研究者データベース

研究者情報

マスター

アカウント(マスター)

  • 氏名

    荻野 勲(オギノ イサオ), オギノ イサオ

所属(マスター)

  • 工学研究院 応用化学部門 化学工学分野

所属(マスター)

  • 工学研究院 応用化学部門 化学工学分野

独自項目

syllabus

  • 2020, 応用分子化学A(分離プロセス工学), Applied Molecular Chemistry A (Separation Process Engineering), 修士課程, 総合化学院, 多孔質材料,吸着,膜分離,クロマトグラフィー
  • 2020, 一般教育演習(フレッシュマンセミナー), Freshman Seminar, 学士課程, 全学教育, 応用化学、化学工学、触媒、吸着、多孔質材料、炭素材料、材料科学、電池材料、水素エネルギ-、材料加工、鋳造
  • 2020, 化学プロセス工学, Chemical Process Engineering, 学士課程, 工学部, 移動現象,流動,伝熱
  • 2020, 物理化学Ⅲ, Physical Chemistry Ⅲ, 学士課程, 工学部, 化学反応の速度,反応機構,反応速度の理論
  • 2020, 物質変換工学, Applied Chemistry and Biochemistry, 学士課程, 工学部, 有機合成,有機材料,化学プロセス,反応器設計,生体材料,高分子材料,分子機能,無機材料,複合材料,電子材料,光機能材料
  • 2020, 応用化学学生実験Ⅳ, Applied Chemistry Laboratory Ⅳ, 学士課程, 工学部, 単位操作、物質収支、エネルギー収支、反応速度、プロセス工学

researchmap

プロフィール情報

学位

  • Ph.D.(Advisor: Distinguished Professor Bruce C. Gates)(University of California, Davis)
  • 修士(京都大学)

プロフィール情報

  • 荻野, オギノ
  • 勲, イサオ
  • ID各種

    201301009973830684

対象リソース

業績リスト

研究キーワード

  • 反応速度論   担持触媒   マイクロ波   ゼオライト   炭素触媒   

研究分野

  • ものづくり技術(機械・電気電子・化学工学) / 移動現象、単位操作
  • ものづくり技術(機械・電気電子・化学工学) / 触媒プロセス、資源化学プロセス
  • ものづくり技術(機械・電気電子・化学工学) / 反応工学、プロセスシステム工学

経歴

  • 2011年 北海道大学 工学(系)研究科(研究院) 准教授

委員歴

  • 2021年04月 - 現在   大学院アンビシャスプログラム「スマート物質科学」   学生選抜委員会委員
  • 2020年04月 - 現在   総合化学院   留学生相談員
  • 2019年 - 現在   化学工学会   北海道支部 幹事(会計)
  • 2014年04月 - 現在   リーディングプログラム国際連携委員会委員
  • - 現在   Journal of Energy Chemistry, Editorial Board Member
  • 2015年 - 2016年   化学工学会   北海道支部 幹事(庶務)

論文

  • Mutjalin Limlamthong, Minseong Lee, Bunjerd Jongsomjit, Isao Ogino, Shusheng Pang, Jungkyu Choi, Alex C.K.Yip
    Advanced Powder Technology Elsevier BV 2021年09月 [査読有り][通常論文]
  • Ryo Obunai, Keisuke Tamura, Isao Ogino, Shin R. Mukai, Wataru Ueda
    Applied Catalysis A: General 624 118294 - 118294 Elsevier BV 2021年08月25日 [査読有り][通常論文]
  • Wasim Ullah Khan, Iris K.M. Yu, Yuqing Sun, Matthew I.J. Polson, Vladimir Golovko, Frank L.Y. Lam, Isao Ogino, Daniel C.W. Tsang, Alex C.K. Yip
    Environmental Pollution 279 15 116899 - 116899 Elsevier BV 2021年06月 [査読有り][通常論文]
  • Isao Ogino
    Heterogeneous Catalysts 617 - 632 2021年03月22日 [査読有り]
  • Isao Ogino, Rei Tanaka, Shin R. Mukai
    Catalysis Today 356 1 11 - 17 Elsevier 2020年10月 [査読有り][通常論文]
  • Cawas Cooper, Kerry M. Dooley, Juan C. Fierro-Gonzalez, Javier Guzman, Rolf Jentoft, H. Henry Lamb, Isao Ogino, Ron C. Runnebaum, Ajit Sapre, Alper Uzun
    ACS Catalysis 11912 - 11935 American Chemical Society (ACS) 2020年09月10日 [査読有り][招待有り]
     
    On the occasion of his 80th birthday, we take stock of the remarkable and ongoing career of Professor Bruce C. Gates. This Account highlights his key scientific achievements in three areas of significance: supported metal clusters and atomically dispersed metal complexes, hydroprocessing reaction networks and catalysts, and strong acid catalysis. His contributions in all three areas are noteworthy and have been sustained over 50 years. The work of his group evolved from mainly catalyst synthesis and reaction studies to also incorporate sophisticated characterization techniques based on X-ray absorption spectroscopies and improved scanning transmission electron microscopic examination of catalytic surfaces. In the course of this work, he has addressed, and contributed to the solutions of some of the most significant and challenging problems in catalysis of the last half century.
  • Isao Ogino, Yuki Hirayama, Shin R. Mukai
    New Journal of Chemistry 44 10002 - 10010 Royal Society of Chemistry 2020年06月28日 [査読有り][通常論文]
  • Isao Ogino, edited by James Spivey, Yi-Fan Han, Dushyant Shekhawat
    The Royal Society of Chemistry 31 166 - 197 2019年02月 [査読有り][招待有り]
     
    Catalysts are required for a variety of applications and industrialists and academics are increasingly challenged to find cost effective and environmentally benign catalysts to use. This volume looks at modern approaches to catalysis and reviews the extensive literature including direct methane conversion, nanocomposite catalysts for transformation of biofuels into syngas and hydrogen and catalytic wet air oxidation technology for industrial wastewater treatment.
  • Seiichiro Yoshida, Shinichiroh Iwamura, Isao Ogino, Shin R. Mukai
    Adsorption 25 6 1089 - 1098 2019年 [査読有り][通常論文]
  • Yu Iwai, Takuya Ikka, Akira Miura, NC Rosero-Navarro, Shinichiroh Iwamura, Isao Ogino, Shin R Mukai, Kiyoharu Tadanaga
    Chemistry Letters 48 7 696 - 699 2019年 [査読有り][通常論文]
  • Kazuya Takahashi, Seiichiro Yoshida, Kasama Urkasame, Shinichiroh Iwamura, Isao Ogino, Shin R. Mukai
    Adsorption 25 6 1241 - 1249 2019年 [査読有り][通常論文]
  • Rei Tanaka, Isao Ogino, Shin R. Mukai
    ACS Omega 3 12 16916 - 16923 2018年12月 [査読有り][招待有り]
  • Kasama Urkasame, Seiichiro Yoshida, Taihei Takanohashi, Shinichiroh Iwamura, Isao Ogino, Shin R Mukai
    ACS Omega 3 10 14274 - 14279 2018年10月31日 [査読有り][通常論文]
     
    Immobilization of TiO2-based photocatalysts usually suffers from lowered surface area and mass transfer limitation compared with their suspended counterpart. In this work, TiO2-SiO2 monolithic photocatalysts having straight macropores, called microhoneycombs, were synthesized. The obtained samples had straight macropores with a diameter in the range of 15-40 μm formed by walls having a thickness up to 5 μm. The samples also contain micropores and small mesopores inside their walls, which contribute to high surface areas of more than 500 m2 g-1. Synthesized photocatalysts were tested in a continuous flow system using the decolorization of methylene blue as a model reaction. It was found that the unique morphology of the samples can be used to promote the uniform distribution of the target fluid while reducing the pressure drop across the photocatalyst to less than a hundredth compared with a packed bed system. In addition, calcination at 600-800 °C improved the strength and photocatalytic activity of the monoliths while preserving the high surface area of the samples.
  • Isao Ogino, Yukei Suzuki, Shin R. Mukai
    Catalysis Today 314 15 62 - 69 2018年09月15日 [査読有り][通常論文]
     
    Analysis of literature data on acid-catalyzed esterification reaction of levulinic acid (LA) with ethanol (EtOH) has suggested that some sulfonated carbon catalysts exhibit higher active-site performance than other solid acid catalysts such as macroreticular resins bearing sulfonic acid groups, zeolites, mesoporous silica functionalized with alkyl- and arene-sulfonic acid groups. To elucidate factors that enable the higher performance of sulfonated carbon catalysts, a series of sulfonated carbon catalysts was synthesized by sulfonating various carbon materials whose concentrations of surface oxygen-containing functional groups, porous structure, and swelling ability differ significantly. The catalysts were tested not only in the liquid-phase esterification reaction of LA with EtOH but also in the reaction of acetic acid (AcA) with EtOH because the latter reaction serves as a test reaction to probe the performance of –SO3H sites with minimal influence by mass transfer limitation and to provide an insight into a role of γ-keto group of LA in catalysis. The results show that all catalysts exhibit nearly the same turnover frequency per –SO3H site in the esterification reaction of AcA with EtOH despite widely different structural properties. In contrast, the data indicate that neighboring functional groups such as –COOH and –OH facilitate the reaction of LA with EtOH presumably through hydrogen-bonding interaction between these surface functional groups and γ-keto group of LA. These results suggest a general design strategy to improve the performance of solid acid catalysts further by precisely tuning the distance between –SO3H sites and neighboring functional groups.
  • Isao Ogino, Go Fukazawa, Shunsuke Kamatari, Shinichiroh Iwamura, Shin R. Mukai
    Journal of Energy Chemistry 27 1468 - 1474 2018年09月 [査読有り][招待有り]
  • Isao Ogino, Rei Tanaka, Shuichiroh Kudo, Shin R. Mukai
    Microporous and Mesoporous Materials 263 181 - 189 2018年06月01日 [査読有り][通常論文]
     
    Mg-Al mixed oxides with highly accessible basic sites were synthesized from Mg-Al layered double hydroxides bearing interlayer isethionates (Ise). Anion-exchange of interlayer carbonates in synthetic hydrotalcites with Ise induces stacking disorders in layered structure, and subsequent delamination in water followed by drying causes further disordering as characterized by X-ray diffraction technique. However, thermal activation of these materials in air formed Mg-Al mixed oxides with low surface area and low CO2 adsorption capacity. In contrast, thermal activation in N2 or N2 followed by air formed materials exhibiting marked increases in CO2 adsorption capacity up to ∼800% relative to those obtained by thermal activation in air. Thermogravimetric and elemental analyses and IR spectroscopy characterization indicate that thermal activation in N2 enables removal of sulfur species formed from Ise at ∼400 °C, and limits the formation of sulfate species that bridge nanosheets and cause irreversible stacking of them. The proper thermal activation procedure in addition to disordered structure of aggregates of Mg-Al double hydroxide nanosheets enabled the formation of Mg-Al mixed oxides with higher surface area and larger micropore volume than those obtained from the initial hydrotalcites. These results highlight the critical importance of thermal activation steps for such materials, and demonstrate a prospective route to synthesize new porous materials based on Mg-Al mixed oxides.
  • 荻野勲, 深澤剛, 鎌足俊輔, 岩村振一郎, 向井紳
    月刊Material Stage 17 12 2018年
  • Kazuki Sakai, Shinichiroh Iwamura, Ryo Sumida, Isao Ogino, Shin R Mukai
    ACS Omega 3 1 691 - 697 2018年 [査読有り][通常論文]
     
    To improve the performance of carbon paper used for applications such as electrodes for electrochemical devices and air filters, two types of long carbon nanofibers (CNFs) with average diameters of 20 and 49 nm were prepared by the liquid pulse injection (LPI) technique by adjusting reaction conditions. Carbon paper was made from the CNFs through a simple filtration process. The paper prepared from the CNFs with an average diameter of 20 nm (LPI-CNF(20) paper) was firm and flexible even though it was prepared without using any binders. LPI-CNF(20) paper also had a high surface area and showed a high electrical conductivity and a moderate gas permeability according to its void size. These properties are required for cathodes in the latest battery systems such as lithium−air batteries. In electrochemical experiments conducted to evaluate the performance of LPI-CNF(20) paper as a cathode, the paper showed a larger discharge capacity on the basis of the cathode weight than a conventional cathode (a commercially available carbon paper combined with a porous carbon), which indicated that it has a high potential to be used as a cathode in lithium−air batteries.
  • Takeshi Mori, Shinichiroh Iwamura, Isao Ogino, Shin R. Mukai
    Separation and Purification Technology 214 174 - 180 2018年 [査読有り][通常論文]
     
    Activated carbons for electrodes of non-aqueous electric double layer capacitors were prepared from composites of poly(methymethacrylate) particles and phenolic resins. Their surface areas can be increased up to 3000 m2 g−1 through simple CO2 activation. Through the characterization of pore properties of the resulting carbons, it was found that the activation process appears to be composed of two steps. The pore properties of the activated carbons were optimized to maximize their performances as electrodes for non-aqueous electric double layer capacitor electrodes.
  • Takeshi Mori, Shinichiroh Iwamura, Isao Ogino, Shin R. Mukai
    JOURNAL OF POROUS MATERIALS 24 6 1497 - 1506 2017年12月 [査読有り][通常論文]
     
    For the preparation of physically-activated carbons with ultra-high surface areas that are comparable to those of chemically-activated carbons, we synthesized meso-, macroporous carbons from phenolic resins using poly(methylmethacrylate) particles as a template and activated them using CO2. Our aim was to achieve uniform activation by reducing the practical depth within the carbon which needs to be activated. Our results show that the shorter the practical depth becomes, the higher the achievable BET surface area becomes. Extremely high BET surface areas (similar to 3000 m(2) g(-1)) can be attained by reducing this depth to the order of a few tens of nanometers. We also relate the practical length of the developed nanopores with the practical depth through the results obtained from EDLC measurements. The results reveal that the shortening of the practical activation depth also leads to the shortening of the lengths of the nanopores introduced during activation.
  • Isao Ogino
    CHINESE JOURNAL OF CATALYSIS 38 9 1481 - 1488 2017年09月 [査読有り][招待有り]
  • Isao Ogino, Pedro Serna, Bruce C. Gates, edited, by, R. Dronskowski, S. Kikkawa, A. Stein
    Wiley-VCH 313 - 337 2017年08月 [査読有り][招待有り]
     
    Catalysts make chemical reactions go faster, often by many orders of magnitude in comparison with purely thermal processes. The dominant technological catalysts are solids, which offer the important practical benefit of being readily separated from fluid‐phase products. Solid catalysts are usually porous, having high internal surface areas and therefore high numbers of catalytically active species per unit of reactor volume to facilitate high rates of catalytic reaction. The preparation of common supported catalysts involves support synthesis, deposition of catalyst precursor components, and treatment to convert the supported species into catalytically active species. Industrial catalysts are also subjected to additional processing to control the sizes and shapes of the final product. The effect of the structure of a crystal face on catalysis is typically diagnosed in experiments with single crystals exposing various faces and often rationalized on the basis of relationships between the crystallographic orientations and the adsorbate‐adsorbent (reactant‐catalyst) binding energies.
  • Takeshi Mori, Shinichiroh Iwamura, Isao Ogino, Shin R. Mukai
    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN 50 4 315 - 323 2017年04月 [査読有り][通常論文]
     
    Independent controlling of micro-(< 2 nm), meso-(2-50 nm) and macropore (> 50 nm) structures in monolithic carbon gels (CGs) was achieved by simply adjusting three independent synthetic parameters. Monolithic composites of resorcinol- formaldehyde (RF) gel and poly(methylmethacrylate) (PMMA) particles were prepared and subsequently carbonized yielding carbonized monoliths. Macropores were successfully introduced as traces of the PMMA particles without hardly affecting the structures of the micro-and mesopores of CGs. The size of the macropores can be controlled in the range of 0.05-1.0 mu m by adjusting the size of the PMMA particles. The size of the mesopores can also be controlled in the range of a few to a few tens of nanometers by adjusting the concentration of the catalyst in the starting RF solution. Micropores can be efficiently developed by activating the CG monoliths with CO2 gas yielding monoliths having extremely high BET surface areas up to similar to 3000 m(2) g(-1).
  • Seiichiro Yoshida, Kazuya Takahashi, Shuichiro Kudo, Shinichiroh Iwamura, Isao Ogino, Shin R. Mukai
    INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH 56 10 2834 - 2839 2017年03月 [査読有り][通常論文]
     
    Silica microhoneycombs (SMHs) loaded with an ionic liquid (IL) (IL-SMHs) were successfully synthesized by impregnating SMHs with an IL bearing an amino group, trihexyl(tetradecyl)-phosphonium alanate ([P-66614][Ala]). SMHs can incorporate at least 50 wt % [P-66614] [Ala] without its straight channels being clogged as demonstrated by a low pressure drop when He was passed through the material. The IL-SMH containing 50 wt % [P-66614] [Ala] shows a CO2 capacity of similar to 0.26 mmol-CO2.g(-1) in a CO2 33%-N-2 67% atmosphere at 303 K IL-SMHs can be readily regenerated by heating them at 393 K and can be reused at least three times without losing the CO2 absorption ability. IL-SMH can also effectively separate CO2 in a flow system. The length of unused bed was very short (only 19 mm). These results demonstrate the high potential of IL-SMHs to be used for effective CO2 separation in flow systems.
  • Seiichiro Yoshida, Shinichiroh Iwamura, Isao Ogino, Shin R. Mukai
    ADSORPTION-JOURNAL OF THE INTERNATIONAL ADSORPTION SOCIETY 22 8 1051 - 1058 2016年11月 [査読有り][通常論文]
     
    Adsorption of phenol from an aqueous solution in batch and continuous flow systems using carbon gels with a microhoneycomb structure (carbon gel microhoneycombs, CMHs) was studied. The obtained monolithic CMHs had fairly straight channels, 25-45 mu m in diameter, and the thickness of the walls which form the channels was around 5 mu m. The CMHs showed 370 times lower hydraulic resistance when compared with a column packed with particles having the same diffusion path length as it. The obtained CMHs have a hierarchical micro-meso porous structure giving BET surface area in the range of 513-1070 m(2)center dot g(-1).When used for phenol adsorption from an aqueous solution, the CMHs quickly adsorbed phenol at first, and then, the uptake gradually increased, which indicates that the adsorption mechanism is based on not only simple physisorption. The phenol adsorption capacity increased with the increase in carbonization temperature of the CMH and the decrease in its hydrophilicity. CMHs carbonized at temperatures higher than 1073 K showed the highest phenol adsorption capacity which was around 160 mg center dot g(-1). The CMHs could continuously adsorb phenol from aqueous solutions, and their length of unused bed (LUB) values depended on operation conditions but were in the range of 0.3-0.7 cm. The experimental results indicated that carbon cryogels with a microhoneycomb structure have a high potential to be used for effective separation of phenol.
  • Shinichiroh Iwamura, Kohei Kitano, Isao Ogino, Shin R. Mukai
    MICROPOROUS AND MESOPOROUS MATERIALS 231 171 - 177 2016年09月 [査読有り][通常論文]
     
    Carbon microhoneycombs (CMHs), which can be prepared from a resorcinol formaldehyde (RF) hydrogel using ice crystals as a template, are attractive materials for industrial applications such as solid catalysts and adsorbents in flow system reactors. For such applications, pores in a material are important for mass transfer, but the mesopore volumes of CMHs are smaller than that of typical RF-derived carbons because ice crystals compress RF gels during freezing, and mesopores partly collapse. The introduction of mesopores into CMHs requires an additional step such as HCl treatment in the preparation process, and this increases the preparation time. In this work, we developed a convenient method for introducing mesopores into CMHs, in which dextran was added to the initial RF solution. This simple step increased the mesopore volume from 0.015 to 0.191 cm(3)/g. We investigated the porous structure of the sample at each step in the preparation, and found that dextran protected the porous structure of the RF hydrogel from growth of ice crystals, enabling mesopore introduction. A combination of dextran addition and HCl treatment further increased the mesopore volume to 0.753 cm3/g; this cannot be achieved using HCl treatment alone. This may be because the HCl solution can diffuse through the mesopores introduced by dextran addition, and this promotes pore formation. (C) 2016 Elsevier Inc. All rights reserved.
  • Napan Narischat, Tatsuya Takeguchi, Takeshi Mori, Shinichiroh Iwamura, Isao Ogino, Shin R. Mukai, Wataru Ueda
    INTERNATIONAL JOURNAL OF HYDROGEN ENERGY 41 31 13697 - 13704 2016年08月 [査読有り][通常論文]
     
    To investigate the effects of the porous structure of carbon support for bimetallic PtRu PEFC anode catalysts on their CO tolerance, a series of Resorcinol-formaldehyde carbon gels with different resorcinol to catalyst (R/C) ratios (i.e., 200, 800 and 1000) were synthesized and used to support Pt2Ru3 nanoparticles. Synthesized catalysts were characterized by powder X-ray diffraction, N-2 gas adsorption/desorption experiments, and scanning transmission electron microscopy. CO tolerances were evaluated by using a single cell in a H-2 feed in the presence of CO ranging from 100 to 2000 ppm. The potential difference of the cell using Pt2Ru3/RC1000ac58 anode catalyst was 0.655 V whereas the cell using a commercial Pt2Ru3/C catalyst showed a voltage of 0.570 V in the presence of 500 ppm CO. The results reveal that high modal size and volume of mesopore enhance diffusivity of CO resulted in effectively oxidization of CO. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
  • 荻野勲, 向井紳
    ケミカルエンジニヤリング 61 5 2016年
  • Sohei Yamazaki, Takeshi Mori, Isao Ogino, Shin R. Mukai
    CHEMICAL ENGINEERING JOURNAL 278 15 122 - 128 2015年10月 [査読有り][通常論文]
     
    Flexible film-type catalysts were synthesized by encapsulating urease within a kappa-carrageenan gel network supported on a cellulose-acetate membrane filter. Synthesized film-type catalysts are flexible and can be easily formed into a shape that is suitable for a specific process configuration. The filter membrane has macropores about 200 nm, which are formed by interconnected bead-shaped membrane material. Scanning electron microscopy shows that the surface of the membrane material is coated homogeneously with the kappa-carrageenan hydrogel. Urease entrapped within the gel network hardly leaches out during urea hydrolysis catalysis conducted at 310 K in a batch reactor and exhibits high catalytic performance. Analysis of the reaction data by the Michaelis-Menten equation shows that the film-type catalyst shows kinetic parameters (K-M and V-max) and apparent activation energy (24 kJ mol(-1)), which are all similar to those found for free urease. Estimation of the mass transfer rate of urea within the kappa-carrageenan network and the urea hydrolysis rate show that the diffusion rate of urea within the thin film is five orders of magnitude higher than the reaction rate. The film catalyst can be recycled at least 7 times with <20% decrease in activity. High flexibility as well as high catalytic performance of the film catalyst shows prospective features of this catalyst for future applications. (C) 2014 Elsevier B.V. All rights reserved.
  • Isao Ogino, Yukei Suzuki, Shin R. Mukai
    ACS CATALYSIS 5 8 4951 - 4958 2015年08月 [査読有り][通常論文]
     
    A series of sulfonic-acid-containing carbon catalysts were synthesized through the pyrolyzation of resorcinol-formaldehyde resins and subsequent sulfonation to investigate the tunability of their pore structure and surface properties. These catalysts were characterized by nitrogen gas adsorption, water vapor adsorption, elemental analysis, Boehm titration, and IR spectroscopy. Catalytic consequences of these properties were examined using two esterification reactions in which reactants of substantially different sizes (oleic acid vs acetic acid) are involved as well as the condensation of furfural with 2-methylfuran. The esterification of acetic acid with ethanol proceeded at nearly the same activity (TOF similar to 0.02 s(-1)) for all synthesized catalysts regardless of the variation of their surface and pore properties. Poisoning experiments of acid groups in the synthesized catalysts with NaCl indicate that nearly all -SO3H groups are accessible to the reactants. However, the esterification of oleic acid with methanol requires a large volume of mesopores (>0.4 cm(3) g(-1)) to proceed as efficiently as that using p-toluenesuffonic acid (p-TSA) as the catalyst. The condensation reaction requires both hydrophobic surfaces and a large volume of mesopores. A synthesized carbon-based catalyst having a large mesopore volume (1.1 cm(3) g(-1)) and surfaces with a relatively high hydrophobicity catalyzes this reaction at a much higher rate and higher selectivity (>90%) than Amberlyst-15. The results reported here show that the pore structure and surface properties of phenolic-resin-derived carbon catalysts can be easily tuned to maximize their catalytic performance in the reaction for which they are intended.
  • Ilke Arslan, John D. Roehling, Isao Ogino, K. Joost Batenburg, Stacey I. Zones, Bruce C. Gates, Alexander Katz
    JOURNAL OF PHYSICAL CHEMISTRY LETTERS 6 13 2598 - 2602 2015年07月 [査読有り][通常論文]
     
    Zeolite delamination increases the external surface area available for catalyzing the conversion of bulky molecules, but a fundamental understanding of the delamination process remains unknown. Here we report morphological changes accompanying delamination on the length scale of individual zeolite clusters determined by 3-D imaging in scanning transmission electron microscopy. The results are tomograms that demonstrate delamination as it proceeds on the nanoscale through two distinct key steps: a chemical treatment that leads to a swelled material and a subsequent calcination that leads to curling and peeling off of delaminated zeolite sheets over hundreds of nanometers. These results characterize the direct, local, 3-D morphological changes accompanying delaminated materials synthesis and, with corroboration by mercury porosimetry, provide unique insight into the morphology of these materials, which is difficult to obtain with any other technique.
  • Isao Ogino, Yuya Yokoyama, Shin R. Mukai
    TOPICS IN CATALYSIS 58 7-9 522 - 528 2015年05月 [査読有り][招待有り]
     
    Efficacy of a new approach for the synthesis of graphene oxide (GO) nanosheets that has been recently reported (Ogino et al. in Chem Mater 26:3334-3339, 2014) was investigated further using graphite oxides with various degrees of oxidation and average particle sizes. The approach consists of rapid freeze-thaw cycles of water containing graphite oxide, which enables the efficient exfoliation of graphite oxide layers with the minimal fragmentation of GO sheets. The method is effective for the exfoliation of graphite oxides with C/O atomic ratios <= 2.6 as shown by experiments with various degrees of oxidation of graphite oxides. When this method was tested for large particle-size graphite oxide that had been prepared from graphite with the average particle size of 60 mu m, it formed approximately tenfold larger GO sheets than those prepared using sonication. Exfoliation experiments conducted at different freezing rates of water demonstrate that a faster freezing rate of water yielded a higher concentration of a dispersed GO solution. Thus, the results support the hypothesis that rapid phase change enables efficient layer exfoliation.
  • Tatsuya Kikuchi, Ryoma Ishida, Shungo Natsui, Takehiko Kumagai, Isao Ogino, Norihito Sakaguchi, Mikito Ueda, Ryosuke O. Suzuki
    ECS SOLID STATE LETTERS 4 9 M19 - M22 2015年 [査読有り][通常論文]
     
    The novel fabrication of multi-walled carbon nanotube (MWCNT)/cementite (Fe3C) nanocomposites was demonstrated via the calciothermic reduction of carbon dioxide (CO2) through electrolysis in molten CaCl2/CaO with iron additives at 1173 K. In this technique, CO2 generated from a graphite anode is reduced to carbon with a metallic calcium reductant formed on a graphite cathode via electrolysis in molten salt. Calciothermic reduction without iron additives resulted in the formation of onion-like carbons (OLCs) with spherical graphite layers and thin graphite sheets. In contrast, MWCNT/Fe3C nanocomposites and OLCs were successfully fabricated via calciothermic reduction with iron additives through their catalytic activities. (C) The Author(s) 2015. Published by ECS. All rights reserved.
  • Shin R. Mukai, Yoshinao Kimura, Seiichiro Yoshida, Isao Ogino
    Chemical Engineering Transactions 42 181 - 186 2014年12月01日 [査読有り][通常論文]
     
    Prussian blue analogues (PBAs) such as K2[CuFe(CN)6] are expected to become the key material for efficient cesium recovery. However to use this material efficiently, it must have a morphology that doesn't cause a severe hydraulic resistance, as a high throughput is required during recovery. This is very difficult, as this material is usually obtained in the form of small particles. In this work, we developed a cesium adsorbent with a low hydraulic resistance using PBAs as the adsorption sites. Silica-alumina was selected as the substrate. As for the morphology of the adsorbent, we adopted a microhoneycomb structure, which can be obtained by the Ice Templating Method, a new micromolding method developed in our laboratory. The obtained adsorbent showed a significantly lower hydraulic resistance than conventional adsorbents in the particle form, and could be used to continuously remove ppm-ordered cesium from solutions.
  • Isao Ogino, Sophie Hermans, Thierry Visart, de Bocarme Ed
    The Royal Society of Chemistry 27 - 54 2014年11月 [査読有り][招待有り]
  • Napan Narischat, Tatsuya Takeguchi, Takanori Tsuchiya, Takeshi Mori, Isao Ogino, Shin R. Mukai, Wataru Ueda
    JOURNAL OF PHYSICAL CHEMISTRY C 118 40 23003 - 23010 2014年10月 [査読有り][通常論文]
     
    Resorcinol-formaldehyde carbon gels (RFCs) show several advantageous properties as a catalyst support over other carbons, as their pore volume and pore size can be readily tailored, for example, via CO2 activation. In this study, RFCs were synthesized with various activation degrees (burn-off) as 0, 37, 58, and 88% and used as the support for a PtRu anode electrode; a commercial Pt2Ru3/C anode catalyst was used as a reference. The catalysts were characterized by powder X-ray diffraction (PXRD), BET surface area, transmission electron microscopy (TEM), and scanning transmission electron microscopy (STEM). The performance and CO tolerance of the obtained catalysts were tested through single cell performance analysis with CO contaminations ranging from 100 to 2000 ppm. The prepared Pt2Ru3/RFC catalysts showed superior CO tolerance. Especially Pt2Ru3/RFC prepared using an RFC with a burn-off of 58% (RC1000Ac58) showed the highest performance and best CO tolerance. The activation degree could affect the volumes and sizes of mesopores and micropores, resulting in differences in size and dispersion of PtRu particles, and accessibility to the particles both of which govern the performance and CO tolerance of the catalysts. Pt2Ru3/RC1000Ac58 showed the highest cell voltage of 0.787 V and highest CO tolerance at 2000 ppm of CO (0.655 V, only 16.8% overvoltage. Supporting PtRu particles by using a carbon support with an optimum activation degree could be a practical method to improve the performance and CO tolerance of a PtRu electrocatalyst.
  • Takanori Tsuchiya, Takeshi Mori, Shinichiroh Iwamura, Isao Ogino, Shin R. Mukai
    CARBON 76 240 - 249 2014年09月 [査読有り][通常論文]
     
    High-surface-area carbon xerogels were prepared in the form of disks via carbonization of precursor resorcinol-formaldehyde (RP) polymer disks and subsequent activation of the resultant RF carbon xerogels by CO2. RF carbon xerogels allow the preparation of a set of pre-activated carbon disks having different mesopore volumes. Analysis of the relationship between the mesopore volume of the samples and their CO2 activation efficiency showed that the presence of mesopores is crucial for obtaining a high-surface-area carbon with minimal burn-off of carbon atoms. Activation of an RF carbon disk with a mesopore volume of 1.0 cm(3) g(-1) up to a bum-off of 81% yielded an activated carbon disk with a high BET surface area of similar to 3000 m(2) g(-1). Such disks could be readily used as electrode materials for an electric double layer capacitor without filler or binder addition and exhibited competitive EDLC performance against other electrode materials previously reported. (C) 2014 Elsevier Ltd. All rights reserved.
  • Isao Ogino, Yuya Yokoyama, Shinichiro Iwamura, Shin R. Mukai
    CHEMISTRY OF MATERIALS 26 10 3334 - 3339 2014年05月 [査読有り][通常論文]
     
    Dispersed graphene oxide (GO) nanosheets in water were synthesized via a new approach involving sonication-free exfoliation, as promoted by repetitive simple freeze-thaw cycles. These cycles consist of rapid freezing of an aqueous solution containing graphite oxide and subsequent thawing of the resultant solid. This approach is effective for exfoliation of graphite oxide and yields approximately 80% GO after six repetitive freeze-thaw cycles. The GO synthesized by the new method experiences minimal fragmentation during the exfoliation process and has a lateral size at least 3-fold larger than that of GO prepared by using sonication, as evidenced by atomic force microscopy and dynamic light scattering. We also demonstrate use of the resulting exfoliated GO that is synthesized using this approach as a building block for the synthesis of a low-density (approximate to 0.02 g cm(-3)) macroporous monolithic material, using directional freezing, which forms ice rods within the solution that served as the template to direct the assembly of the solution-dispersed GO nanosheets into a honeycomb-like morphology with a 10 mu m macropore opening and sheet-like walls. Such a unique morphology of the synthesized monolith has broad applicability for advanced functional materials that allow extremely high throughput with minimal pressure drop as well as electronic and energy storage materials.
  • Isao Ogino, Kazuki Sakai, Shin R. Mukai
    J. Phys. Chem. C 118 13 6866 - 6872 2014年04月 [査読有り][通常論文]
     
    Monolithic carbon cryogels having a honeycomb structure with pore openings a few tens of micrometers in diameter (Carbon Micro Honeycomb, CMH) were synthesized by directional freezing of precursor resorcinol formaldehyde (RF) hydrogels and subsequent carbonization at temperatures >= 674 K. Aging of precursor RF monoliths with 1 N HCl aq. was found to markedly increase the hydrophobicity of the corresponding CMHs as characterized by water vapor adsorption experiments conducted at 298 K. Analysis of the water vapor adsorption data indicates that levels of hydrophobicity of CMHs are similar to those exhibited by other types of highly hydrophobic adsorbents, such as a coal-derived activated carbon and a defect-free pure silica zeolite Beta. HCl aging also drastically changes the porous structure of CMHs from microporous to micro/mesoporous as characterized by nitrogen adsorption/desorption experiments. Because of significantly enhanced hydrophobicity of CMHs as well as hierarchical pore structure (straight macropores connected with micro/mesopores), CMHs can readily separate 1-butanol molecules from a diluted aqueous solution at 310 K and demonstrate high capacities (up to approximate to 3.13 mol kg(-1) at a 1-butanol concentration of 135 mM). The unique morphology of CMHs, consisting of straight macropores coupled with micro/mesopores embedded within honeycomb walls, and the highly hydrophobic surface properties offer future prospects of CMHs in various applications that require fast separation of hydrophobic molecules from a large volume of aqueous solutions.
  • Shin R. Mukai, Yoshinao Kimura, Seiichiro Yoshida, Isao Ogino
    SDEWES: THE 8TH CONFERENCE ON SUSTAINABLE DEVELOPMENT OF ENERGY, WATER AND ENVIRONMENT SYSTEMS 42 181 - 186 2014年 [査読有り][通常論文]
     
    Prussian blue analogues (PBAs) such as K-2[CuFe(CN)(6)] are expected to become the key material for efficient cesium recovery. However to use this material efficiently, it must have a morphology that doesn't cause a severe hydraulic resistance, as a high throughput is required during recovery. This is very difficult, as this material is usually obtained in the form of small particles. In this work, we developed a cesium adsorbent with a low hydraulic resistance using PBAs as the adsorption sites. Silica-alumina was selected as the substrate. As for the morphology of the adsorbent, we adopted a microhoneycomb structure, which can be obtained by the Ice Templating Method, a new micromolding method developed in our laboratory. The obtained adsorbent showed a significantly lower hydraulic resistance than conventional adsorbents in the particle form, and could be used to continuously remove ppm-ordered cesium from solutions.
  • Yoshitaka Satoh, Yuya Yokoyama, Isao Ogino, Shin R. Mukai
    INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH 52 44 15293 - 15297 2013年11月 [査読有り][通常論文]
     
    A honeycomb-type silica monolith was functionalized with sulfonic acid groups to synthesize a solid acid catalyst for flow reaction systems. The sulfonic acid groups were introduced via anchoring of 3-mercaptopropyltrimethoxysilane (MPTS) on the silica surface and subsequent oxidation using a H2O2 solution. The honeycomb-type monolith used as the substrate was prepared using ice crystals as a template and was found to have a high open frontal area of approximate to 85% and flow-through macropores (approximate to 27 mu m in diameter) that are surrounded by silica walls (approximate to 2 mu m in thickness). The catalyst was tested by the liquid phase esterification of ethanol with acetic acid at 333 K in a batch reactor as well as a flow reactor. The catalyst was found to exhibit about 2-fold higher catalytic activity than Amberlyst-15 in a batch reactor. The catalyst also showed a stable catalytic activity for 24 h in a flow reactor.
  • Shin R. Mukai, Yuusuke Rikima, Riku Furukawa, Isao Ogino
    INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH 52 44 15281 - 15286 2013年11月 [査読有り][通常論文]
     
    In this work, the growth behavior of carbon nanofibers synthesized using the liquid pulse injection technique was clarified by analyzing samples collected at different growth stages. It was confirmed that, due to the high catalytic activity of the ultrafine metal catalyst particles generated through this technique, the fibers elongate at an extremely high rate during the initial stage of growth, which leads to the high efficiency of carbon nanofiber production. Owing to this high elongation rate, the elongation process and thickening process can be practically considered as two consecutive processes. This allows the modification of the production sequence, resulting in a significant enhancement in production efficiency.
  • Kazuhiro Murakami, Yoshitaka Satoh, Isao Ogino, Shin R. Mukai
    INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH 52 44 15372 - 15376 2013年11月 [査読有り][通常論文]
     
    A carbon-based monolithic acid catalyst with a honeycomb structure (CMHC) was synthesized via carbonization of a resorcinol-formaldehyde resin and subsequent sulfonation using sulfuric acid. The CMHC has nearly straight flow-through macropores (e.g., 47-78 mu m) formed by the directional freezing of the resin precursor. These macropores are surrounded by thin carbon walls of approximately 6-mu m thickness that are micro- and mesoporous as characterized by nitrogen adsorption experiments. The straight macropores enable a low hydraulic resistance to a liquid flow as demonstrated by >1000-fold less pressure drops of water flowing through the CMHC than those calculated for a packed bed of spherical particles with the same diameter as the approximate wall thickness of the CMHC. The CMHC shows a stable catalytic activity in the liquid-phase esterification of acetic acid with ethanol at 333 K in a flow reaction system for 50 h of operation. These results show prospective features of the CMHC for applications in flow reaction systems.
  • Isao Ogino, Einar A. Eilertsen, Son-Jong Hwang, Thomas Rea, Dan Xie, Xiaoying Ouyang, Stacey I. Zones, Alexander Katz
    CHEMISTRY OF MATERIALS 25 9 1502 - 1509 2013年05月 [査読有り][通常論文]
     
    The synthesis of the first delaminated borosilicate layered zeolite precursor is described, along with its aluminosilicate analogue, which consists of Al-containing UCB-3 and B-containing UCB-4 from as-made SSZ-70. In addition, the delamination of PREFER (which is the precursor to ferrierite zeolite) under similar conditions yields delaminated layered zeolite precursors consisting of Al-containing UCB-5 and Ti-containing UCB-6. Multinuclear solid-state NMR spectroscopy (B-11 and Al-27), diffuse-reflectance UV-vis spectroscopy, and heteroatom/Si ratios measured via elemental analysis are consistent with a lack of heteroatom leaching from the framework following delamination. Such mild delamination conditions are achieved by swelling the zeolite precursor in a fluoride/chloride surfactant mixture in DMF solvent, followed by sonication. Powder X-ray diffraction, argon gas physisorption, and chemisorption of bulky base probes strongly suggest delamination, and demonstrate a 1.5-fold increase in the number density of external acid sites and surface area of calcined UCB-3, relative to calcined Al-SSZ-70. The synthesis of microporous pockets in materials UCB-3-UCB-5 suggests the possibility of interlayer porosity in SSZ-70, which is a layered zeolite precursor material whose structure remains currently unknown. The mildness of the delamination method presented here, as well as the lack of need for acidification in the synthesis procedure, enables the delamination of heteroatom-containing zeolites while preserving the framework integrity of labile heteroatoms, which could otherwise be leached under harsher conditions.
  • Takanobu Masuda, Isao Ogino, Shin R. Mukai
    ADVANCED POWDER TECHNOLOGY 24 2 520 - 524 2013年03月 [査読有り][通常論文]
     
    Magnesium ammonium phosphate (MgNH4PO4.6H(2)O:MAP) releases approximately 70% of its ammonia at a mild temperature of 378 K. The resultant material (magnesium hydrogen phosphate (MgHPO4:MHP)-like material), which appears to be an amorphous phase, to remove ammonia from wastewater was investigated. Because the original size of MAP crystals was found to critically affect the kinetics of ammonia uptake by the corresponding MHP-like material, MAP with different sizes were synthesized by changing concentration, pH and temperature of the synthesis solution. The variation in the synthesis concentration was found to change the size of MAP as well as the aspect ratio of the long-axis to the short-axis. The rate of ammonia uptake depends primarily on the dimension of the short-axis of the corresponding MAP crystals. Furthermore, analysis of ammonia uptake using a method similar to the shrinking-core model shows approximately 0.5 mu m from the surface is effectively used for ammonia uptake over a period of a realistic process time. Thus, the results suggest it is crucial to synthesize small MAP crystals with the size of short-axis less than 11 mu m. Our results also show that small MAP crystals can be used at least four times repeatedly for ammonia uptake. (C) 2012 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved,
  • Seiichiro Yoshida, Yoshinao Kimura, Isao Ogino, Shin R. Mukai
    Journal of Chemical Engineering of Japan 46 9 616 - 619 2013年 [査読有り][通常論文]
     
    The present study investigates a monolithic silica microhoneycomb including ammonium molybdophosphate (AMPSMH) that was synthesized for cesium separation in a continuous flow system. The honeycomb structure of the AMP-SMH causes significantly less hydraulic resistance to a liquid flow than a conventional bed of particles as demonstrated by pressure-drop measurements using water. AMP particles were dispersed as small particles ≈10 μm in diameter on or within the microchannels of the silica microhoneycomb as characterized by SEM. These AMP particles function as effective sorbents to remove ppm-level cesium ions effectively from a solution, as shown by the breakthrough curve. These data suggest the potential features of the AMP-SMH for processing a large volume of a solution containing radioactive cesium. © 2013 The Society Of Chemical Engineers, Japan.
  • Takanobu Masuda, Isao Ogino, Shin R. Mukai
    WATER SCIENCE AND TECHNOLOGY 67 2 359 - 365 2013年 [査読有り][通常論文]
     
    Magnesium ammonium phosphate was formed in flow-through microchannels of silica monoliths using two different methods to fabricate materials that show efficient ammonia adsorption performance from wastewater with low hydraulic resistance. Magnesium ammonium phosphate crystals in these materials release ammonia when heated at 378 K, yielding primarily magnesium hydrogen phosphate. When this material was used for ammonia removal from an aqueous solution containing 100 ppm ammonia in a flow system, the material readily removed ammonia, decreasing the ammonia concentration to 25 ppm. The material can be reactivated by the same procedure and used again for ammonia removal. Hydrodynamic resistance through the lengths of the materials depend on the shape of the immobilized crystals, showing that needle-like crystals are more effective to cause less resistance than plate-like particles. The material containing needle-like crystals causes only approximately one-eighth of the hydraulic resistance that a packed column consisted of spherical particles with a typical bed porosity of 0.5 does. Thus, these results demonstrate the high applicability of the material for ammonia removal from wastewater in a continuous process.
  • Einar A. Eilertsen, Isao Ogino, Son-Jong Hwang, Thomas Rea, Sheila Yeh, Stacey I. Zones, Alexander Katz
    CHEMISTRY OF MATERIALS 23 24 5404 - 5408 2011年12月 [査読有り][通常論文]
     
    The delamination of layered zeolite precursor PREFER is demonstrated under mild nonaqueous conditions using a mixture of cetyltrimethylammonium bromide, tetrabutylammonium fluoride, and tetrabutylammonium chloride in N,N-dimethylformamide (DMF) as solvent. The delamination proceeds through a swollen material intermediate which is characterized using powder X-ray diffraction (PXRD). Subsequent addition of concentrated HCl at room temperature leads to synthesis of UCB-2 via delamination of the swollen PREFER material and is characterized using PXRD, transmission electron microscopy (TEM), and argon gas physisorption, which shows lack of microporosity in UCB-2. (29)Si magic angle sinning (MAS) NMR spectroscopy indicates lack of amorphization during delamination, as indicated by the entire absence of Q(2) resonances, and (27)Al MAS NMR spectroscopy shows exclusively tetrahedral aluminum in the framework following delamination. The delamination process requires both chloride and fluoride anions and is sensitive to solvent, working well in DMF. Experiments aimed at synthesizing UCB-2 using aqueous conditions previously used for UCB-1 synthesis leads to partial swelling and lack of delamination upon acidification. A similar lack of delamination is observed upon attempting synthesis of UCB-1 under conditions used for UCB-2 synthesis. The delamination of PREFER is reversible between delaminated and swollen states in the following manner. Treatment of as-made UCB-2 with the same reagents as used here for the swelling of PREFER causes the delaminated UCB-2 material to revert back to swollen PREFER. This causes the delaminated UCB-2 material to revert back to swollen PREFER. Altogether, these results highlight delamination as the reverse of zeolite synthesis and demonstrate the crucial role of noncovalent self-assembly involving the zeolitic framework and cations/anions/structure-directing agent and solvent during the delamination process.
  • Isao Ogino, Michael M. Nigra, Son-Jong Hwang, Jeong-Myeong Ha, Thomas Rea, Stacey I. Zones, Alexander Katz
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 133 10 3288 - 3291 2011年03月 [査読有り][通常論文]
     
    New material UCB-1 is synthesized via the delamination of zeolite precursor MCM-22 (P) at pH 9 using an aqueous solution of cetyltrimethylammonium bromide, tetrabutylammonium fluoride, and tetrabutylammonium chloride at 353 K. Characterization by powder X-ray diffraction, transmission electron microscopy, and nitrogen physisorption at 77 K indicates the same degree of delamination in UCB-1 as previously reported for delaminated zeolite precursors, which require a pH of greater than 13.5 and sonication in order to achieve exfoliation. UCB-1 consists of a high degree of structural integrity via Si-29 MAS NMR and Fourier transform infrared spectroscopies, and no detectable formation of amorphous silica phase via transmission electron microscopy. Porosimetry measurements demonstrate a lack of hysteresis in the N-2 adsorption/desorption isotherms and macroporosity in UCB-1. The new method is generalizable to a variety of Si:Al ratios and leads to delaminated zeolite precursor materials lacking amorphization.
  • Namal de Silva, Jeong-Myeong Ha, Andrew Solovyov, Michael M. Nigra, Isao Ogino, Sheila W. Yeh, Kathleen A. Durkin, Alexander Katz
    NATURE CHEMISTRY 2 12 1062 - 1068 2010年12月 [査読有り][通常論文]
     
    In enzymes, the electronic and steric environments of active centres, and therefore their activity in biological processes, are controlled by the surrounding amino acids. In a similar manner, organic ligands have been used for the 'passivation' of metal clusters, that is, inhibition of their aggregation and control of their environment. However, the ability of enzymes to maintain large degrees of accessibility has remained difficult to mimic in synthetic systems in which little room, if any, is typically left to bind to other species. Here, using calix[4]arene macrocycles bearing phosphines as crude mimics of the rigid backbones of proteins, we demonstrate the synthesis of gold clusters and the control of their accessibility through an interplay between the sizes of the calixarene ligands and metal cores. For 0.9-nm cores, 25% of all the gold atoms within the cluster bind to the chemisorption probe 2-naphthalenethiol. This accessibility dramatically decreases with 1.1-nm and 4-nm gold cores.
  • Isao Ogino, Bruce C. Gates
    JOURNAL OF PHYSICAL CHEMISTRY C 114 18 8405 - 8413 2010年05月 [査読有り][通常論文]
     
    A zeolite H-beta-supported mononuclear rhodium diethene complex (Rh(C(2)H(4))(2){O(2)Al}, where the braces indicate a part of the zeolite) was formed by the reaction of Rh(acac)(eta(2)-C(2)H(4))(2) (acac = acetylacetonate, C(5)H(7)O(2)(-)) with the zeolite. Transient characterization of the sample by X-ray absorption near edge structure (XANES) and infrared (IR) spectroscopies (combined with mass spectrometry of the effluent gas) while the sample was in contact with flowing CO indicates a simple stoichiometric conversion of the supported metal complex into another species, identified by the spectra as the zeolite-supported rhodium gem-dicarbonyl (Rh(CO)(2){O(2)Al}). The sharpness of the nu(CO) bands in the IR spectrum indicates a high degree of uniformity of the supported rhodium gem-dicarbonyl, and isosbestic points in the XANES spectra as the transformation was occurring imply that the rhodium diethene complex was also highly uniform. Spectra similarly show that treatment of the supported rhodium gem-dicarbonyl with flowing C(2)H(4) resulted in another stoichiometrically simple transformation, giving a species suggested to be Rh(C(2)H(4))(CO)(2){O(2)Al}. The intermediate was ultimately transformed when the sample was purged with helium into another highly uniform supported species, inferred on the basis of IR spectra to be Rh(C(2)H(4))(CO){O(2)Al}. Extended X-ray absorption fine structure spectra characterizing the supported rhodium diethene complex and the species formed from it show how the Rh-O bond distance at the Rh-support interface varied in response to the changes in the ligands bonded to the rhodium.
  • Isao Ogino, Bruce C. Gates
    JOURNAL OF PHYSICAL CHEMISTRY C 114 6 2685 - 2693 2010年02月 [査読有り][通常論文]
     
    Mononuclear complexes of rhodium and of ruthenium, Rh(acac)(eta(2)-C2H4)(2) and cis-Ru(acac)(2)(eta(2)-C2H4)(2) (acac = C5H7O2-), were used as precursors to synthesize metal complexes bonded to zeolite beta. Infrared (IR) and extended X-ray absorption fine structure (EXAFS) spectra show that the species formed from Rh(acac)(eta(2)- C2H4)(2) was Rh(eta(2) -C2H4)(2)(+), which was bonded to the zeolite at aluminum sites via two Rh-O bonds. Reaction of this supported rhodium complex with CO gave the supported rhodium gem-dicarbonyl Rh(CO)(2)(+), which was characterized by two nu(co) bands in the IR spectrum, at 2048 and 2115 cm(-1), that were sharp (fwhm of 2115-cm(-1) band = 5 cm(-1)), indicating a high degree of uniformity of the supported species. Nearly the same result was observed (Liang, A. et al. J. Am. Chem. Soc. 2009, 131, 8460) for the isostructural rhodium complex supported on dealuminated MY zeolite, which was characterized by frequencies of the vco bands that were 4 and 2 cm(-1), respectively, greater than those characterizing the zeolite beta-supported complex. This comparison indicates that the Rh atoms in Rh(eta(2)-C2H4)(2)(+) anchored on zeolite beta were slightly more electron-rich than those on zeolite Y. This inference is supported by EXAFS results showing shorter Rh-C bonds in the zeolite beta-supported rhodium ethene complex than in the zeolite Y-supported rhodium ethene complex. In contrast to these supported rhodium complexes, the zeolite beta-supported ruthenium samples were shown by IR and EXAFS spectroscopies to consist of mixtures of mononuclear ruthenium complexes with various numbers of acac ligands; when CO reacted with the supported ruthenium complexes, the resultant ruthenium carbonyls were characterized by vco spectra characteristic of both ruthenium dicarbonyls and ruthenium tricarbonyls.
  • Isao Ogino, Cong-Yan Chen, Bruce C. Gates
    DALTON TRANSACTIONS 39 36 8423 - 8431 2010年 [査読有り][招待有り]
     
    A general method for synthesis of supported metal complexes having a high degree of uniformity is presented, whereby organometallic precursors incorporating acetylacetonate (C(5)H(7)O(2)(-), acac) ligands react with zeolites incorporating OH groups near Al sites. The method is illustrated by the reactions of Rh(acac)(CO)(2) and of cis-Ru(acac)(2)(eta(2)-C(2)H(4))(2) with zeolites slurried in n-pentane at room temperature. The zeolites were H-Beta, H-SSZ-42, H-Mordenite, and HZSM-5. Infrared (IR) and extended X-ray absorption fine structure spectra of the zeolites incorporating rhodium complexes indicate the formation of Rh(CO)(2)(+) bonded near Al sites; similar results have been reported for the formation of zeolite-supported Rh(eta(2)-C(2)H(4))(2+) from Rh(acac)(eta(2)-C(2)H(4))(2). IR spectra of the supported rhodium gem-dicarbonyls include sharp, well-resolved nu(CO) bands, demonstrating that the sites surrounding each metal complex are nearly equivalent. The frequencies of the nu(CO) bands show how the composition of the zeolite influences the bonding of the supported species, demonstrating subtle differences in the roles of the zeolite as ligands. When the zeolite has pore openings larger than the critical diameter of the precursor organometallic compound, the latter undergoes facile transport into the interior of the zeolite, so that a uniform distribution of the supported species results, but when the precursors barely fit through the zeolite apertures, the mass transport resistance is significant and the supported metal complexes are concentrated near the pore mouths.
  • Isao Ogino, Mingyang Chen, Jason Dyer, Philip W. Kletnieks, James F. Haw, David A. Dixon, Bruce C. Gates
    CHEMISTRY-A EUROPEAN JOURNAL 16 25 7427 - 7436 2010年 [査読有り][通常論文]
     
    An essentially molecular ruthenium-benzene complex anchored at the aluminum sites of dealuminated zeolite Y was formed by treating a zeolite-supported mononuclear ruthenium complex, [Ru(acac)(eta(2)-C2H4)(2)](+) (acac = acetylacetonate, C5H7O2-), with (C6H6)-C-13 at 413 K. IR, C-13 NMR, and extended X-ray absorption fine structure (EXAFS) spectra of the sample reveal the replacement of two ethene ligands and one acac ligand in the original complex with one (C6H6)-C-13 ligand and the formation of adsorbed protonated acac (Hacac). The EXAFS results indicate that the supported [Ru(eta(6)-C6H6)](2+) incorporates an oxygen atom of the support to balance the charge, being bonded to the zeolite through three Ru-O bonds. The supported ruthenium benzene complex is analogous to complexes with polyoxometalate ligands, consistent with the high structural uniformity of the zeolite-supported species, which led to good agreement between the spectra and calculations at the density functional theory level. The calculations show that the interaction of the zeolite with the Hacac formed on treatment of the original complex with (C6H6)-C-13 drives the reaction to form the ruthenium-benzene complex.
  • Isao Ogino, Bruce C. Gates
    JOURNAL OF PHYSICAL CHEMISTRY C 113 46 20036 - 20043 2009年11月 [査読有り][通常論文]
     
    A mononuclear ruthenium complex anchored to dealuminated zeolite HY, Ru(acac)(C(2)H(4))(2)(+) (acac = acetylacetonate, C(5)H(7)O(2)(-)), was characterized in flow reactors by transient infrared (IR) spectroscopy and Ru K edge X-ray absorption spectroscopy. The combined results show how the supported complex was converted into a form that catalyzes ethene conversion to butene. The formation of these species resulted from the removal of acac ligands from the ruthenium (as shown by IR and extended X-ray absorption fine structure (EXAFS) spectra) and the simultaneous decrease in the symmetry of the ruthenium complex, with the ruthenium remaining mononuclear and its oxidation state remaining essentially unchanged (as shown by EXAFS and X-ray absorption near-edge structure spectra). The removal of anionic acac ligands from the ruthenium was evidently compensated by the bonding of other anionic ligands, such as hydride from H(2) in the feed stream, to form species suggested to be Ru(H)(C(2)H(4))(2)(+), which is coordinatively unsaturated and inferred to react with ethene, leading to the observed formation of butene in a catalytic process.
  • Isao Ogino, Bruce C. Gates
    CHEMISTRY-A EUROPEAN JOURNAL 15 28 6827 - 6837 2009年 [査読有り][通常論文]
     
    A set of supported ruthenium complexes with systematically varied ratios of chemisorbed to physisorbed species was formed by contacting cis-[Ru(acac)(2)(C(2)H(4))(2)] (I; acac = C(5)H(7)O(2)(-)) with dealuminated zeolite Y. Extended X-ray absorption fine structure (EXAFS) spectra used to characterize the samples confirmed the systematic variation in the loadings of the two supported species and demonstrated that removal of bidentate acac ligands from I accompanied chemisorption to form [Ru(acac)(C(2)H(4))(2)](+) attached through two Ru-O bonds to the Al sites of the zeolite. A high degree of uniformity in the chemisorbed species was demonstrated by sharp bands in the infrared (IR) spectrum characteristic of ruthenium dicarbonyls that formed when CO reacted with the anchored complex. When the ruthenium loading exceeded 1.0 wt% (Ru/Al approximate to 1:6), the additional adsorbed species were simply physisorbed. Ethene ligands on the chemisorbed species reacted to form butenes when the temperature was raised to approximately 393 K: acac ligands remained bonded to Ru. In contrast, ethene ligands on the physisorbed complex simply desorbed under the same conditions. The chemisorption activated the ruthenium complex and facilitated dimerization of the ethene, which occurred catalytically. IR and EXAFS spectra of the supported samples indicate that 1) Ru centers in the chemisorbed species are more electron deficient than those in the physisorbed species and 2) Ru-ethene bonds in the chemisorbed species are less symmetric than those in the physisorbed species, which implies the presence of a preferred configuration for the catalytic dimerization.
  • Isao Ogino, Bruce C. Gates
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 130 40 13338 - 13346 2008年10月 [査読有り][通常論文]
     
    Dealuminated zeolite Y was used as a crystalline support for a mononuclear ruthenium complex synthesized from cis-Ru(acac)(2)(C2H4)(2). Infrared (IR) and extended X-ray absorption fine structure spectra indicated that the surface species were mononuclear ruthenium complexes, Ru(acac)(C2H4)(2)(2+), tightly bonded to the surface by two Ru-O bonds at Al3+ Sites of the zeolite. The maximum loading of the anchored ruthenium complexes was one complex per two Al3+ sites; at higher loadings, some of the cisRu(acac)(2)(C2H4)(2) was physisorbed. In the presence of ethylene and H-2, the surface-bound species entered into a catalytic cycle for ethylene dimerization and operated stably. IR data showed that at the start of the catalytic reaction, the acac ligand of the Ru(acac)(C2H4)(2)(2+) species was dissociated and captured by an Al3+ site. Ethylene dimerization proceeded similar to 600 times faster with a cofeed of ethylene and H2 than without H-2. These results provide evidence of the importance of the cooperation of the Al3+ sites in the zeolite and the H-2 in the feed for the genesis of the catalytically active species. The results presented here demonstrate the usefulness of dealuminated zeolite Y as a nearly uniform support that allows precise synthesis of supported catalysts and detailed elucidation of their structures.
  • A Burton, RJ Darton, ME Davis, SJ Hwang, RE Morris, Ogino, I, SI Zones
    JOURNAL OF PHYSICAL CHEMISTRY B 110 11 5273 - 5278 2006年03月 [査読有り][通常論文]
     
    Single crystals Of pure silica zeolite SSZ-55 were prepared using the fluoride route. Single-crystal X-ray diffraction at a synchrotron source revealed the framework structure of the material, but the unit cell (orthorhombic a = 12.905(2) angstrom, b = 21.344(4) angstrom, c = 5.1279(10)) is too small to accommodate ordered arrays of the organic structure-directing agent. Molecular modeling was used to simulate the docking of the structure-directing agent in the channels of the material, and this revealed a strong space-filling interaction with a number of possible orientations of the organic cation. The overall non-centrosymmetric structure of the solid (spacegroup C222(1)) was confirmed using second harmonic generation experiments.
  • SI Zones, SJ Hwang, S Elomari, Ogino, I, ME Davis, AW Burton
    COMPTES RENDUS CHIMIE 8 3-4 267 - 282 2005年03月 [査読有り][通常論文]
     
    This study surveys the use of a range of structure-directing agents (SDA) in zeolite synthesis experiments under the conditions using HE The studies made are all for systems containing only silica as the inorganic component. Key points to emerge from the study are a reinforcement of the concept of more open-framework host structures forming when the reactions are more concentrated (lower H(2)O/SiO(2) ratios). This discovery had been reported previously from the research group at ITQ in Valencia, Spain. Our studies show that some novel all-silica compositions have been achieved using this route for synthesis. Two new relationships we explore are whether the use of fluoride anion in synthesis has different nucleation selectivities as a function of dilution, and whether guest molecules can achieve tighter packing in the host structures using the fluoride route as contrasted with the hydroxide route. We explore this with MAS NMR studies. We find that some large organo-cations, which produce no products in alkaline media, give interesting host structure in the fluoride reactions. (c) 2005 Published by Elsevier SAS on behalf of Academie des sciences.
  • Ogino, I, ME Davis
    MICROPOROUS AND MESOPOROUS MATERIALS 67 1 67 - 78 2004年01月 [査読有り][通常論文]
     
    (-)-Sparteine is alkylated to prepare a series of compounds that are used as structure-directing agents (SDAs) to specifically crystallize large pore molecular sieves. Two new sparteine derivatives, N-ethylsparteinium (EtSPA) and N,N'-dimethylsparteinium (Me(2)SPA), are synthesized and their single crystal X-ray structures obtained. The results from molecular sieve syntheses using EtSPA and Me(2)SPA are compared to previously reported preparations that employed N (16)-methylsparteinium (MeSPA). In general, crystalline phases obtained with MeSPA, e.g., SSZ-24, CIT-5, ITQ-21, can also be prepared using EtSPA and Me(2)SPA. However, Me(2)SPA did produce what appears to be a new phase from a reaction mixture containing Zn2+. (C) 2003 Elsevier Inc. All rights reserved.
  • Shin R. Mukai, Isao Ogino, Litsu Lin, Yumi Kondo, Takao Masuda, Kenji Hashimoto
    Reaction Kinetics and Catalysis Letters 69 2 253 - 258 2000年 [査読有り][通常論文]
     
    The stability of a "ship in the bottle" type 12-molybdophosphoric acid encaged catalyst was drastically enhanced by stabilizing the acidic species of the catalyst by partial exchange of its protons with cesium cations. This catalyst practically acted as a solid catalyst in the esterification of acetic acid with ethanol.
  • Mukai, SR, T Masuda, Ogino, I, K Hashimoto
    APPLIED CATALYSIS A-GENERAL 165 1-2 219 - 226 1997年12月 [査読有り][通常論文]
     
    12-molybdophosphoric acid encaged in the supercages of Y-type zeolite was synthesized from molybdenum oxide and phosphoric acid, in a slurry mixture of Y-type zeolite crystals and deionized water. After thorough washing in hot water, the 12-molybdophosphoric acid was found to remain in the Y-type zeolite, at an amount estimated to be 0.09 g (g-support)(-1). Catalysts thus obtained were found to show activity for the esterification of acetic acid with ethanol, indicating that this catalyst could be used as a solid acid catalyst in various liquid phase reactions which involve water. (C) 1997 Elsevier Science.

MISC

書籍等出版物

  • Conversion of Carbohydrates to High Value Products (in Heterogeneous Catalysts: Emerging Techniques for Design, Characterization and Applications)
    Isao Ogino, edited, by Wey, Yang Teoh, Atsushi Urakawa, Yun Hau Ng, Patrick Si (担当:分担執筆)
    Wiley-VCH 2021年03月
  • Understanding Atomically Dispersed Supported Metal Catalysts: Structure and Performance of Active Sites (in SPR Catalysis Volume 31)
    Isao Ogino, edited by James Spivey, Yi-Fan Han, Dushyant Shekhawat (担当:分担執筆)
    The Royal Society of Chemistry 2019年 (ISBN: 9781788014540) 
    Catalysts are required for a variety of applications and industrialists and academics are increasingly challenged to find cost effective and environmentally benign catalysts to use. This volume looks at modern approaches to catalysis and reviews the extensive literature including direct methane conversion, nanocomposite catalysts for transformation of biofuels into syngas and hydrogen and catalytic wet air oxidation technology for industrial wastewater treatment.
  • Supported Catalysts (in Handbook of Solid State Chemistry)
    Isao Ogino, Pedro Serna, Bruce C. Gates, edited, by, R. Dronskowski, S. Kikkawa, A. Stein (担当:分担執筆)
    Wiley-VCH 2017年08月 (ISBN: 9783527325870) 
    Catalysts make chemical reactions go faster, often by many orders of magnitude in comparison with purely thermal processes. The dominant technological catalysts are solids, which offer the important practical benefit of being readily separated from fluid‐phase products. Solid catalysts are usually porous, having high internal surface areas and therefore high numbers of catalytically active species per unit of reactor volume to facilitate high rates of catalytic reaction. The preparation of common supported catalysts involves support synthesis, deposition of catalyst precursor components, and treatment to convert the supported species into catalytically active species. Industrial catalysts are also subjected to additional processing to control the sizes and shapes of the final product. The effect of the structure of a crystal face on catalysis is typically diagnosed in experiments with single crystals exposing various faces and often rationalized on the basis of relationships between the crystallographic orientations and the adsorbate‐adsorbent (reactant‐catalyst) binding energies.
  • 2Dゼオライトの合成(ゼオライトナノシート)の合成
    荻野勲 (担当:分担執筆)
    CMC 2015年11月 (ISBN: 9784781310954) 11 
    高機能ゼオライトの最新技術 馬場俊秀 監修
  • Zeolite-supported Molecular Metal Complex Catalysts (in Atomically-Precise Methods for Synthesis of Solid Catalysts)
    Isao Ogino, Sophie Hermans, Thierry Visart, de Bocarme Ed (担当:分担執筆)
    The Royal Society of Chemistry 2014年11月 (ISBN: 9781849738293) 
    There is much interest in preparing catalysts with specific structures for a desired catalytic activity. Although there has been a great amount of research into correlating particles sizes and microstructure to catalytic activity, knowledge about practical catalysts still remain ill-defined. The current challenge is now to understand atomic control.
  • 氷晶テンプレート法 (in ゲルテクノロジーハンドブック)
    荻野勲, 向井紳 (担当:分担執筆)
    NTS 2014年

講演・口頭発表等

  • マイクロ波加熱を利用した窒素ドープ炭素系触媒の高性能化  [招待講演]
    荻野勲
    第 3 回 ワークショップ 2021年07月 シンポジウム・ワークショップパネル(指名)
  • Efficient Microwave-Assisted Annealing of Reduced Graphene Oxides in an up-Flow Reactor
    Konosuke Minakami, Isao Ogino, Shinichiroh Iwamura, Hironobu Ono, Shin R. Mukai
    2020 Virtual AIChE Annual Meeting 2020年11月
  • Scalable Synthesis of Metal Oxide Supports with High Surface Area and Basic Site Density from Mg-Al Layered Double Hydroxides
    Isao Ogino, Rei Tanaka, Kudo Suichiroh, Shin R. Mukai
    26th North American Catalysis Society Meeting 2019年06月
  • Enhancing Oxygen Reduction Reaction Performance of Nitrogen-doped Carbon through Microwave-assisted Annealing in NH3
    Isao Ogino, Takuya Ikka, Shinichiroh Iwamura, Hironobu Ono, Shin R. Mukai
    26th North American Catalysis Society Meeting 2019年06月
  • Confined-Space Synthesis of Nanocrystalline Mo-VO Mixed Oxides Using a Mesoporous Carbon
    Ryo Obunai, Keisuke Tamura, Isao Ogino, Shin Mukai, Wataru Ueda
    2019 North American Catalysis Society Meeting 2019年06月
  • マイクロ波処理による酸化グラフェン還元体の結晶性と欠陥密度の制御  [招待講演]
    Isao Ogino
    機能性ナノ材料セミナー 2018年09月 口頭発表(招待・特別)
  • Locations of Defective SiO– Sites in Lamellar Precursors of Pure-Silica MWW-Type Molecular Sieves
    Isao Ogino, Taichi Shirobe, Shin Mukai
    25th North American Catalysis Society Meeting 2017年06月
  • On the Influence of Mass Transport in Sulfonated Carbon Catalysts Derived from Various Carbon Sources on Liquid-Phase Esterification Reactions
    Isao Ogino, Yukei Suzuki, Shin R. Mukai
    2016 AIChE Annual Meeting 2016年11月
  • A Mixed-Solvent Approach to Delaminate Layered Zeolitic Precursors
    Isao Ogino, Taichi Shirobe, Shin R. Mukai
    2016 AIChE Annual Meeting 2016年11月
  • Adsorption of Water Contaminants in Continuous Flow Systems Using Carbon Cryogels with a Microhoneycomb Structure
    Seiichiroh Yoshida, Shinichiroh Iwamura, Isao Ogino, Shin R. Mukai
    2016 AIChE Annual Meeting 2016年11月
  • Synthesis of a Non-Conventional Monolithic Catalyst by Immobilizing Mg/Al Layered Double Hydroxides within Microchannels of a Silica Monolith
    Isao Ogino, Daiki Andoh, Shin R. Mukai
    2013 AIChE Annual Meeting 2016年11月
  • Sulfonated carbon catalysts synthesized from various carbon sources
    Yukei Suzuki, Isao Ogino, Shin R. Mukai
    The 16th International Congress on Catalysis 2016年07月
  • The Society of Chemical Engineers, Japan, Autumn Meeting, Sapporo, Japan, September 9, 2015  [招待講演]
    荻野勲
    2015年09月
  • Synthesis of Graphene Oxide Via Sonication-Free Exfoliation of Graphite Oxide
    Isao Ogino, Yuya Yokoyama, Shinchiroh Isamura, Shin R. Mukai
    2014 AIChE Annual Meeting 2014年11月
  • Synthesis of Graphene Oxide Via Sonication-Free Exfoliation of Graphite Oxide
    Isao Ogino, Yuya Yokoyama, Shinichiroh Iwamura, Shin R. Mukai
    2014 AIChE Annual Meeting 2014年11月
  • Synthesis of Carbon Nanofibers from Light Liquid Paraffins Using the Liquid Pulse Injection Technique
    Shin R. Mukai, Ryoto Hirahashi, Riku Furukawa, Yuusuke Rikima, Shinichiro Iwamura, Isao Ogino
    2014 AIChE Annual Meeting 2014年11月
  • Continuous Cesium Separation Using a Silica Microhoneycomb Supporting Ammonium Molybdophosphate
    Seiichiroh Yoshida, Shin R. Mukai, Kimura Yoshinao, Isao Ogino
    2014 AIChE Annual Meeting (ISBN: 978-0-8169-1086-1) 2014年11月
  • ISC Seminar, National Institute of Advanced Industrial Science and Technology (AIST), Japan, October 8, 2014  [招待講演]
    荻野勲
    2014年10月
  • Nagoya Univ.-Tsinghua Univ.-Toyota Motor Corp.-Hokkaido Univ. Joint Symposium, Sapporo, Japan, July 22, 2014  [招待講演]
    荻野勲
    2014年07月
  • 247th ACS National Meeting & Exposition, Gabor A. Somorjai Award for Creative Research in Catalysis: Symposium in Honor of Mark E. Davis, Dallas, Texas, March 17, 2014  [招待講演]
    荻野勲
    2014年03月
  • The Japan Petroleum Institute Seminar, Sapporo, Japan, January 25, 2013  [招待講演]
    荻野勲
    2013年01月
  • Electrochemistry Seminar, Nogata, Japan, September 6, 2012  [招待講演]
    荻野勲
    2012年09月
  • Catalysis Seminar, Tokachi, Japan, August 8, 2012  [招待講演]
    荻野勲
    2012年08月

担当経験のある科目(授業)

  • 応用化学実験(流動)北海道大学
  • 応用分子化学A(分離プロセス工学)北海道大学
  • 化学プロセス工学(輸送現象論)北海道大学
  • 物理化学III(速度論)北海道大学
  • 物質変換工学 (オムニバス講義)

共同研究・競争的資金等の研究課題

  • マイクロ波を用いた高性能炭素系非白金触媒合成プロセスの創出
    科学技術振興機構:A-STEP機能検証フェーズ
    -2021年03月 
    代表者 : 荻野勲, 岩村振一郎, 向井紳
  • 日本学術振興会:科学研究費助成事業 基盤研究(B)
    研究期間 : 2017年04月 -2020年03月 
    代表者 : 荻野 勲, 岩村 振一郎, 向井 紳
     
    金属種が原子レベルで分散担持された固体触媒を環境・エネルギー分野の化学反応に利用する研究が活発に行われている。本研究では,層状構造をもつゼオライト前駆体を利用し,その微細孔空間内に金属超微粒子を担持する手法の創出を目指した。層状前駆体の合成条件,層間からの有機構造規定剤の抽出条件,層間に導入するアミノアルコールと金属錯体混合物の種類と組成,得られた試料の熱処理条件について検討を行った。その結果,金属錯体とアミノアルコールの選択,そして試料の活性化処理条件を工夫することで,sub-nmサイズの超微粒子が担持可能であること,得られた触媒が試験反応において特に高い活性を示すことが明らかとなった。
  • 日本学術振興会:科学研究費助成事業 基盤研究(B)
    研究期間 : 2016年04月 -2019年03月 
    代表者 : 向井 紳, 荻野 勲, 岩村 振一郎
     
    本研究では独自に開発した長くて径が小さいカーボンナノファイバーの高効率製造法である液パルスインジェクション法を発展させて、高機能化された、あるいは新機能が導入されたナノファイバー(微小径繊維)を効率よく製造する技術を確立した。続いてこれらの技術によって得られた機能性ナノファイバーを種々の用途で使いやすくするためにシートやモノリス(一体物のブロック)に成型する技術について検討し、得られたシートやモノリスは電気二重層キャパシター等の蓄電デバイスの性能向上のために活用した。
  • 日本学術振興会:科学研究費助成事業 挑戦的萌芽研究
    研究期間 : 2016年04月 -2018年03月 
    代表者 : 向井 紳, 荻野 勲, 岩村 振一郎
     
    本研究では,Mg/Al系層状複水酸化物から得られるナノシート材料をもとに,水素製造プロセスへの利用を想定した,高温向けCO2吸着剤の創出を目指した。また,フィルターなどへの成型が容易なファイバー状物質の開発も行った。その結果,イセチオン酸含有Mg/Al系複水酸化物ナノシートから数百nm径のナノファイバー状物質の調製に成功した。さらに,複水酸化物の熱処理を窒素気流下で行うことにより,空気気流下で行う場合に比べ,得られる複合酸化物のCO2吸着量が最大8倍増加することを見出した。本研究を実施することにより,Mg/Al系複合酸化物の課題であるCO2性能を向上させる因子を見出すことができた。
  • 日本学術振興会:科学研究費助成事業 基盤研究(C)
    研究期間 : 2014年04月 -2017年03月 
    代表者 : 荻野 勲
     
    本研究は,層状化合物の新規層剥離法創出と,得られたナノシートの再構築を通して,新しい触媒・吸着剤・電極材料などの開発を行うことを目的にした。本研究の実施により,今後の研究活動の基盤となる以下の成果が得られた。 1.水の急速な相変化を利用した方法により,シート径の大きな酸化グラフェンを得た。 2.酸化グラフェン乾燥体を短時間マイクロ波処理することで,欠陥密度が極めて低く,かつ純度の高いグラフェン系炭素材料を得た。3.Mg/Al系層状複水酸化物から得られるナノシート分散液を急速に凍結させることで,ナノファイバー状物質を得た。また,この物質が固体塩基触媒として有効に機能することを示した。
  • 日本学術振興会:科学研究費助成事業 挑戦的萌芽研究
    研究期間 : 2014年04月 -2016年03月 
    代表者 : 向井 紳, 荻野 勲, 岩村 振一郎
     
    本研究では,薄膜イオン液体(IL)固定化触媒開発の第一ステップとして,CO2吸着サイトを有するILを直状マクロ孔を有するマイクロハニカム型シリカモノリス体(SMH)壁面に薄膜状で固定化することで,低流体抵抗を示しかつ効率的にCO2を分離できる材料の開発を目指した。検討の結果,SMHの直状マクロ孔を閉塞させることなく55 wt%ものILを固定化できること,得られた試料は,大気圧下,303 KでCO2濃度を33%含む窒素ガスからCO2を迅速に分離できること,393 Kの加熱再生処理により少なくとも4回の再利用ができること,さらに流通試験においても効率的にCO2を分離できることを確認した。
  • 日本学術振興会:科学研究費助成事業 基盤研究(B)
    研究期間 : 2012年04月 -2015年03月 
    代表者 : 向井 紳, 荻野 勲, 岩村 振一郎
     
    本研究ではCsと選択的に不溶性塩を形成するヘテロポリ酸や、共存カチオン存在下においてもCs+に対する高い選択性を示す不溶性金属フェロシアン化物をシリカやシリカアルミナのゲル中に凍結を利用して分散固定化することで、希薄な状態で存在するCsを高い選択性で回収可能な分離材の開発を目指した。また、凍結の方法を工夫することで、固定化と同時に材料を流体抵抗の低いマイクロハニカム等に成型し、吸着に対する応答性を高めることで分離の高速化を図った。
  • 日本学術振興会:科学研究費助成事業 挑戦的萌芽研究
    研究期間 : 2012年04月 -2014年03月 
    代表者 : 向井 紳, 荻野 勲
     
    凍結・融解に伴う水の相変化を利用した新しい層剥離法を開発し,層状化合物から層剥離により機能性ナノシート材料を効率的に得ること,また得られたナノシートを水の相変化を利用して再構築して機能性材料を合成することを目的として研究を実施した。 (1)迅速な凍結・融解操作により,酸化グラファイトから高収率で酸化グラフェン(ナノシート)分散溶液を得ることに成功した。(2)氷晶をテンプレートとして得られた酸化グラフェンからハニカム状モノリス体の調製に成功した。
  • 日本学術振興会:科学研究費助成事業 若手研究(B)
    研究期間 : 2012年04月 -2014年03月 
    代表者 : 荻野 勲
     
    本研究では,ゼオライトの微粒子をマイクロチャネル壁面に集積固定化することで,ゼオライトの分子認識能とマイクロリアクターの機能を併せ持った高度な機能を有する固体触媒材料の創製に取り組んだ。ゼオライト微粒子として,ゼオライトナノシートやゼオライトナノクリスタルを用い,マイクロチャネルを有する担体の前処理条件や,ゼオライト微粒子の固定化手法を検討することにより,目標とする固体触媒の開発を行った。

産業財産権

  • 特開2021-006497:低欠陥化炭素材料の製造方法  
    向井紳, 荻野勲, 岩村振一郎, 皆上昂ノ介, 小野博信
  • 特開2020-090409:低欠陥化含窒素炭素材料の製造方法  
    向井紳, 荻野勲, 岩村振一郎, 一家拓矢, 小野博信
  • WO2018105570:低欠陥化グラフェン系炭素材料及びその製造方法  
    向井紳, 荻野勲, 岩村振一郎, 深澤剛
  • 特許6569101:カーボンナノファイバーの製造方法  
    向井 紳、荻野 勲、岩村 振一郎、鎌足 俊輔、山口 東吾、西川 翔悟
  • 特開2015-026482:多孔質炭素材料及びその製造方法  
    向井 紳, 荻野 勲, 森 武士, 広瀬 寛, 錦織 英孝
  • 特許6214028:酸化グラフェン含有液の製造方法及びその利用  
    向井 紳, 荻野 勲, 横山 裕也
  • 特開2013-159515:メソポーラスカーボンゲルとその製造方法  
    向井 紳, 三浦 雄一郎, 荻野 勲

社会貢献活動

  • Board Member, The Society of Chemical Engineers for Japan, Hokkaido Region
    期間 : 2015年 - 現在
    役割 : その他
  • Member, National Advisory Board, International Symposium on Zeolite and Microporous Crystals 2018, August 5–9
    期間 : 2018年08月05日 - 2018年08月08日
    役割 : 運営参加・支援
  • Session Chair, International Symposium on Zeolite and Microporous Crystals 2018, August 5–9
    期間 : 2018年08月06日 - 2018年08月06日
    役割 : その他
  • Member, Organizing Committee, Catalysis Seminar in Hokkaido, Catalysis Society of Japan, July 8–9
    期間 : 2018年07月08日 - 2018年07月09日
    役割 : 運営参加・支援
  • Organizing Committee, The 5th International Symposium on Ambitious Leader’s Program Fostering Future Leaders to Open New Frontiers in Materials Science, Hokkaido University, November 21–22
    期間 : 2017年11月21日 - 2017年11月22日
    役割 : 運営参加・支援
  • Session Chair, the 17th Asia Pacific Confederation of Chemical Engineers Congress (APCChE 2017), August 23–27
    期間 : 2017年08月23日 - 2017年08月27日
    役割 : その他
  • Session Chair, Hokkaido University – University of California, Berkeley, Joint Symposium on Chemical Sciences and Engineering, January 7
    期間 : 2017年01月06日 - 2017年01月08日
    役割 : その他
  • Member, Organizing Committee, Hokkaido University – University of California, Berkeley, Joint Symposium on Chemical Sciences and Engineering, January 7
    期間 : 2017年01月06日 - 2017年01月08日
    役割 : 運営参加・支援
  • Secretary, The Society of Chemical Engineers for Japan, Hokkaido Region
    期間 : 2015年 - 2016年
    役割 : その他
  • Session Chair, 5th German-Japanese Joint Symposium “Development and Technology of Carbon Materials,” July 20–21, 2015, TU Bergakademie Freiberg Reiche Zeche, IEC-Haus1 Fuchsmühlenweg 9, 09599, Germany
    期間 : 2015年07月20日 - 2015年07月21日
    役割 : その他
  • Member, Organizing Committee, International Symposium on Zeolite and Microporous Crystals 2015, June 28–July 2
    期間 : 2015年06月28日 - 2015年07月02日
    役割 : 運営参加・支援
  • Chair, Department Seminar (Speaker, Distinguished Prof. Bruce C. Gates)
    期間 : 2013年09月06日 - 2013年09月06日
    役割 : その他
  • Member, Organizing Committee, 22th Chemical Engineering and Particle Engineering Research Conference, The Society of Chemical Engineers for Japan, Hokkaido Region, February 1–2
    期間 : 2013年02月01日 - 2013年02月02日
    役割 : その他


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