研究者詳細 - 中西　和樹

論文 - 中西　和樹

分割表示 377 件中 61 - 80 件目／全件表示 >>

Polymer-assisted shapeable synthesis of porous frameworks consisting of silica nanoparticles with mechanical property tuning 査読有り

Sato Kanako, Ishii Kanji, Oaki Yuya, Nakanishi Kazuki, Imai Hiroaki

POLYMER JOURNAL 49 巻 ( 12 ) 頁： 825 - 830 2017年12月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Polymer Journal

We report the shapeable synthesis of porous silica frameworks using polyacrylamide (PAAm) gel as an organic template and hydrolyzed silicon alkoxide as a silica source. Macroscopically shaped porous frameworks - such as plates, tablets and sheets - comprised of 20- to 40-nm diameter silica particles are obtained via PAAm-silica precursor gels. The mechanical properties (i.e., hardness and Young's modulus) of the silica frameworks depend on the packing density and are controlled by changing the silica content in PAAm gels.

DOI： 10.1038/pj.2017.62

Synthesis, Reduction, and Electrical Properties of Macroporous Monolithic Mayenite Electrides with High Porosity 査読有り

Wang R., Yang H., Lu Y., Kanamori K., Nakanishi K., Guo X.

ACS Omega 2 巻 ( 11 ) 頁： 8148 - 8155 2017年11月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：ACS Omega

Room-temperature stable macroporous mayenite electride (C12A7:e-) has been successfully prepared via a sol-gel method accompanied by phase separation, followed by heat-treatment and reduction processes. The obtained xerogel monoliths possess controllable macrostructure and a porosity of more than 60%, depending on adjusting the amount of poly(ethylene oxide) as a phase separation inducer. Heat-treatment allows the formation of multicrystals Ca12Al14O32Cl2 and Ca12Al14O33 (C12A7), and the porosity increases to 78.67% after being heat-treated at 1100 °C. Further reduction promotes the transformation from Ca12Al14O32Cl2 or C12A7 to C12A7:e- as well as the conversion from an insulator to a semiconductive electride. The carrier concentration of the electride reaches 3.029 × 1018 cm-3 after being reduced at 1100 °C under Ar atmosphere, and the porosity still remains 66%. The macrostructure of the resultant mayenite electride before and after heat-treatment and reduction is perfectly preserved, indicating that the obtained macroporous monolithic mayenite electride could be utilized in the electronic components.

DOI： 10.1021/acsomega.7b01121

Very Compact Millimeter Sizes for Composite Star-forming/AGN Submillimeter Galaxies 査読有り

Ikarashi S., Caputi K.I., Ohta K., Ivison R.J., Lagos C.D.P., Bisigello L., Hatsukade B., Aretxaga I., Dunlop J.S., Hughes D.H., Iono D., Izumi T., Kashikawa N., Koyama Y., Kawabe R., Kohno K., Motohara K., Nakanishi K., Tamura Y., Umehata H., Wilson G.W., Yabe K., Yun M.S.

Astrophysical Journal Letters 849 巻 ( 2 ) 2017年11月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Astrophysical Journal Letters

We report the study of the far-infrared (IR) sizes of submillimeter galaxies (SMGs) in relation to their dustobscured star formation rate (SFR) and active galactic nuclei (AGN) presence, determined using mid-IR photometry. We determined the millimeter-wave (λobs = 1100 μm) sizes of 69 Atacama Large Millimeter/ submillimeter Array (ALMA)-identified SMGs, selected with ≥10 δ confidence on ALMA images (F1100 μm = 1.7-7.4 mJy). We found that all of the SMGs are located above an avoidance region in the sizeflux plane, as expected by the Eddington limit for star formation. In order to understand what drives the different millimeter-wave sizes in SMGs, we investigated the relation between millimeter-wave size and AGN fraction for 25 of our SMGs at z=1-3. We found that the SMGs for which the mid-IR emission is dominated by star formation or AGN have extended millimeter-sizes, with respective median Rc,e = 1.6-0.21+0.34 and 1.5 -0.24+0.93 kpc. Instead, the SMGs for which the mid-IR emission corresponds to star-forming/AGN composites have more compact millimeter-wave sizes, with median Rc,e1.0 -0.20+0.20kpc. The relation between millimeter-wave size and AGN fraction suggests that this size may be related to the evolutionary stage of the SMG. The very compact sizes for composite star-forming/AGN systems could be explained by supermassive black holes growing rapidly during the SMG coalescing, star-formation phase.

DOI： 10.3847/2041-8213/aa9572

Aerogels from chloromethyltrimethoxysilane and their functionalizations 査読有り

Tomoki KIMURA, Taiyo SHIMIZU, Kazuyoshi KANAMORI, Ayaka MAENO, Hironori KAJI, Kazuki NAKANISHI

Langumuir 2017年11月

Nanostructured titanium phosphates prepared via hydrothermal reaction and their electrochemical Li- and Na-ion intercalation properties 査読有り

Zhu Y., Hasegawa G., Kanamori K., Kiyomura T., Kurata H., Hayashi K., Nakanishi K.

CRYSTENGCOMM 19 巻 ( 31 ) 頁： 4551 - 4560 2017年8月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CrystEngComm

In this report, we demonstrate a facile and versatile methodology for synthesizing a series of titanium phosphates (TiPs) with various morphologies. The hydrothermal reactions of TiO2 in different concentrations of H3PO4 aq. yield 4 types of crystal structures with diverse shapes, such as nanoparticles, nanorods and nanosheets, which are assembled into a variety of flower-like morphologies. The dependence of the crystal phases and morphologies of TiPs on the synthesis conditions have been comprehensively investigated. This synthetic process can be further extended to other TiP derivatives incorporated with guest cations (e.g. NH4+ and Na+) simply by adding the corresponding phosphate salts to the starting composition, which leads to the morphological variation associated with the change of the crystal phase. The mechanism for the formation of the TiPs is discussed in terms of the stable Ti-based ion species relying on the pH value of the reaction solution. In addition, the correlation between the crystal structures and morphologies of TiPs and their electrochemical Li- and Na-ion storage behaviors are demonstrated as well, which discloses the different tendencies of morphological effects between the Li- and Na-ion systems.

DOI： 10.1039/c7ce01123g

Ultralow-Density, Transparent, Superamphiphobic Boehmite Nanofiber Aerogels and Their Alumina Derivatives (vol 27, pg 3, 2015) 査読有り

Hayase Gen D, Nonomura Kazuya, Hasegawa George, Kanamori Kazuyoshi, Nakanishi Kazuki

CHEMISTRY OF MATERIALS 29 巻 ( 12 ) 頁： 5413 - 5413 2017年6月

Fabrication of hydrophobic polymethylsilsesquioxane aerogels by a surfactant-free method using alkoxysilane with ionic group 査読有り

Hayase Gen, Nagayama Shuya, Nonomura Kazuya, Kanamori Kazuyoshi, Maeno Ayaka, Kaji Hironori, Nakanishi Kazuki

JOURNAL OF ASIAN CERAMIC SOCIETIES 5 巻 ( 2 ) 頁： 104 - 108 2017年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of Asian Ceramic Societies

Phase separation control is an important factor to prepare a porous monolith by an aqueous sol–gel reaction. Here, we report a surfactant-free synthesis method to obtain hydrophobic polymethylsilsesquioxane aerogels by copolymerizing a cationic-functionalized alkoxysilane N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride. The resultant materials have low-density, high visible-light transmittance, and high thermal insulating equivalent to those of prepared under the presence of surfactant.

DOI： 10.1016/j.jascer.2017.02.003

Functionalization of hierarchically porous silica monoliths with polyethyleneimine (PEI) for CO2 adsorption 査読有り

Guo Xingzhong, Ding Li, Kanamori Kazuyoshi, Nakanishi Kazuki, Yang Hui

MICROPOROUS AND MESOPOROUS MATERIALS 245 巻頁： 51 - 57 2017年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Microporous and Mesoporous Materials

A novel CO2 sorbent was prepared by modifying polyethyleneimine (PEI) on hierarchically porous silica (HPS) monoliths with well-defined macro-mesopores through wet impregnation method. HPS monoliths before and after functionalization were characterized by scanning electron microscopy (SEM), differential thermal analysis/thermogravimetry (DTA/TG), fourier transform infrared spectroscopy (FT-IR) and nitrogen adsorption/desorption analysis (BET), and the CO2 adsorption-regeneration properties of as-synthesized sorbents were investigated by thermogravimetric analysis (TG). The effects of loaded PEI amount as well as adsorption temperature and CO2 partial pressure on the CO2 adsorption performance of the as-prepared sorbents were also studied. The results showed that the porous structure of HPS-PEI sorbents was preserved after functionalization, while the specific surface area and pore volume decreased with increasing amount of amines to some extent. The use of PEI had a remarkable improvement on the CO2 adsorption capacity. With the increasing amount of PEI loaded, the CO2 adsorption capacity improved significantly. The highest CO2 adsorption capacity of 2.44 mmol (g sorbent)−1 was obtained at 75 °C in the CO2 partial pressure of 100 kPa for the HPS loaded with 60 wt% PEI. Adsorption/desorption cycles indicated that the PEI-modified HPS sorbents had a good stability and regeneration.

DOI： 10.1016/j.micromeso.2017.02.076

Transparent Ethenylene-Bridged Polymethylsiloxane Aerogels: Mechanical Flexibility and Strength and Availability for Addition Reaction 査読有り

Shimizu T., Kanamori K., Maeno A., Kaji H., Doherty C.M., Nakanishi K.

Langmuir 33 巻 ( 18 ) 頁： 4543 - 4550 2017年5月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Langmuir

Transparent, low-density ethenylene-bridged polymethylsiloxane [Ethe-BPMS, O2/2(CH3)Si-CHCH-Si(CH3)O2/2] aerogels from 1,2-bis(methyldiethoxysilyl)ethene have successfully been synthesized via a sol-gel process. A two-step sol-gel process composed of hydrolysis under acidic conditions and polycondensation under basic conditions in a liquid surfactant produces a homogeneous pore structure based on cross-linked nanosized colloidal particles. Visible-light transmittance of the aerogels varies with the concentration of the base catalyst and reaches as high as 87% (at a wavelength of 550 nm for a 10 mm thick sample). Gelation and aging temperature strongly affect the deformation behavior of the resultant aerogels against uniaxial compression, and the obtained aerogels prepared at 80 °C show high elasticity after being unloaded. This highly resilient behavior is primarily derived from the rigidity of ethenylene groups, which is confirmed by a comparison with other aerogels with similar molecular structures, ethylene-bridged polymethylsiloxane and polymethylsilsesquioxane. Applicability of the addition reaction using a Diels-Alder reaction of benzocyclobutene has also been investigated, revealing that a successful addition takes place on the ethenylene linkings, which is verified using Raman and solid-state NMR spectroscopies. Insights into the effect of molecular structure on mechanical properties and the availability of surface functionalization provided in this study are important for realizing transparent aerogels with the desired functionality.

DOI： 10.1021/acs.langmuir.7b00434

Silicone-Based Organic–Inorganic Hybrid Aerogels and Xerogels 査読有り

Shimizu T., Kanamori K., Nakanishi K.

Chemistry - A European Journal 23 巻 ( 22 ) 頁： 5176 - 5187 2017年4月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry - A European Journal

Aerogels are attracting increasing attention due to their high thermal insulation ability as well as unique properties such as high porosity, surface area, and transparency. However, low mechanical strengths, originating from their unique porous structure, impede handling, formability, mass production, and extended applications. This minireview focuses on the strengthening of aerogels by several organic–inorganic hybridization strategies. In particular, successful strengthening methodologies, which employ organo-substituted alkoxysilanes as the single precursor for the sol–gel preparations, developed by the authors are highlighted. Moreover, improvements in compressive strength and elasticity lead to monolithic aerogel-like xerogels through ambient pressure drying. Correlations between structures in different length scales (e.g., molecular, network, and pore structure levels) and resultant mechanical properties are discussed for further understandings and better design toward mechanically improved aerogels/xerogels and their applications.

DOI： 10.1002/chem.201603680

Transparent polyvinylsilsesquioxane aerogels: investigations on synthetic parameters and surface modification 査読有り

Shimizu T., Kanamori K., Nakanishi K.

Journal of Sol-Gel Science and Technology 82 巻 ( 1 ) 頁： 2 - 14 2017年4月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of Sol-Gel Science and Technology

Abstract: Systematic investigations on the effect of synthetic conditions onto the properties of polyvinylsilsesquioxane (CH2=CHSiO3/2) aerogels have been conducted. As previously reported, transparent polyvinylsilsesquioxane aerogels can be obtained by utilizing a liquid surfactant as a solvent and a two-step sol–gel reaction involving hydrolysis catalyzed by a strong acid and subsequent polycondensation by a strong base. In this study, effects of base catalyst, gelation and aging conditions, amount of surfactant and concentration of acid catalyst have been investigated. With the optimized synthetic condition, the value of light transmittance reaches as high as 70% (at the wavelength of 550 nm for a 10-mm thick sample). Applicability of addition reactions utilizing thiol-ene reactions and hydrosilylation has also been surveyed. Thiol-ene reactions are relatively effective and can modify surface hydrophobicity and mechanical properties of polyvinylsilsesquioxane aerogels. In the case of hydrosilylation, a partial addition of a hydrosilane compound onto the polyvinylsilsesquioxane gel surface can be observed. Addition reactions, in particular thiol-ene reactions, are found to be profitable for implementing chemical functionality on the transparent aerogels. Graphical Abstract: [InlineMediaObject not available: see fulltext.]

DOI： 10.1007/s10971-017-4339-6

Highly Flexible Hybrid Polymer Aerogels and Xerogels Based on Resorcinol-Formaldehyde with Enhanced Elastic Stiffness and Recoverability: Insights into the Origin of Their Mechanical Properties 査読有り

Hasegawa George, Shimizu Taiyo, Kanamori Kazuyoshi, Maeno Ayaka, Kaji Hironori, Nakanishi Kazuki

CHEMISTRY OF MATERIALS 29 巻 ( 5 ) 頁： 2122 - 2134 2017年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry of Materials

Flexible low-density materials, such as aerogels and polymer foams, have received increasing attention as energy absorbers and cushions that protect artificial products and human bodies. Microscopic geometry is a crucial factor determining their mechanical functions, i.e. strength and toughness (flexibility). However, it is a formidable challenge to combine these two properties because they are mutually elusive in general; stiff materials are brittle, while flexible ones are soft. Here, we demonstrate lightweight porous polymeric materials based on a common phenolic resin, resorcinol-formaldehyde (RF) gels, with salient combinatorial properties of high stiffness (up to 100 MPa) and good recoverable compressibility (against 80-90% strain), which can deliver remarkable energy absorption and dissipation performances repetitively. The detailed investigation reveals that the unique mechanical features originate from the synergetic effect of interdigitated hard and soft components in polymer matrices as well as exquisitely designed highly branched microstructures both generated through the spontaneous supramolecular self-assembly of the nonionic block copolymer (F127) and RF oligomer, which is essentially analogous to how natural organisms create biological structural materials, e.g. nacre and bone.

DOI： 10.1021/acs.chemmater.6b04706

Amine/Hydrido Bifunctional Nanoporous Silica with Small Metal Nanoparticles Made Onsite: Efficient Dehydrogenation Catalyst 査読有り

Zhu Yang, Nakanishi Takahiro, Kanamori Kazuyoshi, Nakanishi Kazuki, Ichii Shun, Iwaida Kohji, Masui Yu, Kamei Toshiyuki, Shimada Toyoshi, Kumamoto Akihito, Ikuhara Yumi H., Jeon Mina, Hasegawa George, Tafu Masamoto, Yoon Chang Won, Asefa Tewodros

ACS APPLIED MATERIALS & INTERFACES 9 巻 ( 1 ) 頁： 36 - 41 2017年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ACS Applied Materials and Interfaces

Multifunctional catalysts are of great interest in catalysis because their multiple types of catalytic or functional groups can cooperatively promote catalytic transformations better than their constituents do individually. Herein we report a new synthetic route involving the surface functionalization of nanoporous silica with a rationally designed and synthesized dihydrosilane (3-aminopropylmethylsilane) that leads to the introduction of catalytically active grafted organoamine as well as single metal atoms and ultrasmall Pd or Ag-doped Pd nanoparticles via on-site reduction of metal ions. The resulting nanomaterials serve as highly effective bifunctional dehydrogenative catalysts for generation of H2 from formic acid.

DOI： 10.1021/acsami.6b12972

Grafted Polymethylhydrosiloxane on Hierarchically Porous Silica Monoliths: A New Path to Monolith-Supported Palladium Nanoparticles for Continuous Flow Catalysis Applications 査読有り

Pelisson Carl-Hugo, Nakanishi Takahiro, Zhu Yang, Morisato Kei, Kamei Toshiyuki, Maeno Ayaka, Kaji Hironori, Muroyama Shunki, Tafu Masamoto, Kanamori Kazuyoshi, Shimada Toyoshi, Nakanishi Kazuki

ACS APPLIED MATERIALS & INTERFACES 9 巻 ( 1 ) 頁： 406 - 412 2017年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ACS Applied Materials and Interfaces

Polymethylhydrosiloxane has been grafted on the surface of a hierarchically porous silica monolith using a facile catalytic reaction between Si-H and silanol to anchor the polymer. This easy methodology leads to the functionalization of the surface of a silica monolith, where a large amount of free Si-H bonds remain available for reducing metal ions in solution. Palladium nanoparticles of 15 nm have been synthesized homogeneously inside the mesopores of the monolith without any stabilizers, using a flow of a solution containing Pd2+. This monolith was used as column-type fixed bed catalyst for continuous flow hydrogenation of styrene and selective hydrogenation of 3-hexyn-1-ol, in each case without a significant decrease of the catalytic activity after several hours or days. Conversion, selectivity, and stereoselectivity of the alkyne hydrogenation can be tuned by flow rates of hydrogen and the substrate solution, leading to high productivity (1.57 mol g(Pd)-1 h-1) of the corresponding cis-alkene.

DOI： 10.1021/acsami.6b12653

Low-density, transparent aerogels and xerogels based on hexylene-bridged polysilsesquioxane with bendability 査読有り

Aoki Yosuke, Shimizu Taiyo, Kanamori Kazuyoshi, Maeno Ayaka, Kaji Hironori, Nakanishi Kazuki

JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY 81 巻 ( 1 ) 頁： 42 - 51 2017年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of Sol-Gel Science and Technology

Abstract: Low-density, transparent aerogels based on a hexylene-bridged polysilsesquioxane ([O1.5Si–(CH2)6–SiO1.5]n) network have been prepared for the first time via a simple sol–gel process. An optimized base-catalyzed one-step hydrolysis–polycondensation process of a bridged alkoxysilane precursor 1,6-bis(trimethoxysilyl)hexane in a low-polarity solvent N,N-dimethylformamide allows for the formation of a pore structure of a length scale of several tens nanometers, resulting in low-density, transparent aerogels after supercritical drying. Because of the incorporated organic moiety that bridges the silicon atoms in the network, these aerogels show higher flexibility and strength against compression and bending as compared to silica aerogel counterparts. In addition, minimizing the residual silanol groups in the network by a surface modification with hexamethyldisilazane has further improved resilience after compression and bending flexibility and strength, due to the decreased chance of the irreversible formation of the siloxane bonds upon compression. The resulting trimethylsilylated hydrophobic gels have been subjected to ambient pressure drying to obtain xerogels, resulting in low-density (0.13 g cm−3, 90 % porosity), transparent (71 % transmittance) xerogels. These results are promising for the development of transparent thermal superinsulators applicable to window insulating systems that manage heat transfer in a more efficient way. Graphical Abstract: [Figure not available: see fulltext.]

DOI： 10.1007/s10971-016-4077-1

Effects of nanostructured biosilica on rice plant mechanics 査読有り

Sato Kanako, Ozaki Noriaki, Nakanishi Kazuki, Sugahara Yoshiyuki, Oaki Yuya, Salinas Christopher, Herrera Steven, Kisailus David, Imai Hiroaki

RSC ADVANCES 7 巻 ( 22 ) 頁： 13065 - 13071 2017年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：RSC Advances

Nanostructured amorphous silica in rice plants (biosilica or plant opal) plays an important role in plant growth related to food production. However, the same silica has a structural supporting role as well that has not been uncovered. The current study focuses on the structural design of the two main types of biosilicas in rice plants for the improvement of their mechanical properties. One structural motif is plate-like silicas, which cover most of the surfaces of leaf blades. Another is fan-shaped silicas, which are aligned inside leaf blades, providing a stiff backbone. These biosilica structures consist of 10-100 nm diameter nanoparticles. The mechanical properties, such as hardness and Young's modulus, of the biosilicas are associated with their relative density. Thus, the rice plant mechanics is inferred to be designed by changing the packing of the nanoparticles. Silica plates consisting of loosely packed particles have relatively low density and high flexibility enabling coverage of leaf blade surfaces, while fan-shaped silicas, which consist of tightly packed nanoparticles, are rigid to support the leaf blades as a backbone.

DOI： 10.1039/c6ra27317c

Highly Efficient Encapsulation of Ingredients in Poly(methyl methacrylate) Capsules Using a Superoleophobic Material 査読有り

Takei Takayuki, Araki Kiyotaka, Terazono Keita, Ozuno Yoshihiro, Hayase Gen, Kanamori Kazuyoshi, Nakanishi Kazuki, Yoshida Masahiro

POLYMERS & POLYMER COMPOSITES 25 巻 ( 2 ) 頁： 129 - 134 2017年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Polymers and Polymer Composites

Increasing the efficiency of encapsulation of ingredients into spherical capsules can decrease the manufacturing costs of the capsules. Ingredients can be encapsulated with high efficiency (>99%) into nondegradable hard resin capsules prepared by polymerization of spherical droplets of trimethylolpropane trimethacrylate (TRIM) monomer placed on a superoleophobic material. Poly(methyl methacrylate) (PMMA) resin is a more versatile capsule material than poly-TRIM resin. In this study, the efficiency of encapsulation in PMMA resin capsules prepared from methyl methacrylate (MMA) monomer was investigated. To reduce the volatility of the MMA monomer, pre-polymerized MMA was used for capsule preparation. Although non-volatile α-tocopherol and doxorubicin could be encapsulated in the capsules with high efficiency by heat polymerization at 60°C for 3 h, the efficiency for volatile tetradecane was much lower (approximately 60%) because it evaporated. Furthermore, even when using pre-polymerized MMA, more than 70% of the prepolymer evaporated during polymerization. To prevent the evaporation of tetradecane and the prepolymer, ultraviolet photopolymerization was adopted because it was faster and could be conducted at a lower temperature. The photopolymerization prevented the evaporation of the prepolymer and increased the efficiency of encapsulation of tetradecane (approximately 90% efficiency). This polymerization system is effective for encapsulation of ingredients in PMMA capsules with high efficiency.

DOI： 10.1177/096739111702500202

Transparent Ethylene-Bridged Polymethylsiloxane Aerogels and Xerogels with Improved Bending Flexibility. 査読有り

Shimizu T, Kanamori K, Maeno A, Kaji H, Nakanishi K

Langmuir : the ACS journal of surfaces and colloids 32 巻 ( 50 ) 頁： 13427 - 13434 2016年12月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Langmuir

Transparent, monolithic aerogels with nanosized colloidal skeletons have been obtained from a single precursor of 1,2-bis(methyldiethoxysilyl)ethane (BMDEE) by adopting a liquid surfactant and a two-step process involving strong-acid, followed by strong-base, sol-gel reactions. This precursor BMDEE forms the ethylene-bridged polymethylsiloxane (EBPMS, O2/2(CH3)Si-CH2CH2-Si(CH3)O2/2) network, in which each silicon has one methyl, two bridging oxygens, and one bridging ethylene, exhibiting an analogous structure to that of the previously reported polymethylsilsesquioxane (PMSQ, CH3SiO3/2) aerogels having one methyl and three bridging oxygen atoms. Obtained aerogels consist of fine colloidal skeletons and show high visible-light transparency and a flexible deformation behavior against compression without collapse. Similar to the PMSQ aerogels, a careful tuning of synthetic conditions can produce low-density (0.19 g cm-3) and highly transparent (76% at 550 nm, corresponding to 10 mm thick samples) xerogels via ambient pressure drying by solvent evaporation due to their high strength and resilience against compression. Moreover, EBPMS aerogels exhibit higher bending strength and bending strain at break against the three-point bending mode compared to PMSQ aerogels. This improved bendability is presumably derived from the introduced ethylene-bridging parts, suggesting the potential for realizing transparent and bendable aerogels in such polysiloxane materials with organic linking units.

DOI： 10.1021/acs.langmuir.6b03249

Monolithic acidic catalysts for the dehydration of xylose into furfural 査読有り

Zhu Yang, Kanamori Kazuyoshi, Brun Nicolas, Pelisson Carl-Hugo, Moitra Nirmalya, Fajula Francois, Hulea Vasile, Galarneau Anne, Takeda Kazuyuki, Nakanishi Kazuki

CATALYSIS COMMUNICATIONS 87 巻頁： 112 - 115 2016年12月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Catalysis Communications

We report the application of hierarchically porous zirconium phosphate monoliths with high surface area as acidic heterogeneous catalysts for the dehydration of xylose into furfural. Analyses by NH3-temperature programmed desorption and 31P solid state NMR reveal the presence of both Lewis and Brønsted acid sites in the as-synthesized zirconium phosphate monolith and that calcined at 600 °C. High accessibility and availability of the acidic sites and easy separation of the monolith from the liquid medium result in good catalytic activity (initial reaction rate for furfural production as 8.7 mmol gcat− 1 h− 1) with easy handling of the catalyst.

DOI： 10.1016/j.catcom.2016.09.014

Transparent, Highly Insulating Polyethyl- and Polyvinylsilsesquioxane Aerogels: Mechanical Improvements by Vulcanization for Ambient Pressure Drying 査読有り

Shimizu T., Kanamori K., Maeno A., Kaji H., Doherty C., Falcaro P., Nakanishi K.

Chemistry of Materials 28 巻 ( 19 ) 頁： 6860 - 6868 2016年10月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry of Materials

Silica aerogels are unique porous materials possessing high visible-light transparency and low thermal conductivity. However, the practical applications are limited due to the native fragility of silica, and a lot of research focuses on the improvement of mechanical properties by organic-inorganic hybridization, and so forth. Here, the first synthesis of polyethylsilsesquioxane (PESQ; CH3CH2SiO1.5) and polyvinylsilsesquioxane (PVSQ; CH2 - CHSiO1.5) aerogels is reported. The resultant PESQ and PVSQ aerogels obtained through a two-step acid-base sol-gel reaction in a surfactant-based solution exhibit visible-light transmittance and flexibility against compression without collapsing. The microstructural variations of these aerogels are systematically investigated by positron annihilation lifetime spectroscopy (PALS) in order to clarify the differences in properties derived from substituent groups. Furthermore, a post cure on the PVSQ wet gel using a radical initiator induces polymerization of vinyl groups in the solid network, resulting in mechanically reinforced aerogels with higher compressive modulus and resilience. This chemical modification, similar to vulcanization in silicone rubber materials, helps to produce xerogels with comparable properties to those of aerogels via ambient pressure drying. Since the resultant xerogel obtained from the vulcanization of PVSQ shows sufficiently low thermal conductivity of 15.3 mW m-1 K-1, these novel polysilsesquioxane materials are promising for transparent aerogels/xerogels superinsulators.

DOI： 10.1021/acs.chemmater.6b01936

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