文部科学省ナノテクノロジー・ネットワークプロジェクト
第7回ナノテクノロジー
総合シンポジウム
.$%) $%"% - %'$' -$$+ '%$#$)/
) %$" $() )*) %')' "( $
$() )*) %$(&') &) $ $) $%) $%"% -),%'!'% )
%!! %$ +'( )- )%( $() )*)% $$ $%"% -% %!*$ +'( )-
%-%$ +'( )-) %$" $() )*)% +$ $*()' " $$ $%"% -
$ +'( )-% %!-%%!-% $() )*)% $%"% -($ +'( )-
) %$" $() )*)(% )*'" $( $() )*) %'%"*"' $
%-$ +'( )- %- $() )*)% $%"% -%-%) $%"% " $() )*)
-%)%$ +'( )- &$+$ $() )*)% $$ $%"% -
' $() )*)% $$ $%"% -(!$ +'( )-
&$)%# $' - $- )(*# !$$ +'( )- '%( #$ +'( )-
# * $ +'( )- -*( *$ +'( )-
' )*'" %$" $*()'-*&&%')$)'
)!-*( * %*$) %$ %') +$#$)% $*()'- $$ $%"% -
$ +'( )-文部科学省ナノテクノロジー・ネットワークプロジェクト
第 7 回ナノテクノロジー総合シンポジウム
JAPAN NANO 2009
プログラム
February 18th 2009, Reception Hall A, B
2009年2月18日（水）会議棟1階レセプションホールA, B
10:00-10:55 【Opening Session / オープニングセッション】
Chair: Sukekatsu Ushioda (National Institute for Materials Science) / 潮田資勝（物質・材料研究機構） 【Opening Remarks / 挨拶】
Mr. Fumio Isoda (Director-General, Research Promotion Bureau, Ministry of Education, Culture, Sports, Science and Technology)
磯田文雄（文部科学省研究振興局長）
Prof. Teruo Kishi (President, National Institute for Materials Science)
岸 輝雄（物質・材料研究機構理事長） 【Plenary Lecture / 基調講演】
10:15 Prof. Yoichi Kaya (Director General, Research Institute of Innovative Technology for the Earth (RITE))
茅 陽一（（財）地球環境産業技術研究機構副理事長・研究所長） “Technologies for Mitigating Global Warming”
「温暖化抑止に向けての技術」
10:55-14:00 【Session 1: Generation and Consumption of Eenergy / エネルギーの生成と利用】
Chair: Kazuo Furuya (National Institute for Materials Science) / 古屋一夫（物質・材料研究機構）
10:55 Dr. Heinz Frei (Helios - Solar Energy Research Center, U.S.A.)
“Helios Solar Energy Research Center - A Nanomaterials Approach to Artificial Photosynthesis” 「米国ヘリオス・プロジェクトにおける太陽エネルギー利用−人工光合成へのナノ材料的アプローチ−」
11:35 Dr. Liyuan Han (National Institute for Materials Science, Japan)
韓 礼元（物質・材料研究機構）
“Dye-sensitized Solar Cells with Nanotechnologies” 「ナノテクノロジーを用いた色素増感太陽電池」
12:00-13:10 Lunch /昼食
Chair: Naotoshi Nakashima (Kyushu University) / 中嶋直敏（九州大学）
13:10 Prof. Kazunari Sasaki (Kyushu University, Japan)
佐々木一成（九州大学）
“Nanostructured Alternative Materials for Fuel Cells: Perspectives and case studies” 「ナノテクノロジーを駆使した次世代燃料電池の開発」
13:35 Prof. Matsuhiko Nishizawa (Tohoku University, Japan)
西沢松彦（東北大学）
“Enzyme-Based Bionic Batteries and Fuel Cells” 「バイオニック発電デバイスの研究開発動向」
14:00-16:15 【Session 2 : Transport and Storage of Energy / エネルギーの輸送と貯蔵】 Chair: Masakazu Sugiyama (The University of Tokyo) / 杉山正和（東京大学）
14:00 Dr. Karl-Heinz Haas (Fraunhofer-Institut für Silicatforschung, Germany) “Nanotechnology for Energy and Environment in Germany”
「ドイツにおける環境・エネルギーに対応したナノテクノロジー」 14:40 Prof. Kazunari Domen (The University of Tokyo, Japan)
堂免一成（東京大学）
“Development of Photocatalytic System for Hydrogen Production from Water with Solar Energy” 「太陽光と水から水素を生成する光触媒システムの開発」
15:05-15:25 Break /休憩
Chair: Yasuyuki Miyamoto (Tokyo Institute of Technology) / 宮本恭幸（東京工業大学） 15:25 Prof. Susumu Kitagawa (Kyoto University, Japan)
北川 進（京都大学）
“Chemistry and Application of Porous Coordination Polymers” 「新しい多孔性金属錯体材料の化学と応用」
15:50 Prof. Hideo Hosono (Tokyo Institute of Technology, Japan) 細野秀雄（東京工業大学）
“Iron-based Superconductors: Recent Advances” 「新しい超電導物質：鉄系高温超電導」
16:15-17:45 【Session 3 : Energy Saving and Environment / 環境・省エネルギー】
Chair: Hiroyuki Akinaga (National Institute of Advanced Industrial Science and Technology) / 秋永広幸（産業技術総合研究所） 16:15 Dr. Spike Narayan (IBM, Almaden Research Center, U.S.A.)
“Na notechnology for Global Environmental Challenges
- Saudi projects at IBM Almaden for Desalination, Photovoltaics and Green Chemistry” 「地球環境へのナノテクノロジーの挑戦−IBMアルマデン・サウジプロジェクトの脱塩、太陽電池及びグリーンケミストリへの取り組み」 16:55 Prof. Kunihito Koumoto (Nagoya University, Japan)
河本邦仁（名古屋大学）
“Nano Thermoelectrics for E2 Technology”
「ナノ熱電変換と環境・エネルギー技術」
17:20 Dr. Koji Tajiri (National Institute of Advanced Industrial Science and Technology, Japan) 田尻耕治（産業技術総合研究所）
“Development of energy efficient building materials for saving air conditioning energy” 「空調エネルギーの削減を図る省エネルギー型建築部材の開発」
17:45-17:50 【Closing Remarks / 挨拶】
Chair: Yoshimasa Sugimoto (National Institute for Materials Science) / 杉本喜正（物質・材料研究機構） Prof. Sukekatsu Ushioda ( Chairperson of the Organizing Committee of JAPAN NANO
2009 / Director General, NIMS Center for Nanotechnology Network,National Institute for Materials Science, Japan)
Contents / 目次
Plenary Lecture /基調講演
“Technologies for Mitigating Global Warming” ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ 2 「温暖化抑止に向けての技術」
Prof. Yoichi Kaya / Director General, Research Institute of Innovative Technology for the Earth (RITE)) 茅 陽一（（財）地球環境産業技術研究機構副理事長・研究所長）
Session 1: Generation and Consumption of Eenergy /エネルギーの生成と利用
“Helios Solar Energy Research Center - A Nanomaterials Approach to Artificial Photosynthesis” ‥‥‥‥‥‥‥‥ 6 「米国ヘリオス・プロジェクトにおける太陽エネルギー利用−人工光合成へのナノ材料的アプローチ−」
Dr. Heinz Frei / Helios - Solar Energy Research Center, U.S.A.
“Dye-sensitized Solar Cells with Nanotechnologies” ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ 8 「ナノテクノロジーを用いた色素増感太陽電池」
Dr. Liyuan Han / National Institute for Materials Science, Japan 韓 礼元（物質・材料研究機構）
“Nanostructured Alternative Materials for Fuel Cells: Perspectives and case studies” ‥‥‥‥‥‥‥‥‥‥‥‥‥ 10 「ナノテクノロジーを駆使した次世代燃料電池の開発」
Prof. Kazunari Sasaki / Kyushu University, Japan 佐々木一成（九州大学）
“Enzyme-Based Bionic Batteries and Fuel Cells” ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ 12 「バイオニック発電デバイスの研究開発動向」
Prof. Matsuhiko Nishizawa / Tohoku University, Japan 西沢松彦（東北大学）
Session 2 : Transport and Storage of Energy / エネルギーの輸送と貯蔵
“Nanotechnology for Energy and Environment in Germany” ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ 16 「ドイツにおける環境・エネルギーに対応したナノテクノロジー」
Dr. Karl-Heinz Haas / Fraunhofer-Institut für Silicatforschung, Germany
“Development of Photocatalytic System for Hydrogen Production from Water with Solar Energy” ‥‥‥‥‥‥‥ 18 「太陽光と水から水素を生成する光触媒システムの開発」
Prof. Kazunari Domen / The University of Tokyo, Japan 堂免一成（東京大学）
“Chemistry and Application of Porous Coordination Polymers” ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ 20 「新しい多孔性金属錯体材料の化学と応用」
Prof. Susumu Kitagawa / Kyoto University, Japan 北川 進（京都大学）
“Iron-based Superconductors: Recent Advances” ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ 22 「新しい超電導物質：鉄系高温超電導」
Prof. Hideo Hosono / Tokyo Institute of Technology, Japan 細野秀雄（東京工業大学）
Session 3 : Energy Saving and Environment / 環境・省エネルギー “Na notechnology for Global Environmental Challenges
- Saudi projects at IBM Almaden for Desalination, Photovoltaics and Green Chemistry” ‥‥‥‥‥‥‥‥‥‥ 26 「地球環境へのナノテクノロジーの挑戦− IBM アルマデン・サウジプロジェクトの脱塩、太陽電池及びグリーンケミストリへの取り組み」
Dr. Spike Narayan / IBM, Almaden Research Center, U.S.A.
“Nano Thermoelectrics for E2 Technology” ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ 28
「ナノ熱電変換と環境・エネルギー技術」 Prof. Kunihito Koumoto / Nagoya University, Japan 河本邦仁（名古屋大学）
“Development of energy efficient building materials for saving air conditioning energy” ‥‥‥‥‥‥‥‥‥‥‥ 30 「空調エネルギーの削減を図る省エネルギー型建築部材の開発」
Dr. Koji Tajiri / National Institute of Advanced Industrial Science and Technology, Japan 田尻耕治（産業技術総合研究所）
“Technologies for Mitigating Global Warming”
「温暖化抑止に向けての技術」
Prof. Yoichi Kaya
(Director General, Research Institute of Innovative Technology for the
Earth (RITE))
茅 陽一
（（財）地球環境産業技術研究機構副理事長・研究所長）
Technologies for Mitigating Global Warming
Yoichi Kaya
Research Institute of Innovative Technology for the Earth
9-2, Kizugawadai, Kizugawa-Shi,
Kyoto, 619-0292, JAPAN
Curriculum Vitae
Yoichi Kaya, born on May 18, 1934 in Sapporo, Japan
1. Current Position
Director General, Research Institute of Innovative Technologies for the Earth (RITE)
2. Education and Degrees
B.A. in engineering the University of Tokyo, 1957 M.A. in engineering the University of Tokyo, 1959 Doctor of Engineering the University of Tokyo, 1962 3. Teaching and Research
Lecturer, Department of Electrical Engineering, the University of Tokyo, 1963
Associate Professor, 1964 Professor, 1978
Senator of the University of Tokyo, 1993
Professor Emeritus, the University of Tokyo, 1995 Professor, Keio University (SFC), 1995-Present Director General, RITE, 1998-present
Program Director for the Nuclear Research Development, Japan Science and Technology
Agency (JST) 2005-Present 4. Research Area
Systems Engineering in the field of Energy and Environment 5. Awards
7 awards from 4 Japanese academic institutions 3 publication awards
6. Activities in Academic Societies
President, Institute of Electrical Engineers of Japan, 1993-1994 President, Japan Association of Energy and Resources, 1997-2000 7. Governmental Activities
Chairman, Energy Council, METI (by June 2004)
Chairman, Sub-committee on global environment policy, METI 8. Industry related activities
External auditor, Shin Nittetsu Company External auditor, Toyota Motor Corporation 9. International Activities
Chairman of National Committee, International Institute of Applied Systems Analysis (IIASA)
Luxembourg, Austria
10. Principal Publications (only books)
New Energy Era, Energy Conservation Center, 1987 (in Japanese)
Electrical Energy in the Global Era, Nikkei, 1995 (in Japanese) Low Carbon Economy, Nikkei, 2008 (in Japanese)
【Session 1】
Generation and Consumption of Eenergy
“Helios Solar Energy Research Center - A Nanomaterials Approach to
Artificial Photosynthesis”
「米国ヘリオス・プロジェクトにおける太陽エネルギー利用
−人工光合成へのナノ材料的アプローチ−」
Dr. Heinz Frei
(Helios - Solar Energy Research Center, U.S.A.)
“Dye-sensitized Solar Cells with Nanotechnologies”
「ナノテクノロジーを用いた色素増感太陽電池」
Dr. Liyuan Han
(National Institute for Materials Science, Japan)
韓 礼元
（物質・材料研究機構）
“Nanostructured Alternative Materials for Fuel Cells: Perspectives and
case studies”
「ナノテクノロジーを駆使した次世代燃料電池の開発」
Prof. Kazunari Sasaki
(Kyushu University, Japan)
佐々木一成
（九州大学）
“Enzyme-Based Bionic Batteries and Fuel Cells”
「バイオニック発電デバイスの研究開発動向」
Prof. Matsuhiko Nishizawa
(Tohoku University, Japan)
西沢松彦
（東北大学）
HELIOS SOLAR ENERGY RESEARCH CENTER – A NANOMATERIALS
APPROACH TO ARTIFICIAL PHOTOSYNTHESIS
Heinz Frei
Physical Biosciences Division and Helios Solar Energy Research Center,
Lawrence Berkeley National Laboratory, Berkeley, CA 94720
Abstract
The long term goal of the research at the Helios Solar Energy Research Center (SERC) is the efficient conversion of carbon dioxide and water by sunlight to a fuel that matches at least the energy density of methanol. The effort of the Center focuses on breaking down the scientific barriers that have prevented so far the light capturing and charge separating components, the fuel forming catalysts and the electrochemical elements to be sufficiently efficient, durable, made of abundant materials and with scalable processes. Equally challenging scientific issues for the efficient integration of the components into a complete solar fuel generator are addressed. Inorganic materials for components and scaffolds for integration are particularly attractive because of the robustness; hence, our focus is on these materials. Because light driven processes and chemical transformations need to be manipulated and controlled on the nanometer scale, advances in inorganic nanostructured materials are particularly relevant for our effort. This overview of the SERC will be complemented by a discussion of recent research highlights.
RESEARCH HIGHLIGHTS
Recent progress in overcoming efficiency limitations of individual components as well as challenges in the integration of the components into complete solar fuel generators will be presented. Several designs of integrated systems are being explored.
I. COUPLING OF NANO PVs TO METAL CATALYSTS AND SURFACES
Research teams explore nanoscale photovoltaic elements as building blocks of nano photoelectrochemical cells (nano PECs). Light absorbing/charge separating semiconductor elements prepared on the nanoscale offer unique advantages over bulk-sized materials, such as more facile manipulation of electronic properties for achieving efficient visible light absorption and band edge alignment with redox potentials of catalysts, or exploitation of extreme aspect ratios for the simultaneous optimization of light absorption and charge collection efficiencies. Moreover, certain alloys of special interest for solar applications can only by made on the nanometer scale. A critical issue is poor electrical contact between the PV element and a metal electrode or catalytic particle. We have developed liquid solution-based methods for generating very efficient contacts of Cd chalcogenide nanorods with metal clusters or electrode surfaces. Characterization of the contacts by electrical measurements using nanoscale electrodes reveals ohmic behavior and a current increase by 6 orders of magnitude. Monitoring of photogenerated electrons and holes by ultrafast optical laser pump-probe experiments shows very efficient transport of charges from a PV nanorod to metal catalyst [1].
II. NANOSTRUCTURED WATER OXIDATION CATALYSTS
A critical component of an artificial photosynthetic system is an efficient scalable catalyst for water oxidation. While robust catalysts like Ir oxide clusters essentially fulfill the kinetic, thermodynamic and stability requirements of an oxygen evolving catalyst, Ir is the least abundant element on earth and not suitable for use on a very large scale. In search of a metal oxide nanocatalyst made of an abundant element, we have found that nanostructured clusters of Co3O4 (spinel, bundle of parallel nanorods)
prepared in the pores of SBA-15 mesoporous silica support evolve oxygen efficiently from aqueous solution under mild conditions and modest overpotential [2]. Mass spectrometric monitoring of O2
evolution from aqueous suspension of the SBA-15/Co3O4 particles using visible light-generated
Ru+3(bpy)
3 species as oxidant gave a turnover frequency per Co oxide nanocluster of 1140 s-1. The rate
and size of this first nanometer-sized multi-electron catalyst made of abundant transition metal oxide lie in a range of values adequate for quantitative use of photons at maximum solar intensity.
III. Si/TiO
2CORE/SHELL NANOWIRE PHOTOCATALYST ARRAY
For developing integrated systems for visible light splitting of water into hydrogen and oxygen based on semiconductor nano PECs, a critical task is to make arrays of asymmetrically functionalized heterojunctions that afford separation of the products. Highly dense Si/TiO2 core/shell nanowire arrays with the
heterojunctions in defined orientation have been prepared in which the TiO2 shell is confined to one section of the
wire while the exposed Si core is decorated with Pt nanocluster catalysts for H2 generation [3]. Photocurrent
enhancement by a factor of 2.5 compared to planar Si/TiO2 structures is observed, which is attributed to their low reflectance and high surface area of the nanowire array.
IV. POLYNUCLEAR PHOTOCATALYTS IN NANOPOROUS SILICA SCAFFOLDS
To take advantage of the flexibility and precision by which light absorption, charge transport and catalytic properties can be controlled by discrete molecular structures, we are exploring an inorganic ‘molecular’ approach for building integrated artificial photosynthetic systems. Photocatalytic units anchored on silica nanopore surfaces consist of an oxo-bridged binuclear metal-to-metal charge-transfer chromophore (MMCT) serving as visible light electron pump, which is coupled to a multi-electron transfer catalyst. We have developed mild synthetic methods for assembling a variety of hetero-binuclear chromophores with high selectivity (e.g. TiOCoII, ZrOCuI, TiOMnII, TiOCrIII) [4,5]. When coupling the TiOCrIII unit to an Ir
oxide nanocluster inside the nanopores of MCM-41 silica support, water oxidation was observed upon irradiation of an aqueous suspension under visible light with good quantum efficiency [5,6]. In parallel work, we have demonstrated CO2 splitting to CO at a ZrOCrI MMCT chromophore of ZrCuI-MCM-41
sieve loaded with gaseous carbon dioxide [7].
References
[1] G. Dukovic, M.G. Merkle, J.H. Nelson, S.M. Hughes, and A.P. Alivisatos, Adv. Mater. 20 (2008), pp. 4306-4311.
[2] F. Jiao and H. Frei, Angew. Chem. Int. Ed. 49 (2009), p. 000 (Web release January 2009). [3] Y.J. Hwang, A. Boukai, and P.D. Yang, Nano Lett. 9 (2009), pp. 410-415.
[4] W. Lin and H. Frei, J. Phys. Chem. B 109 (2005), pp. 4929-4935.
[5] H. Han and H. Frei. J. Phys. Chem. C 112 (2008), pp. 16156-16159; 112 (2008), pp. 8391-8399. [6] R. Nakamura and H. Frei. J. Am. Chem. Soc. 128 (2006), pp. 10668-10669.
[7] W. Lin and H. Frei, J. Am. Chem. Soc. 127 (2005), pp. 1610-1611.
Biographical
Education: Dr.sc. (Physical Chemistry), ETH Zurich (1977)
Appointments, Awards: 1978-1981, Postdoctoral Fellow of the Swiss National Science Foundation, UC Berkeley, Chemistry Dept.; 1981-1984, Staff Scientist, Laboratory of Chemical Biodynamics; 1985-1990, Division Fellow and Principal Investigator, LBNL; 1990 – present, Senior Scientist; 1998-2007, Deputy Director, Physical Biosciences Division; 2007 – present, Deputy Director, Solar Energy Research Center;
Werner-Prize of the Swiss Chemical Society
Dye-Sensitized Solar Cells with Nanotechnologies
Liyuan Han
WPI Center for Materials Nanoarchitectnics, National Institute for Materials Science
1-2-1 Sengen Tsukuba, Ibaraki, 305-0047, Japan
Dye-sensitized solar cells (DSCs) have been widely investigated as a next-generation solar cell because of low manufacturing cost1). As shown in Fig. 1, DSCs are comprised of a nanocrystalline titanium dioxide (TiO
2)
electrode modified with a dye fabricated on a transparent conducting oxide (TCO), counterelectrode (CE), and an electrolyte solution with a dissolved iodide ion/tri-iodide ion redox couple between the electrodes. The mechanism of power generation in DSCs is a process whereby the dye on the nanocrystalline TiO2 is excited by
light, generating a fast electron transfer to the conduction band of the TiO2 electrode and further movement
toward the front electrodes. The oxidized dye is subsequently reduced by the electrolyte containing the iodide/triiodide redox couple, the formation of holes with movement toward the counter electrode through the electrolyte. The principles of DSCs are therefore different from those that govern conventional solar cells. They are, in fact, more similar to plant photosynthesis, as light absorption (dye) and carrier transportations in both TiO2 and electrolyte in DSCs occur separately. In comparison with silicon solar cells, detailed understanding of
DSCs mechanisms has been hindered by the complexity of the TiO2 film with its large surface area.
In this presentation, strategy for improving efficiency of DSCs was reported. Modeling of
equivalent circuit of DSCs, the method for improvement of shirt circuit density (Jsc), open circuit
voltage and fill factor were investigated.
To understand the mechanism of DSC, an internal resistance was studied by the electrochemical impedance spectroscopy and four internal resistance elements were observed2). In our analysis, an equivalent circuit of
DSCs (Fig. 2) was firstly proposed.3) The series resistance of DSCs is the sum of the internal resistance
elements related to the charge transfer processes at the Pt counter electrode (R1), ionic diffusion in the
electrolyte (R3), and the sheet resistance of TCO (Rh).The charge transportation at the TiO2/dye/electrolyte
interface was expressed as a diode because it is
The decrease of the series-internal resistance was studied based on the equivalent circuit of DSCs in order to improve of fill factor. It was found that R1 decreases with increase in roughness factor (RF)of Pt counter
electrode, which suggests that increase in the RF of the Pt counter electrode leads to an accelerated rate of I3
-reduction through the increased surface area of the counter electrode3).
Relationship between R3 and the thickness of the electrolyte layer defined as the distance between the TiO2
CE
I
3-TCO
I
-TiO
2Electrolyte
Dye
I
R
hR
shR
3C
1R
1C
3I
scFig. 2 Equivalent circuit of DSCs. R1, R3 and Rh are series resistance elements, Rsh is shunt resistance, C1 and C3 are capacitance element.
Fig. 3 Structure of the DSC.
electrode and the Pt counter electrode, and the dependence of Rh on the sheet resistance of the TCO were also
investigated. It was found that both R3 and Rh are proportional to the thickness of the electrolyte layer and the
sheet resistance of the TCO respectively.
For the purpose of improving Jsc, we attempted a use of haze factor to estimate the effect of light scattering of TiO2 electrodes. Fig. 3 shows
dependence of incident photon to current
conversion efficiency (IPCE) spectra on haze factor, which is varied in the range from 3% to 76%. IPCE is widely increased by the increase of haze of TiO2
film, especially in infrared region4). Jsc of 21
mA/cm2 was obtained using the haze of over 67%. A cell
with the series-internal resistance of 1.8 :cm2 and high
haze factor was fabricated. Current-voltage characteristics were measured by Research Center for Photovoltaic, National Institute of Advanced Industrial Science and Technology (AIST, Japan) using a metal mask and with an aperture area of 0.219 cm2 under standard AM 1.5
sunlight (100.0 mW/cm2). An overall conversion efficiency of 11.1% was achieved5) which is the highest
confirmed efficiency.
References (Times New Roman / 11 point / Boldface)
[1] B. O’Regan and M. Grätzel, Nature, 353, 737 (1991).
[2] L. Han, N. Koide, Y. Chiba and T. Mitate, Appl. Phys. Lett., 84, 2433 (2004).
[3] L. Han, N. Koide, Y. Chiba, A. Islam, R. Komiya, N. Fuke, A. Fukui and R. Yamanaka, Appl. Phys. Lett., 86, 213501 (2005).
[4] Y. Chiba, A. Islam, R. Komiya, N. Koide, and L. Han, Appl. Phys. Lett. 88, 223505-1 (2006).
[5] Y. Chiba, A. Islam, R. Komiya, N. Koide and L. Han, Jpn. J. Appl. Phys., 45, L638 (2006).
Dr. Han is a leader of next generation photovoltaics group, innovative materials engineering laboratory principal investigator, international center for materials nanoarchitectonics, National Institute for Materials Science (NIMS). He received a doctor’s degree from the University of Osaka Prefecture. His major is organic chemistry. He had studied dye-sensitized solar cells for 13 years at Sharp Corporation and moved to current position from June 2008.
0 10 20 30 40 50 60 70 80 90 100 400 500 600 700 800 900 1000 Wavelength (nm) IP C E (% ) Haze 76% Haze 60% Haze 53% Haze 36% Haze 3%
Fig. 3. Dependence of IPCE spectra on haze factor of TiO2 electrodes
－ － Haze 76% Haze 60% Haze 53% Haze 36% Haze 3%
Fig. 1: Issues for fuel cell materials R&D.
Nanostructured Alternative Materials for Fuel Cells:
Perspectives and case studies
Kazunari Sasaki
Kyushu University, Hydrogen Technology Research Center & Faculty of Engineering
Motooka 744, Nishi-ku, Fukuoka 819-0395, Japan
Case studies and perspectives are presented to consider possibilities / opportunities of nanostructuring to improve fuel cell performance, especially for the electrode
materials.
I. Introduction
Fuel cells are environmentally compatible promising energy technologies. More than 2000 stationary co-generation systems have been demonstrated in Japan, and mass production will be started this year. For automobile applications, considerable efforts have been made for the commercialization around 2015. In addition, alternative
power units e.g. for notebook-PC are under development as their possible portable applications. Materials development should be therefore oriented to solve technological issues in commercialization of these technologies. Longer durability and lower materials/system cost are essential, as well as improved properties of materials and devices (see Fig. 1).
II. Case studies for polymer electrolyte fuel cells
For polymer electrolyte fuel cells (PEFCs), nanostructuring is useful in tailoring electrocatalyst nano-particles, catalyst support, and electrocatalytic layers. Alloy electrocatalyst can be prepared using thermochemically-stable materials. For examples, Pt-Ti alloy electrocatalyst with a diameter of ca. 3-5 nm has been prepared with satisfactory electrochemical properties [1]
Since the improvement of noble metal utilization and gas transport is also important to optimize PEFC electrodes, carbon-nanofiber supported electrocatalysts could be applied to design nano-network in the electrocatalyst layers (see Fig. 2)[2]. In addition, steam activation procedure was applied in nanostructuring electrocatalyst particles impregnated “in” the surface of the catalyst support (see Fig. 3).
While carbon black is the state-of-the-art electrocatalyst support material, corrosion of the carbon-based support is one of the important technological issues which should be solved in order to improve long-term durability of the PEFCs. Oxidation-induced carbon support corrosion in cathode electrocatalysts occurs especially under high-potential conditions, associated with (i) start-up and shut-down, (ii) potential cycling, as well as (iii) open circuit preservation of the PEFCs. Alternative carbon-free electrocatalysts, using nanocrystalline SnO2
catalyst support (see Fig. 4), have been developed to fundamentally solve the carbon corrosion problem. Pt particles, distinguished as bright particles in Fig. 4, can be prepared with a diameter of ca. 3 nm,
Fuel Cell Materials R&D Improved Properties Catalytic/Electrochemical activity Higher conductivity Longer Durability
Stability under operational conditions Stability up to a decade
Lower Cost
Materials Components Systems
Fig. 4: FESEM micrograph of Pt/SnO2 electrocatalysts.
Fig. 2: FESEM micrograph of Pt/CNF electrocatalyst layer with network structures.
Fig. 3: Pt electrocatalyst particles impregnated “in” the surface of carbon nanofibers. Electrolyte Electrode catalyst layer 20 Pm 50 nm － 0 －
Fig. 5: FESEM micrograph of anode surface of nanostructured Ni0.95Mn0.05 / ScSZ, tolerant to
the H2S-containing SOFC fuels.
homogeneously distributed on the SnO2 support materials with a diameter of several tens nm. The
electrochemical measurements revealed the tolerance against cell voltage cycling [3].
III. Case studies for solid oxide fuel cells
For solid oxide fuel cells (SOFCs), the state-of-the-art co-generation system can exhibit a higher electric efficiency approaching 50%. Generally speaking, it becomes, however, much more difficult to tailor nanostructures which must be stable even at the SOFC operational temperatures between 600 and 1000oC at least up to several thousand
hours. As a stable nanostructured anode material, a composite electrode material consisting of Ni-MnO (see Fig. 5) has been developed to depress the grain growth of Ni catalysts at the operational temperature around 800oC. Longer durability than 1000 hours has been verified, showing a
degradation rate within a few % / 1000h even for H2S- containing
partially pre-reformed SOFC fuels [4].
Perspectives for fuel cell and hydrogen-related technologies will also be discussed.
References
[1] Y. Kawasoe, S. Tanaka, T. Kuroki, H. Kusaba, K. Ito, Y. Teraoka, and K. Sasaki, J. Electrochem. Soc., vol. 154(9) (2007), pp. B969-B975.
[2] K. Sasaki, K. Shinya, S. Tanaka, Y. Kawasoe, T. Kuroki, K. Takata, H. Kusaba, and Y. Teraoka, Mater. Res. Soc. Symp. Proc., vol. 835, (2005) pp. 241-246.
[3] A. Masao, S. Noda, F. Takasaki, K. Ito, and K. Sasaki, submitted.
[4] K. Sasaki, K. Haga, J. Yamamoto, and K. Dobuchi, Proc. 8th Europ. Solid Oxide Fuel Cell Forum, (2008) B1003.
Dr. Kazunari SASAKI was born in 1965. He received a Ph.D degree in 1993 from Swiss Federal Institute of Technology (ETH-Zürich), Switzerland. After spending 10 years in Europe, he became an Associate Professor of Interdisciplinary Graduate School of Engineering Sciences, Kyushu University in 1999. He became a Professor of Faculty of Engineering in 2005. He is now Director of the Hydrogen Technology Research Center, Kyushu University and a Deputy Director of the Research Center for Hydrogen Industrial Use and Storage (HYDROGENIUS), National Institute of Advanced Industrial Science and Technology. His research areas are materials and process research on solid oxide fuel cells and polymer electrolyte fuel cells. He is managing as one of the leaders of the Hydrogen and Fuel Cell Project in Kyushu University.
1987 B. Eng., Tokyo Institute of Technology 1989 M. Eng., Tokyo Institute of Technology
1990 Research associate, Swiss Federal Institute of Technology (ETH-Zürich), Switzerland 1993 Dr. sc. techn. ETH
1995 Visiting scientist (invited by the Max-Planck-Society), Max-Planck-Institute for Solid State Research, Stuttgart, Germany
1999 Associate professor, Kyushu University
2005-present Professor, Kyushu University, Faculty of Engineering
2006-present Director, Kyushu University, Hydrogen Technology Research Center
2006-present Deputy Director, AIST, Research Center for Hydrogen Industrial Use and Storage (HYDROGENIUS)
1 Pm
ENZYME-BASED BIONIC BATTERIES AND FUEL CELLS
1M. Togo,
1H. Kaji,
1,2T. Abe,
1,2M. Nishizawa
1
Department of Bioengineering and Robotics, Tohoku University
6-6-1, Aramaki-Aoba, Sendai 980-8579, Japan
2
JST-CREST
Sanbancho, Chiyoda-ku, Tokyo, 102-0075, Japan
Abstract
Electric power derived from dispersed ambient energy has attracted attention as ubiquitous portable power. A potential option of portable power source is biological fuel cells that use enzymes as the electrocatalysts to generate electricity from such biological fuels as alcohols and carbohydrates. The high reaction selectivity of enzymes would allow separator-free design and power generation from complex natural fuel solutions without purifications, that is, direct utilization of refreshments containing sugar and biological fluids such as blood. We have studied the enzyme anode for glucose oxidation composed of a bi-layer polymer membrane, the inner layer containing diaphorase (Dp) and the outer, glucose dehydrogenase (GDH). The Dp membrane was formed from a newly synthesized Vitamin K3-based mediator polymer. The enzyme cathode for oxygen
reduction can be prepared with bilirubin oxidase (BOD). The important advantage of the enzymatic fuel cells is the easy in miniaturization, and the structural design of the cells in microscale should directly improve the total performance of the cells. I will present here our recent researches on (1) microfluidic bionic cell, (2) semi-automatic air valve for series-connection, (3) relayed biofuel cells, and (4) needle-type biofuel cell.
I. ENZYME-BASED FUEL CELLS
The anode for glucose oxidation was prepared as enzymatic bilayer. The inner Dp membrane was formed on the Ketjenblack (KB; EC-600JD)-immobilized Pt electrode by cross-linking with the VK3-modified
poly-L-lysine (PLL-VK3). The mixture of GDH and PLL was over-coated on the PLL-VK3/Dp-coated KB
electrode. The oxygen cathode was the BOD-immobilized KB electrode. The thickness of both layers was ca. 1 um in dry. Fig. 1 shows the (a) illustration of the cell construction, (b) catalytic oxidation of glucose at the enzyme bilayer anode, and (c) LSV measured in a microfluidic biofuel cell under the flow of 0.3 mL min-1.
ᣞእ )NWEQUG %WTTGPV 1 Vitamin 䌋䋳 NADH #PQFG %CVJQFG &R )&* $1& e e ᣞእ )NWEQUG %WTTGPV 1 Vitamin 䌋䋳 Vitamin 䌋䋳 NADH #PQFG %CVJQFG &R )&* $1& e e
Fig. 1 (A) Schematic illustration of Enzymatic Glucose / Oxygen Fuel Cell. (B) Cyclic voltammograms for a KB/PLL-VK3/Dp/GDH-modified GC electrode in (a) a N2-saturated pH 7.0 phosphate-buffered electrolyte solution at
37 ºC, (b) with 20 mM NADH, (c) with 20 mM glucose, 1.0 mM NAD+, or (d) 30 mM glucose, 1.0 mM NAD+. For
(d), the electrolyte solution was stirred at 1000 rpm. (C) LSVs in a microfluidic cell (at a flow rate of 0.3 mL min-1)
for (a) anode and (b) cathode in N2-bubbled (···), air-saturated (ʊ), and O2-bubbled (---) glucose solutions.
The possible output voltage of single biofuel cell is practically lower than 1 V. Therefore, many applications require cell-stacking (series connection), which is however often troublesome due to short-circuiting of cells through ion-conductive fuel solution. The series-connection of biofuel cells requires a system for ionic isolation between each cell. Our strategy is based on the air-trapping at a superhydrophobic area prepared in the fluidic channel as each cell to be ionically isolated. We prepared lotus leaf-like micropillar array within a microchannel, as shown in Fig. 2. If this automatic air-valve system works as expected, users of this power device have never to introduce fuel solution to each separate chamber.
As for the electricity generation from biological fluids such as blood, a needle type enzymatic fuel cell has been developed. The enzyme-modified wire electrodes were inserted into the insulated needles, of which tip was coated by MPC polymer for protection of clot formation.
References
[1] F. Sato, M. Togo, MK. Islam, T. Matsue, J. Kosuge, N. Fukasaku, S. Kurosawa and M. Nishizawa,
Electrochem. Commun. 7 (2005), p.643.
[2] M. Togo, A. Takamura, T. Asai, H. Kaji and M. Nishizawa, Electrochim. Acta, 52 (2007), p.4669.
[3] M. Togo, A. Takamura, T. Asai, H. Kaji and M. Nishizawa, J. Power Sources, 178 (2008), p.53.
Matsuhiko Nishizawa
E-mail: [email protected]
Home page: www.biomems.mech.tohoku.ac.jp
1994: Ph. D. Department of Applied Chemistry, Tohoku University 1994: Research Fellow of the Japan Society for the Promotion of Science 1995: Research Assistant / Osaka University
1997: Research Assistant - Associate Professor / Tohoku University 2003: Professor, Graduate School Engineering, Tohoku University
Fig. 2 (A) Top view and (B) cross-sectional view of a series-connected biofuel cells on a fluidic chip. Inset shows close up top view of valve-area.
Fig. 3 Needle-Type Enzymatic Fuel Cell.
Insulated Needle Enzyme KB MPC 0 1 2 3 4 5 0 0.1 0.2 0.3 0.4 0.5 0 0.1 0.2 0.3 0.4 I / P A m m -2 P / P W m m -2 Voltage / V Insulated Needle Enzyme KB MPC 0 1 2 3 4 5 0 0.1 0.2 0.3 0.4 0.5 0 0.1 0.2 0.3 0.4 I / P A m m -2 P / P W m m -2 Voltage / V Insulated Needle Enzyme KB MPC 0 1 2 3 4 5 0 0.1 0.2 0.3 0.4 0.5 0 0.1 0.2 0.3 0.4 I / P A m m -2 P / P W m m -2 Voltage / V － －
【Session2】
Transport and Storage of Energy
"Nanotechnology for Energy and Environment in Germany"
「ドイツにおける環境・エネルギーに対応したナノテクノロジー」
Dr. Karl-Heinz Haas
(Fraunhofer-Institut für Silicatforschung, Germany)
"Development of Photocatalytic System for Hydrogen Production
from Water with Solar Energy"
「太陽光と水から水素を生成する光触媒システムの開発」
Prof. Kazunari Domen
(The University of Tokyo, Japan)
堂免一成
（東京大学）
"Chemistry and Application of Porous Coordination Polymers
「新しい多孔性金属錯体材料の化学と応用」
Prof. Susumu Kitagawa
(Kyoto University, Japan)
北川 進
（京都大学）
”Iron-Based Superconductors: Recent Advances”
「新しい超電導物質 : 鉄系高温超電導」
Prof. Hideo Hosono
(Tokyo Institute of Technology, Japan)
細野秀雄
（東京工業大学）
Nanotechnology for Energy and Environment
in Germany
Dr. Karl-Heinz Haas
Fraunhofer Nanotechnology Alliance
Fraunhofer Institut für Silicatforschung, Neunerplatz 2
97080 Wuerzburg Germany, [email protected].
The aspects of nanotechnologies in the field of energy and environment became more and more important in recent years [1-3]. Nanomaterials can help to solve some of the main issues of our modern societies concerning the use of energy and raw materials in a sustainable manner (Clean-Tech).
The industrial relevant fields for energy and environment aspects cover a wide range from automotive, construction, production, optics and electronics and many more.
Nanotechnology in Germany is supported since more than 15 years by various governmental support programms. In 2007 the German Ministry of Science and Technology supports Nanotechnology related projects with more than 160 Mio Euros and additionally various Institutes directly (institutional funding) with nearly 180 Mio Euros [4]. In recent years interesting innovation alliances led by industry have also been formed with the support of the government especially in energy related areas of:
- organic photovoltaics (2008-2012) - Lithium-ion batteries (2008-2012) - OLEDs (2006-2011)
- carbon nanotubes (2008-2012)
In 2008 the German government published a masterplan for environmental technologies where various nanotechnology related topics have been adressed [5]. Sustainability issues of nanotechnologies are taken care of in Germany f.e. within the FONA forums [6].
Relevant application areas for nanotechnologies in the fields of energy and environment are: - solar energy: Increasing efficiency, new types of flexible solar cells
- hydrogen storage materials: Nanoporous materials, metal oxide frameworks MOF - thermal energy: heat storage by phase change materials, thermoelectrics, gas turbines - electrical energy storage and conversion (batteries, fuel cells, supercapacitors)
- cleaning of air, water and soil using nanomaterials (coatings, particles, membranes), nanosensors - new highly efficient heat insulating materials (aerogels, nanofoams)
- transport: automotive especially lightweight composites, efficient catalysts - efficient displays and lighting
Environmental aspects of nanotechnologies are twofold: The fate of nanomaterials in the environment (risk analysis) and the use of nanotechnologies for remediation of environmental problems. Various european and german national projects are taking care of the issues of toxicology [7], life cycle investigations of nanoparticles, work place safety etc.
Another very important topic is to make nanotechnologies useful for classical production processes in order to save energy and to use materials more efficiently (Nano for production f.e. wear protection for machining tools).
This contribution will show some industrially implemented examples mainly from Germany, some of them developed by the Fraunhofer Society [8] together with industrial partners. The Fraunhofer society is a private non-profit organization devoted to contract based application oriented research.
References
[1] “Nanotechnology helps to save the worlds energy problems” 1st EuroNanoForum Report August 2003
www.nanoforum.org
[2] “Nanotech impact on energy and environmental technologies” Lux Resarch June 2007 www.luxresearch.com
[3] W. Luther “Application of Nanotechnologies in the Energy Sector” August 2008 www.hessen-nanotech.de [4] www.bmbf.de/en/nanotechnologie.php
[5] Masterplan “Environmental Technologies” Federal German Government 5.11.2008, www.bmbf.de [6] Research for Sustainability www.fona.de/en/index.php
[7] Nanocare-Project BMBF www.nanopartikel.info [8] www.nano.fraunhofer.de www.energie.fraunhofer.de
Dr. Karl-Heinz Haas Deputy Director
Fraunhofer-Institut für Silicatforschung, Fraunhofer ISC
Neunerplatz 2, 97082 Wuerzburg – Germany Phone: ++49-931-4100-500 FAX: ++49-931-4100-559 e-mail: [email protected] www.nano.fraunhofer.de
Personal data:
Born May 4, 1955 Maulbronn/Enzkreis (D) Education:
Ph. D. Physical Chemistry - Electrochemistry, University of Karlsruhe, 1983
M. S. Diploma-Thesis, University of Karlsruhe, 1980 Professional Experiences:
since April, 2008: Head of business unit
“Construction and environment” at Fraunhofer ISC since April, 2004: Spokesman Alliance
Nanotechnology of Fraunhofer-Society since April, 2002: Deputy Director of
Fraunhofer-Institut für Silicatforschung, Würzburg August 1, 1995 – March 30, 2002: Head of Hybrid Polymer Department at Fraunhofer ISC
April 1, 1988 – July 31, 1995: R&D Scientist and Project Leader at Central Polymer Research BASF AG, Ludwigshafen and Tsukuba/Japan working on hybrid polymers (nanoreinforcement of
thermoplastics) and functional polymers for 3rd order nonlinear optics
Jan 1, 1984 – March 30, 1998: R&D Scientist, Project and Group Leader at Fraunhofer ISC in the field of hybrid polymers and sol-gel-processing
Development of Photocatalytic Systems for Hydrogen Production
from Water with Solar Energy
Kazunari Domen
Chemical System Engineering, The University of Tokyo
7-3-1 Hongo, Bunkyo-ku, Tokyo 103-8656, Japan
Overall water splitting into hydrogen and oxygen has been considered as one of the most ideal
reactions to generate clean and recyclable H
2as an energy carrier in future.
Although there are several different types of approaches to achieve the reaction, overall water
splitting on heterogeneous photocatalysts is one of the potential candidates especially from the
view point of large scale application. Key issues to establish an efficient photocatalytic reaction
system using solar energy is to find suitable photocatalytic materials under visible light and
proper modification methods for efficient hydrogen and oxygen formation.
Many photocatalysts for overall water splitting under UV light have already been established.
To efficiently utilize solar energy, of course, visible light driven photocatalysts have to be
developed. At present, however, such photocatalytic systems are still very limited and various
kinds of attempts are being pursued by many researchers.
Recently, we have found that some typical elements containing oxynitride photocatalysts such
as (Ga
xZn
1-x)(N
xO
1-x) actually work under visible light irradiation to accomplish overall water
splitting
1,2. This was the first example that accomplished overall water splitting reaction under
visible light irradiation on a photocatalyst with a band gap less than 3 eV. (Ga
xZn
1-x)(N
xO
1-x) is a
solid solution of GaN and ZnO and has been proved to be stable materials during the reaction
with proper modification.
To further enhance the activity, hydrogen production sites with nano-scale core-shell structure
consisting of Rh metal and Cr
2O
3were constructed on the photocatalysts
3. On this sites, proton
and H
2can penetrate the Cr
2O
3layer without O
2diffusion. Therefore, the reverse reaction is
effectively prevented on this photocatalyst, which is essential to achieve high activity of energy
conversion reaction.
In addition to the above system, two photon excitation systems which are available for a wider
range of visible light region will be briefly introduced.
References
[1] K. Maeda, K. Teramura, D. Lu, T. Takata, N. Saito, Y. Inoue and K. Domen, Nature,
440 (2006), p.295.
[2] K. Maeda, K. Domen, J. Phys. Chem.C, 111 (2007), pp.7851-7861.
－ －[3 ]K. Maeda, K. Teramura, D. Lu, N. Saito, Y. Inoue, K. Domen, Angew. Chem. Int. Ed., 45
(2006), pp.7806-7809.
Curriculum Vitae
Kazunari DOMEN
Professor, Department of Chemical System Engineering,
School of Engineering, the University of Tokyo
Doctor of Science
Major Fields:
Physical Chemistry, Heterogeneous Catalysis, Photocatalysis,
Surface Chemistry, Functional Materials
Research Projects:
Development of Photocatalysts for Water Splitting
Study on Heterogeneous Catalysis Reactions by Infrared Spectroscopy
Surface Reaction Dynamics by Nonlinear Laser Spectroscopy
Development of New Functional Materials for Catalysis
Address:
Department of Chemical System Engineering, School of Engineering, The
University of Tokyo
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
(room 715, 7th floor, Factory of Engineering building 5, Hongo campus)
Tel: +81-3-5841-1148 Fax: +81-3-5841-8838
E-mail: [email protected]
Lab URL: http://www.domen.t.u-tokyo.ac.jp/index_framepage.html
Date of birth: September 24, 1953
Biography:
Graduated from the University of Tokyo in 1976 .
Received a Ph.D. in Science from the University of Tokyo in 1982.
Became Associate Researcher at Tokyo Institute of Technology in 1982 .
Promoted to Associate Professor in 1990 . Professor in 1996 .
Became Professor at The University of Tokyo in 2004 .
(Visiting Scientist at IBM Almaden Research Center from 1985 to 1986.)
Awards:
Encouragement Prize, Catalysis Society of Japan, 1990;
Catalyst Preparation Awards, 1991
Catalysis Society of Japan Awards 2007
－ －Figure 1 Various Functions of PCPs
Chemistry and Application of Porous Coordination Polymers
Susumu Kitagawa1,2,3ERATO Integrated Pores Project, Japan Science and Technology Agency (JST), Kyoto Research Park Bldg 3, 600-8815, Institute for Integrated Cell-Material Sciences,
Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Nishikyo-ku,Kyoto, 615-8510
The recent advent of porous coordination polymers (PCPs) or metal-organic frameworks (MOFs), as new functional microporous adsorbents, have attracted the attention of chemists due to scientific interest in the creation of unprecedented regular nano-sized spaces and in the finding of novel phenomena, as well as commercial interest in their application for storage, for separation and in heterogeneous catalysis[1]. Currently PCPs attract much attention among porous materials, and consequently, the chemistry of PCPs has developed markedly.
G
One of the advantages of PCPs is designability, which provides a variety of surface properties
based on organic ligands with functional groups. This prominent feature leads us to expect that PCP
will show a high adsorption capability for specific molecules. However, few useful concepts and
strategies for specific adsorption of smaller molecules have been established to date. Here, we have
found superb sorption of C
2H
2molecules on the functionalized surface of an PCP and show an
enhanced “confinement effect”, applicable to a highly stable, selective adsorption system.
2We have
succeeded in obtaining interesting array structures of benzene and O
2molecules and observed their
unusual properties in the nanochannel.
3In addition to this confinement phenomena, we have found
flexible porous frameworks,
4which respond to specific guests, common in PCPs but dissimilar to the
conventional porous materials.
1Recently,
we have utilized the regular and tunable
nanochannels of PCPs for fields of
polymerization, which allows controlled
living radical polymerization as well as
stereoregulated
polymerization
of
substituted acetylenes.
5References
[1] S. Kitagawa, et.al., Angew. Chem. Int.
Ed,, 2004, 43, 2334(Reviews). [2]R.
Matsuda, et.al., Nature, 2005, 436, 238.
[3]
S.Kitagawa,
Nature,
2006,441,584.(News
and
Views).
[4]T.P.Maji,
et.al.
Nature
Mater.
2007,6,142.
[5]T.Uemura,
et.al.,Chem.Asian J. 2006, 1,36-44.
Susumu Kitagawa
Institute for Integrated Cell-Material Sciences
Department of Synthetic Chemistry and Biological Chemistry,
Kyoto University
Katsura, Nishikyo-ku, Kyoto, 615-8510, Japan
TEL: +81-75-383-2733
FAX: +81-75-383-2732
e-mail: [email protected]
EDUCATION AND POSITIONS
2007 -
Deputy Director, Institute for Integrated Cell-Material Sciences,
KyotoUniversity
1998-
Professor, Kyoto University, Kyoto, Japan
Department of Synthetic Chemistry & Biological Chemistry
1992-1998
Professor, Tokyo Metropolitan University, Hachiouji, Tokyo, Japan
Department of Chemistry
1988-1992
Associate Professor, Kinki University, Higashi-Osaka, Japan
Department of Chemistry
1986-1987
Visiting Scientist, Department of Chemsitry, Texas A & M University
F.A.Cotton Laboratory
1983-1988
Lecturer, Kinki University, Higashi-Osaka, Japan,
Department of Chemistry
1979-1983
Assistant Professor, Kinki University, Higashi-Osaka, Japan
Department of Chemistry
1975-1979
Kyoto University, Kyoto, Japan
Graduate School, Hydrocarbon Chemistry, PhD degree
Thesis Supervisors: Professor Isao Morishima
1971-1974
Kyoto University, Kyoto, Japan
Undergraduate course, Hydrocarbon Chemistry
PROFESSIONAL RECOGNITION
2008 The Chemical Society of Japan (CSJ) Award
2008 Alexander von Humbolt Research Award
2007 – 2013 Leader of ERATO program of JST, “Kitagawa Integrated Pores”
2007 Earl L. Muetterties Memorial Lectureship Award (University of California,
Berkeley, USA)
2004 -2007
Leader of MEXT Grant; Priority Area, “Chemistry of Coordination
Space”
2007 The Japan Society of Coordination Chemistry Award for 2007
2001
The Chemical Society of Japan Award for Creative Work for 2001
1990
Young Scholars Lecture Series Award, the Chemical Society of Japan.
CURRENT PROFESSIONAL SERVICES
Associate editor
2009 - Chem.Asian J.
2008- CrystEngComm
Advisory Board Member
2008- Inorganic Chemistry
2006 - Chemical Communications, Chemistry, Asian Journal, Chemistry of Materials,
Inorganica Chimica Acta, Coordination Chemistry Reviews, CrystEngComm, European
Journal of Inorganic Chemistry
2004 - Chemistry Letters, Topic Editor for Crystal Growth & Design
2001 - 2002 Vice-president, Japanese Society of Coordination Chemistry
IRON -BASEDE SUPERCONDUCTORS: RECENT ADVANCES
Hideo HOSONO
Frontier Research Center & Materials and Structures Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku,
Yokohama 226-8503, JAPAN
Superconducting transition in a layered ZrCuSiAs-type crystal was first reported for LaFePO in 2006[1] and subsequent a similar Tc was found for LaNiPO with the same crystal structure in 2007. However, Tc of these compounds reminded low (~4K). On February 23, 2008, our paper reporting a layered compound in LaFeAsO1-xFx(x=0.1) exhibiting a superconducting critical temperature Tc (mid-point) =
26K was published on-line in the Journal of the American Chemical Society as a communication [3]. In this presentation I talk the background of this discovery and the subsequent advance in materials. The following points have been clarified to date; (1) Iron-based superconductors reported are 4-types crystal structures, the 1111[3], 122[4], 111[5], and 11 [6] type. All the high Tc iron-based superconductors contain a Fe square lattice and the Fe 3d orbitals dominate the Fermi-level. (2) The occurrence of a crystallographic transition accompanying anti-ferromagnetic to paramagnetic state in the parent compound is a requisite for a high Tc. (3) There exist a vast number of materials containing
the Fe square lattice. (4). A partial substitution of Fe with other transition metal is possible without serious reduction of Tc. Role of the dopant 3d-transition metal ions is totally different between the 1111 and 11 phases (4) A new insulating layer AEF (AE=Ca, Sr)was found to be effective in the 1111 phase[7]. (5) High pressure synthesis was effective to obtain the 1111 phases with higher Tc, (6) Epitaxial thin films exhibiting a Tc almost the same as that in the bulk were fabricated for CaFeAsO:Co[8]. Epitaxial thin films were reported on LaFeAsO[9].
[1]Y.Kamihara et al. JACS, 28 (2006)10012, [2]T.Watanabe et al.Inorg.Chem,46(2007) 7719, [3]Y.Kamihara et al. J.Am.Chem.Soc.130(2008)3296., [4]M.Rotter et al. PRL, 101 (2008) 107006, [5]J.H.Tapp et al. PRB,78(2008)060505 [6]F.C.Hsu et al. PNAS,105(2008)14262., [7]S.Matsuishi et al. JACS 130(2008)14428 [8]H.Hiramatsu et al. Appl.Phys.Express 1(2008)101702, [9] H.Hiramatsu et al. APL. 93(2008) 162504.
䋱䋱䋱䋱䋭
LnO
䋱䋱䋱䋱䋭
AeF
122
111
䋱䋱
FIG.1 Crystal Structure Variation. Ae:alkaline earth, Ln: lanthanoid
Fe Pn Ln Ln-O layer Fe-Pn layer O Ae or Eu,K Fe As A Fe As A Fe As Fe Ch Ae As Fe F (a) (b) (c) (d) (e)
䋱䋱䋱䋱䋭
LnO
䋱䋱䋱䋱䋭
AeF
122
111
䋱䋱
FIG.1 Crystal Structure Variation. Ae:alkaline earth, Ln: lanthanoid
Fe Pn Ln Ln-O layer Fe-Pn layer O Ae or Eu,K Fe As A Fe As A Fe As Fe Ch Ae As Fe F (a) (b) (c) (d) (e) Fe Pn Ln Ln-O layer Fe-Pn layer O Ae or Eu,K Fe As A Fe As A Fe As Fe Ch Ae As Fe F (a) (b) (c) (d) (e) － －
Fi
FIG. 2. Progress in Fe-based superconductors. Upper is for 1111 type and the bottom for
122,111,11-type materials
Progress in superconductors with square Fe lattice
䌋
䌋--doped doped AAFeFe22AsAs22
Other structures with
Other structures with
Fe
Fe--square latticesquare lattice
RE substitution RE substitution 2.4 K 2.4 K 㱍 㱍--FeSeFeSe 200 20077 Ba Ba11--xxKKxxFeFe22AsAs22 55 K 55 K T Tcc(K)(K) 13 13 41~43 K 41~43 K Ce CeFeAsOFeAsO11--xxFFxx SmFeAsO SmFeAsO11--xxFFxx 43 K 43 K LaFeAsO LaFeAsO11--xxFFxx ( (under HPunder HP)) 38 K 38 K Sm SmFeAsOFeAsO11--xxFFxx 1 1/9/9 5 5/29/29 Date Date (Received) (Received) 25 25 4 4/4/4 BaNi BaNi22PP22 ~4 K ~4 K 55 K 55 K Sm(Nd)FeAsO Sm(Nd)FeAsO11--xx 16 16 Li Li1-1-xxFeAsFeAs 18 K 18 K 㱍
㱍--FeSeFeSe28 K28 K((under HPunder HP))
8 K 8 K 30 30 1515 2828 7 7/4/4 BaFe BaFe22--xxCoCoxxAsAs22 22 K 22 K 6 6/6/6 Sr Sr11--xxKKxxFeFe22AsAs22 37 K 37 K 14 K 14 K
New doping approach
New doping approach
LaFe
LaFe11--xxCoCoxxAsOAsO
26 K 26 K 200 20088 4 K 4 K LaFePO LaFePO 2 2/26/26 33/18/18 LaNiAsO LaNiAsO Fe Fe--oxypnictideoxypnictide superconductors superconductors LaFe LaFeAsAsOO11--xxFFxx 200 20066 14 14 0 䌅䌰䌩䌴䌡䌸䌩䌡䌬 䌅䌰䌩䌴䌡䌸䌩䌡䌬 䌆䌩䌬䌭䌆䌩䌬䌭 8/11 14 Tc
Progress in superconductors with square Fe lattice
䌋
䌋--doped doped AAFeFe22AsAs22
䌋
䌋--doped doped AAFeFe22AsAs22
Other structures with
Other structures with
Fe
Fe--square latticesquare lattice
RE substitution RE substitution 2.4 K 2.4 K 㱍 㱍--FeSeFeSe 200 20077 Ba Ba11--xxKKxxFeFe22AsAs22 55 K 55 K T Tcc(K)(K) 13 13 41~43 K 41~43 K Ce CeFeAsOFeAsO11--xxFFxx SmFeAsO SmFeAsO11--xxFFxx 43 K 43 K LaFeAsO LaFeAsO11--xxFFxx ( (under HPunder HP)) 38 K 38 K Sm SmFeAsOFeAsO11--xxFFxx 1 1/9/9 5 5/29/29 Date Date (Received) (Received) 25 25 4 4/4/4 BaNi BaNi22PP22 ~4 K ~4 K 55 K 55 K Sm(Nd)FeAsO Sm(Nd)FeAsO11--xx 16 16 Li Li1-1-xxFeAsFeAs 18 K 18 K 㱍
㱍--FeSeFeSe28 K28 K((under HPunder HP))
8 K 8 K 30 30 1515 2828 7 7/4/4 BaFe BaFe22--xxCoCoxxAsAs22 22 K 22 K 6 6/6/6 Sr Sr11--xxKKxxFeFe22AsAs22 37 K 37 K 14 K 14 K
New doping approach
New doping approach
LaFe
LaFe11--xxCoCoxxAsOAsO
26 K 26 K 200 20088 4 K 4 K LaFePO LaFePO 2 2/26/26 33/18/18 LaNiAsO LaNiAsO Fe Fe--oxypnictideoxypnictide superconductors superconductors LaFe LaFeAsAsOO11--xxFFxx 200 20066 14 14 0 䌅䌰䌩䌴䌡䌸䌩䌡䌬 䌅䌰䌩䌴䌡䌸䌩䌡䌬 䌆䌩䌬䌭䌆䌩䌬䌭 8/11 14 Tc
