structures with the uniform pore size of 20-80 nm were synthesized by polymerization of cyanamide and subsequent dissolution of the SNSs with an aqueous HF solution. Back-filling of the C(3)N(4) pores with tantalum precursors, followed by nitridation in an NH(3) flow gave regularly arranged, crystalline Ta(3)N(5) nanoparticles that are connected with each other. The surface areas of the Ta(3)N(5) samples were as high as 60 m(2) g(-1), and their particle size was tunable from 20 to 80 nm, which reflects the pore size of g-C(3)N(4). Polycrystalline hollow nanoparticles of Ta(3)N(5) were also obtained by infiltration of a reduced amount of the tantalum source into the g-C(3)N(4) template. An improved photocatalytic activity for H(2) evolution on the assembly of the Ta(3)N(5) nanoparticles under visible-light irradiation was attained as compared with that on a conventional Ta(3)N(5) bulk material with low surface area.

Hybrid Porous Materials with High Surface Area Derived from Bromophenylethenyl‐Functionalized Cubic Siloxane‐Based Building Units

Sonogashira cross-coupling of bromophenylethenyl-terminated cubic, double four-ring, siloxane cages with di-/triethynyl compounds results in microporous poly(ethynylene aryleneethenylene silsesquioxane) networks, simply termed as polyorganosiloxane networks (PSNs). In comparison with porous organic polymers reported previously, these PSNs show relatively high surface area and comparable thermal stability. Their apparent BET specific surface areas vary in the range of 850-1040 m(2) g(-1) depending on the length and the connectable sites of the ethynyl compounds. Analyses of pore size distribution revealed bimodal micropores with relatively narrow distribution. The degree of cross-linking affects the degree of cleavage of the siloxane bonds, and this suggests that partial cleavage of the siloxane cages is mainly a result of cage distortion. Hydrogen adsorption was performed to evaluate potential of the PSNs as hydrogen storage media. Uptakes of up to 1.19 wt% at 77 K and 760 Torr and initial isosteric heats of adsorption as high as 8.0 kJ mol(-1) were observed. These materials have been obtained by a combination of structural, synthetic organic, and materials chemistry, which can exploited to synthesize porous hybrid materials with specifically designed structures and functions.

Two-Phase Synthesis of Monodisperse Silica Nanospheres with Amines or Ammonia Catalyst and Their Controlled Self-Assembly

A significant progress has recently been made in the synthesis of monodisperse silica nanoparticles less than 30 nm in diameter by using basic amino acids (e.g., lysine) as a base catalyst for hydrolysis of silicon alkoxide. Alternatively, a more versatile and economical amino acid-free method has been developed to synthesize uniform silica nanospheres (SNSs) with low polydispersity (<12%) in liquid-liquid biphasic systems containing tetraethoxysilane (TEOS), water, and primary amine (or ammonia) under precisely controlled pH conditions (pH 10.8-11.4). The diameter of the SNSs determined from scanning electron microscopy (SEM) can be tuned from ∼12 to ∼36 nm by simply changing the initial pH of the aqueous phase in the reaction mixtures. Furthermore, the as-synthesized sol was taken as the starting material for studying the influences of the type of base catalysts on the solvent evaporation-induced three-dimensional (3D) self-assembly of SNSs. X-ray diffraction (XRD) and nitrogen adsorption-desorption are used to characterize the degree of packing of the resulting 3D arrays. The assembled SNSs with large interparticle mesopores with the diameter of ca. 8.1 nm and low packing fraction of ca. 66.1% are observed upon solvent evaporation of as-synthesized sol in the presence of primary amine. This indicates that SNSs are loosely packed, compared with the packing fraction of 74% for a face-centered cubic array of ideal hard spheres. In contrast, with the aid of an organic buffer or lysine as additives, the assembly of SNSs having smaller mesopores (ca. 3.9 nm) and higher packing fraction of 70.5-71.5% are achieved. It is suggested that the chemical additives with the ability to maintain relatively strong repulsive interaction until the final stage of evaporation play a vital role in the fabrication of well-ordered SNSs arrays.

Self-assembly of alkyl-substituted cubic siloxane cages into ordered hybrid materials.

Siloxane-organic hybrids with well-ordered mesostructures were synthesized through the self-assembly of novel amphiphilic molecules that consist of cubic siloxane heads and hydrophobic alkyl tails. The monoalkyl precursors functionalized with ethoxy groups (C(n)H(2n+1)Si(8)O(12)(OEt)(7), 1 Cn, n=16, 18, and 20) were hydrolyzed under acidic conditions with the retention of the siloxane cages, leading to the formation of two-dimensional hexagonal phases by evaporation-induced self-assembly processes. Analysis of the solid-state (29)Si MAS NMR spectra of these hybrid mesostructures confirmed that the cubic siloxane units were cross-linked to form siloxane networks. Calcination of these hybrids gave mesoporous silica, the pore diameter of which varied depending on the alkyl-chain length. We also found that the precursors that had two alkyl chains formed lamellar phases, thus confirming that the number of alkyl chains per cage had a strong influence on the mesostructures. These results expand the design possibility of novel nanohybrid and nanoporous materials through the self-assembly of well-defined oligosiloxane-based precursors.

Structure and properties of multilayered siloxane–organic hybrid films prepared using long-chain organotrialkoxysilanes containing CC double bonds

Oriented multilayered films composed of alternating siloxane layers and organic layers were prepared from mixtures of tetramethoxysilane [Si(OMe)4] and unsaturated organotrimethoxysilane [RSi(OMe)3, where R is CH2CH(CH2)8– or CH2CH(CH2)2CHCH(CH2)4–], and the structures and macroscopic properties of the films were studied. Hydrolysis and partial condensation of the precursors led to the formation of amphiphilic organosiloxane species which self-assemble into lamellar phases. Polymerization of the organic phase occurred by UV irradiation, as evidenced by substantial decreases of the IR absorption bands due to –CHCH2 or –CHCH– groups. The hardness of the films was remarkably increased by the irradiation, due to the covalent linking of adjacent siloxane layers by organic polymerization. The films after organic polymerization had a much higher resistance to an alkaline solution, which enabled the patterning of the films on the micrometer length scale. These results provide an important insight into the structure–property relationships of nanostructured hybrid materials prepared by sol–gel chemistry.