Faculty Profiles - HIBINO, Takashi

Papers - HIBINO, Takashi

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Erratum: Room-temperature proton transport and its effect on thermopower in a solid ionic semiconductor, TTFCOONH<inf>4</inf> (Journal of Materials Chemistry A (2013) 1 (5089-5096) (DOI:10.1039/C3TA00011G)) Reviewed

Kobayashi Y., Fujii T., Terasaki I., Kino H., Jin Y., Hibino T., Kobayashi T., Nishibori E., Sawa H., Yoshikawa H., Terauchi T., Sumi S.

Journal of Materials Chemistry A Vol. 1 ( 48 ) 2013.12

Oxygen reduction reaction over nitrogen-doped graphene oxide cathodes in acid and alkaline fuel cells at intermediate temperatures Reviewed

Takashi Hibino, Kazuyo Kobayashi, Pilwon Heo

Electrochimica Acta Vol. 112 page： 82 - 89 2013.12

Organometallic Catalysts for Use in a Fuel Cell Reviewed

Matsumoto Takahiro, Kim Kyoungmok, Nakai Hidetaka, Hibino Takashi, Ogo Seiji

CHEMCATCHEM Vol. 5 ( 6 ) page： 1368 - 1373 2013.6

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：ChemCatChem

We report the successful increase in performance of a fuel cell based on organometallic catalysis. An organometallic [NiIIRuIV] peroxo complex functions as cathode catalyst and was designed following mechanistic consideration of the cell. It was confirmed that the organometallic [NiIIRuIV] peroxo catalyst could function in the fuel cell with a 240% increase in power output over our previous systems. This organometallic catalyst can act in both solid and solution phases and allows observation of the mechanism, hence providing us further opportunity for future improvement. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/cctc.201200595

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Proton-conductor-supported ultra-low loading Pt-Rh three-way catalysts Reviewed

Xue Dong, Masakazu Nishida, Takashi Hibino

The Journal of Physical Chemistry C Vol. 117 ( 4 ) page： 1827 - 1832 2013.1

An intermediate-temperature alkaline fuel cell using an Sn_0.92Sb_0.08P₂O₇-based hydroxide-ion-conducting electrolyte and electrodes Reviewed

Takashi Hibino, Kazuyo Kobayashi

Journal of Materials Chemistry A Vol. 1 ( 4 ) page： 1134 - 1140 2013

Hydroxide ion conduction in molybdenum(VI)-doped tin pyrophosphate at intermediate temperatures Reviewed

Takashi Hibino, Kazuyo Kobayashi

Journal of Materials Chemistry A Vol. 1 ( 23 ) page： 6934 - 6941 2013

Intermediate-temperature alkaline fuel cells with non-platinum electrodes Reviewed

Takashi Hibino, Kazuyo Kobayashi

Journal of Materials Chemistry A Vol. 1 ( 24 ) page： 7019 - 7022 2013

Design of proton-conducting Sn_0.95Al_0.05P₂O₇ with mesoporous structure Reviewed

Takashi Hibino, Kazuyo Kobayashi, Satoru Fujita

Journal of Materials Chemistry A Vol. 1 ( 42 ) page： 13082 - 13088 2013

An all-solid-state rechargeable aluminum-air battery with a hydroxide ion-conducting Sb(v)-doped SnP₂O₇ electrolyte Reviewed

Takashi Hibino, Kazuyo Kobayashi, Masahiro Nagao,

Journal of Materials Chemistry A Vol. 1 ( 47 ) page： 14844 - 14848 2013

Room-temperature proton transport and its effect on thermopower in a solid ionic semiconductor, TTFCOONH4 Reviewed

Kobayashi Yuka, Fujii Takenori, Terasaki Ichiro, Kino Hiori, Jin Yongcheng, Hibino Takashi, Kobayashi Tetsuya, Nishibori Eiji, Sawa Hiroshi, Yoshikawa Hideki, Terauchi Takeshi, Sumi Satoshi

JOURNAL OF MATERIALS CHEMISTRY A Vol. 1 ( 16 ) page： 5089 - 5096 2013

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：Journal of Materials Chemistry A

Ammonium proton in a solid ionic semiconductor, TTFCOONH4, is shown to be mobile under anhydrous conditions at room temperature by the hydrogen concentration cell method. Isotope substituted TTFCOOND4 exhibits a 2.2 H/D isotope effect in ion carrier mobility with TTFCOONH 4. First-principles calculations reveal that an efficient proton-transfer pathway via low-barrier N⋯H+⋯N hydrogen bonds reduces the activation energy to 0.12 eV, which is quite small and comparable to that reported in a bulk water system. The ac conductivity of TTFCOONH4 and TTFCOOND4 is similar at room temperature, reflecting similar hole carrier concentrations. In sharp contrast, the thermopower exhibits a large isotope effect: TTFCOONH4 shows 260 μV K-1, which is twice as large as that predicted by the hole carrier concentration and the value of TTFCOOND4, with 138 μV K-1. The 1.9 H/D isotope effect in thermopower closely relates to the 2.2 H/D isotope effect in ion carrier mobility. Proton carriers in the temperature gradient enhance thermopower without cancelling out the effect of holes in the solid state owing to possession of the same positive charge. © The Royal Society of Chemistry 2013.

DOI： 10.1039/c3ta00011g

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Intermediate-temperature, non-humidified proton exchange membrane fuel cell with a highly proton-conducting Fe_0.4Ta_0.5P₂O₇ electrolyte Reviewed

Yanbai Shen, Pilwon Heo, Chanho Pak, Hyuk Chang, Takashi Hibino

Electrochemistry Communications Vol. 24 ( 1 ) page： 82 - 84 2012.10

総説：中温プロトン伝導体のエネルギー・環境技術への応用

日比野高士

化学工業 Vol. 63 ( 10 ) page： 8-16 2012.10

A solid-state particulate matter sensor based on electrochemical oxidation of carbon by active oxygen Reviewed

Shen Y. B., Harada T., Teranishi S., Hibino T.

SENSORS AND ACTUATORS B-CHEMICAL Vol. 162 ( 1 ) page： 159 - 165 2012.2

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：Sensors and Actuators, B: Chemical

The carbon oxidation activity and sensing performance of an electrochemical sensor incorporating a robust SnP 2O 7-SnO 2 composite ceramic as a solid electrolyte were investigated at an operating temperature of 200°C. Specific reactivity of the electrochemically formed active oxygen toward carbon was accomplished with a high current efficiency estimated from the four-electron reaction (C + 2H 2O → CO 2 + 4H + + 4e -). However, this reaction did not occur over the entire electrode layer, which resulted in low sensitivity and a slow response speed. This problem could be overcome by distributing a SnP 2O 7 ionomer over the working electrode at a level of several micrometers. Moreover, an additional benefit of the present sensor for practical applications is that little interference was encountered when sensing carbon at levels of 1000 ppm CO and 1000 ppm C 3H 8 in the sample gas. The resulting amperometric mode sensor could successfully produce a current signal that corresponded to the quantity of particulate matter (PM) in the bench test apparatus. These results demonstrate that the present sensor is able to continuously monitor the PM concentration while self-regenerating. © 2011 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.snb.2011.12.057

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Alternating current electrolysis for production of phenol from benzene Reviewed

Byungik Lee, Hiroto Naito, Masahiro Nagao, Takashi Hibino

Angewandte Chemie-International Edition Vol. 51 ( 28 ) page： 6961 - 6965 2012

Proton conduction in A^Ⅲ_0.5B^Ⅴ_0.5P₂O₇ compounds at intermediate temperatures Reviewed

Yanbai Shen, Keijiro Kojima, Masakazu Nishida, Pilwon Heo, Kyoung Hwan Choi, Hyuk Chang, Takashi Hibino

Journal of Materials Chemistry Vol. 22 ( 30 ) page： 14907 - 14915 2012

Hydroxide ion conducting antimony(Ⅴ)-doped tin pyrophosphate electrolyte for intermediate-temperature alkaline fuel cells Reviewed

Takashi Hibino, Yanbai Shen, Masakazu Nishida, Masahiro Nagao

Angewandte Chemie-International Edition Vol. 51 ( 43 ) page： 10786 - 10790 2012

Electrochemical Oxidation of Benzene to Phenol Reviewed

Lee Byungik, Naito Hiroto, Hibino Takashi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 51 ( 2 ) page： 440 - 444 2012

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：Angewandte Chemie - International Edition

Gas-phase electrochemistry: The direct hydroxylation of benzene to phenol was investigated using an electrochemical cell. The production of phenol over a VO x anode was found to be significant at 50 °C. The resultant current efficiency for phenol production and selectivity toward phenol reached 76.5 and 94.7 %, respectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/anie.201105229

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Proton conduction in non-doped and acceptor-doped metal pyrophosphate (MP2O7) composite ceramics at intermediate temperatures Reviewed

Sato Yousuke, Shen Yanbai, Nishida Masakazu, Kanematsu Wataru, Hibino Takashi

JOURNAL OF MATERIALS CHEMISTRY Vol. 22 ( 9 ) page： 3973 - 3981 2012

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：Journal of Materials Chemistry

Proton conductors capable of operating in the temperature range of 100-600°C have received great interest for many application areas such as fuel cells, sensors, and electrolyzers; however, very few materials that can satisfy these demands have been reported to date. Here, we report a promising candidate for a solid electrolyte in intermediate-temperature electrochemical devices. First, MP 2O 7-MO 2 composite ceramics (M = Sn, Si, Ti, and Zr) were prepared by reacting a porous MO 2 substrate with an 85% H 3PO 4 solution at 600°C. Although all the tested MO 2 could react with H 3PO 4 to form the corresponding metal pyrophosphate layers on the surfaces of the exterior and interior substrate, the extent of MP 2O 7 growth in the obtained samples and their relative density were strongly dependent on the M species. These factors were the best for the SnP 2O 7-SnO 2 composite ceramic, yielding the highest electrical conductivity in the temperature range of interest. Next, different low valence cations (cation = Mg 2+, Sc 3+, Ga 3+, Y 3+, In 3+, La 3+, Sm 3+, Eu 3+, and Gd 3+) were doped into the SnP 2O 7-SnO 2 composite ceramic. The most positive effect on the electrical conductivity was observed when Sm 3+ was used as the dopant; the electrical conductivity of this sample was approximately one order of magnitude higher than that of the non-doped sample, especially at low temperatures below 250°C. Fourier transform infrared (FTIR) and proton magic angle spinning (MAS) nuclear magnetic resonance (NMR) analyses revealed that the quantity of protons incorporated in the SnP 2O 7 layer and their mobility were increased by the doping of Sm into the composite ceramic. As a consequence, the electrical conductivity of the Sm-doped SnP 2O 7-SnO 2 composite ceramic reached ∼10 -2 S cm -1 in the temperature range of 100-600°C. Proton conduction in this sample was also investigated by various electrochemical techniques. The protons function as the predominant charge carrier in the sample, and the proton transport number was almost unity in both static and dynamic conditions. © 2012 The Royal Society of Chemistry.

DOI： 10.1039/c2jm15335a

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総説：ナノ局所電池デバイスのエネルギー・環境技術への応用

日比野高士

ケミカルエンジニヤリング Vol. 56 ( 10 ) page： 48-54 2011.10

Intermediate-temperature proton conductors and their applications to energy and environmental devices Reviewed

Hibino Takashi

JOURNAL OF THE CERAMIC SOCIETY OF JAPAN Vol. 119 ( 1393 ) page： 677 - 686 2011.9

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：Journal of the Ceramic Society of Japan

The development of proton conductors has proceeded rapidly in recent years. A number of organic or inorganic materials show proton conductivities of ∼10-2Scm-1 at temperatures below 100°C. However, although there is great current demand for proton conductors capable of operating in the temperature range of 100400° C in practical applications, very few materials that can satisfy this demand have been reported to date. Acceptor-doped SnP2O7 are promising candidate materials because their proton conductivities reach >10-1Scm-1 in the temperature range of interest. This paper presents an overview of the current status of acceptor-doped SnP2O7, highlighting the mechanism and kinetics of proton conduction and the development of electrochemical devices using these materials. New insights for proton insertion and conduction are proposed that use electrochemical techniques. Two approaches to designing SnP2O7-based composite electrolytes with good mechanical properties have also been developed for different operating temperatures. In addition, the benefits of intermediate-temperature operation using these materials are discussed in terms of practical applications, especially in fuel cells, exhaust sensors, and solid catalysts. © 2011 The Ceramic Society of Japan. All rights reserved.

DOI： 10.2109/jcersj2.119.677

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Papers - HIBINO, Takashi