3rd CCS‐CSJ, Young Chemists ForumEffective Utilization of Elements and its Chemical ApplicationsDate: March 24th (SUN) 9:00‐17:10
Venue: Room S9(CO‐LEARNING HOUSE II C601)
Ritsumeikan University, Biwako‐kusatsu Campus(Shiga, Japan)
Hosted by The Chemical Society of Japan (CSJ)
Co‐hosted by Chinese Chemical Society (CCS)■9:00‐09:10 Opening Remarks from CSJ
(I)
L‐1
L‐2
L‐3
L‐4

Bio‐related System and Asymmetric Synthesis□Chair:ShouFei Zhu
9:10‐9:35
Sanzhong Luo(Institute of Chemistry, CAS)
page1
“Asymmetric Doubly Covalent Catalysis with Chiral In(III)Phosphoric Acid Binary Catalyst”
9:35‐10:00
Lei Liu(Tsinghua University)
page3“Studies on Protein Chemical Synthesis”
10:00‐10:25
Hideki Hashimoto (Okayama University)
page5“Structural Analysis of Nanometric Amorphous Iron Oxide Produced by
Iron‐oxidizing Bacterium, Leptothrix ochracea”
10:25‐10:50
Nanfeng Zheng(Xiamen University)
page7“Multilevel Structure Control of Metal Nanocrystals for Catalysis and Bioapplications”■10:50‐11:00 Coffee Break

(II)
L‐5
L‐6
L‐7

Carbon Material: Synthesis, Application, Simulation□Chair:Sanzhong Luo
11:00‐11:25
Hayato Tsuji(The University of Tokyo)
page9“Novel Carbon Materials toward Efficient Photovoltaics
Carbon‐bridged Phenylenevinylenes and Their Application to Dye‐sensitized Solar Cells”
11:25‐11:50
Wen‐Xiong Zhang (Peking University)
page11“Mechanism‐directed Organic and Organometallic Chemistry of Carbodiimides”
11:50‐12:15
Ryotaro Arita(The University of Tokyo)
page13“Magneto‐orbital Effect without Spin
Orbit Interactions in a Noncentrosymmetric Zeolite‐templated Carbon Structure”■12:15‐13:55 Lunch break

(III)
L‐8
L‐9
L‐10
L‐11

Homogeneous and Heterogeneous Catalysis□Chair: Hayato Tsuji
13:55‐14:20
Shou‐Fei Zhu(Nankai University)
page15“Iron‐catalyzed Carbene Transfer Reactions”
14:20‐14:45
Aiwen Lei
(Wuhan University)
page17“Oxidative Coupling: Chemistry between Two "Nucleophiles"”
14:45‐15:10
Qilong Shen
(Shanghai Inst. of Organic Chemistry, CAS) page19“From Trifluoromethylation to Trifluoromethylthiolation:
Development of New Trifluoromethylthiolated Hypervalent Iodine Reagent”
15:10‐15:35
Takeshi Fujita(Tohoku University)
page21“Catalytic Origins of Nanoporous Metal”■15:35‐15:45 Coffee Break

(IV)
L‐12
L‐13
L‐14

Coordination and Inorganic Chemistry□Chair: Takeshi Fujita
15:45‐16:10
Katsuro Hayashi (Tokyo Institute of Technology)“Refractory Oxides as Novel Electronics and Ionics Materials”
16:10‐16:35
Liang Zhao
(Tsinghua University)“Macrocycle‐directed Metal Cluster‐centered Coordination Self‐assembly”
16:35‐17:00
Yoshiaki Nakamura(Osaka University)“Si‐based Epitaxial Nanodots for Thermoelectric Material”

page23
page25
page27

Welcome Address
Dear Colleagues
Welcome to the 3rd CCS-CSJ Young Chemists Forum, heldat the same venue as the 93rd CSJ Annual Meeting, Ritsumeikan
University, Biwako-Kusatsu Campus, Shiga Prefecture located by
the shore of Lake Biwa, under the co-sponsorship of the Chemical
Society of Japan (CSJ) and the Chinese Chemical Society (CCS).
This series of bilateral meetings started as a result of aninternational cooperation agreement between CCS and CSJ
signed on March 28, 2009 during the CSJ 89th Annual Meeting.
At that time, the leadership of both societies had mutual concernsthat opportunities to communicate between younger chemists in
China and Japan are much less than those of senior chemists, andagreed that we should in principle provide them with meaningful
opportunities to meet face to face. After considerable discussion, we finally agreed a basic
structure. It was decided that the forum should be held periodically, for example during
annual meetings, and high-level scientists under the age of 45 should be invited.
The first event was held at Xiamen University in June, 2010, followed by the second in
April, 2012 at Sichuan University with the themes “Low Dimension Nano Carbon Materials”
and “Electrochemical Energy Conversion and Storage” respectively at the CCS Annual
Meetings.
The second was originally planned to be held at the CSJ 91st Annual Meeting late March2011 at Kanagawa University, which the CSJ was expected to host for the first time, but
unfortunately, it had to be cancelled because of the March 11 natural disasters. In accordancewith the original plan the forum will be held at this 93rd Annual Meeting with the theme“Effective Utilization of Elements and Chemical Applications”.
I would like to thank the symposium chairs Prof. Sanzhong Luo, the Chinese Academyof Science and Prof. Hayato Tsuji, The University of Tokyo, and CCS Executives Prof.
Zhongfan Liu, Beijing University and Prof. Zhigang Shuai, Tsinghua University as well as CSJ
Executive Director Mr. Nobuyuki Kawashima, for their great efforts to make this symposium
possible.
For this symposium sixteen distinguished chemists, nine from China and seven fromJapan, will present their research progress and exchange ideas for further development
under the above-mentioned theme. Effective utilization of elements is effectively more of a
global than local issue for sustainable development worldwide, and I believe that basic
science will play an important role. It is my hope that this bilateral symposium willcontribute greatly not only to the rapid development of this field but also to development ofapplications. I also have great expectations that all of the attendants will strengthen theirfriendships and find new colleagues throughout the symposium for further collaboration.
Kohei Tamao

President
The Chemical Society of Japan

Welcome AddressOn behalf of the Chinese Chemical Society,
I would like to express my sincere
greetings to all of the participants of the 3rd
China-Japan Young Chemist Forum.

C

hinese Chemical Society has a long
history of co-operation and exchange with
Chemical Society of Japan. In recent years therelations between our two societies havebecome closer than ever before with more
frequent bilateral exchanges.

As the best example, the China-Japan
Young Chemist Forum provides an important platform for young
chemists from both sides to exchange ideas and collaborate on the variety
of topics. After two meetings successfully held in 2010 and 2012, we arevery glad to send a delegation consisting of our outstanding young
chemists to visit Japan and meet with outstanding Japanese youth for the
first time.

We do believe that through the forum these young chemists will not
only spark on research ideas, but also make more precious friends
for their chemistry career.

Thank the organizing committee for their excellent work. Wish successof the forum and wish all of the participants happy and healthy.

Jiannian Yao, President
The Chinese Chemical Society

1

3rd CCS-CSJ, Young Chemists Forum

Sanzhong Luo
Professor of Chemistry
Key Laboratory of Molecular Recognition and Function,
Institute of Chemistry, Chinese Academy of Sciences (ICCAS)
Address: 2, North No. 1 Str. Zhongguancun, Beijing, China, 100190
Tel & Fax: (+86)-10-6255-4446
E-mail: luosz@iccas.ac.cn

 Educational Background



1999
2002



2005

B. Sc., Dept. of Chemistry, Zhengzhou University
M. Sc., Dept. of Chemistry, Nankai University(supervisor: Prof. Jin-Pei Cheng)
Ph.D, Institute of Chemistry & Ohio State University(supervisor: Prof. Jin-Pei Cheng & Peng G. Wang)

 Professional Career





2005
2008
2009
2011

Assistant Professor, ICCASAssociate Professor, ICCASCAS visiting scholar, Stanford University (Prof. B. M. Trost)
Professor, ICCAS Research Interests
Our primary research goal is to invent and develop novel enantioselective catalysts that enabletransformations with fundamental synthetic interests and broad utility. We’re particularly interested in
the development of viable small molecular catalysts that operate through novel activation modes using
bio-inspired principles and strategies.

 Awards







2011
2011
2010
2009
2008
2007

Thieme Journal Award
Asia Core Program Lectureship
National Science Fund for Distinguished Young Scholar
Lu Jiaxi Young Scientist Award of the Chinese Academy of Science
Young Chemist Award of the Chinese Chemical Society
Rising Star of Science and Technology Research in Beijing Recent Publications
1.
2.

3.

4.

“Chiral Primary Amine Catalyzed Enantioselective Protonation via an Enamine Intermediate” Fu,
N. K.; Zhang, L.; Li, J. Y.; Luo, S. Z.*, Cheng, J.-P. Angew. Chem. Int. Ed. 2011, 50, 11451.
“Asymmetric Binary Acid Catalysis: A Regioselectivity Switch between Enantioselective 1,2- and
1,4-Addition through Different Counteranions of In (III)” Lv, J.; Zhang, L.; Zhou, Y.; Nie, Z.; Luo,S. Z.; Cheng, J.-P. Angew. Chem. Int. Ed. 2011, 50, 6610.
“Asymmetric Supramolecular Primary Amine Catalysis in Aqueous Buffer: Connections of
Selective Recognition and Asymmetric Catalysis” Hu, S.; Li, J.; Jiang, H.; Pan, J.; Luo, S. Z.*,
Cheng, J.-P.* J. Am. Chem. Soc. 2010, 132, 7216.
“A Simple Primary-Tertiary-Bronsted Acid Catalyst for Asymmetric Direct Aldol Reactions ofLinear Aliphatic Ketones” Luo, S. Z.;* Xu, H.; Li, J. Y.; Zhang, L.; Cheng, J.-P.* J. Am. Chem.
Soc. 2007, 129, 3074.

Effective Utilization of Elements and its Chemical Applications

L-1
Asymmetric Doubly Covalent Catalysis with Chiral
In(III)Phosphoric Acid Binary Catalyst
Sanzhong Luo
Beijing National Laboratory for Molecular Sciences (BNLMS),CAS Key Laboratory of Molecular Recognition and Function,
Institute of Chemistry, CAS, Beijing 100190, P. R. Chinaluosz@iccas.ac.cn

Though catalysis and transformations with simple olefins have been extensively
explored, catalytic activation modes with simple olefin are rather limited. We present
here a double-covalent activation of simple olefins with both the metal and ligand(phosphoric acid) covalently bonded to a single double bond. This distinctive activation
mode enables catalytic enantioselective [4+2] cycloaddition of simple olefins.

2

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3rd CCS-CSJ, Young Chemists Forum

Lei Liu
Professor of Chemistry
Address:Department of Chemistry, Tsinghua University
Tel: (+86)-10-62780027
E-mail: lliu@mail.tsinghua.edu.cn

 Educational Background




1999
2004

B.Sc., University of Science and Technology of China
PhD, Columbia University(supervisor: Prof. R. Breslow)
2004-2007 Research Associate, Scripps Research Institute(supervisor: Prof. C.-H. Wong) Proffesional Career

2007

Professor, Tsinghua University

 Research Interests
Protein chemical synthesis and its applications.

 Awards








2002
2004
2006
2007
2008
2009
2010

Arun Guthikonda Memorial Fellow, Columbia University, USA
Hammett Award, Columbia University, USA
Skaggs Scholar, the Scripps Research Institute, USA
First Prize in Natural Science, Ministry of Education, China
Li Foundation Heritage Prize, USA
Bayer Investigator, Bayer Inc.
Thieme Synlett/Synthesis Journal Award Recent Publications
1. “Protein chemical synthesis by ligation of peptide hydrazides”, Fang, G.-M.; Li, Y.-M.; Shen,F.; Huang, Y.-C.; Li, J.-B.; Lin, Y.; Cui, H.-K.; Liu, L.; Angew. Chem. Int. Ed. 2011, 50, 76457649.
2. “Ligation of expressed protein alpha-hydrazides via genetic incorporation of an alpha-hydroxyacid”, Li, Y.-M.; Yang, M.-Y.; Huang, Y.-C.; Li, Y.-T.; Chen, P. R.; Liu, L.; ACS Chem. Biol.
2012, 7, 1015-1022.
3. “Convergent chemical synthesis of proteins by ligation of peptide hydrazides”, Fang, G.-M.;
Wang, J.-X.; Liu, L.; Angew. Chem. Int. Ed. 2012, 51, 10347-10350.

Effective Utilization of Elements and its Chemical Applications

L-2
Studies on Protein Chemical Synthesis
Lei Liu
Department of Chemistry, Tsinghua University, Beijing,
100084, P. R. China
lliu@mail.tsinghua.edu.cn

Protein chemical synthesis is a fundamental problem at the interface ofchemistry and biology. We found some new reactions in this field including theligation of protein hydrazides and irreversible NS acyl transfer reaction. These
new methods enable the chemical synthesis of several biomedicinally interesting
proteins.

4

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3rd CCS-CSJ, Young Chemists Forum

Hideki Hashimoto
Graduate School of Natural Science and Technology,
Okayama University
Address: 3-1-1 Tsushima-naka, Kita-ku, Okayama-shi,
Okayama 700-8530, Japan
Tel & Fax: (+81)-86-251-8107
E-mail: hideki-h@cc.okayama-u.ac.jp

 Educational Background

P
h
o
t
o
g
r
a
p
h
(

 2005 Bachelor of Engineering in Department of Applied Chemistry, Faculty of Engineering,
Okayama University, Japan(supervisor: Prof. Jun Takada) 2006 Master of Engineering in Division of Chemical and Biological Technology,
Graduate School of Natural Science and Technology, Okayama University, Japan(supervisor: Prof. Jun Takada) 2009 Ph.D in Division of Chemistry and Biochemistry,
Graduate School of Natural Science and Technology, Japan(supervisor: Prof. Jun Takada) Professional Career 2008 Research Fellow of the Japan Society for the Promotion of Science(JSPS Research Fellow)
 2009 Assistant professor, Okayama University

 Research Interests
Inorganic/organic hybrid materials produced by microorganisms and their applications forfunctional materials

 Awards
 2010 The Award for Young Scientist, Okayama Foundation for Science and Technology 2012 The Award for Conference 2012, Japan Society of Colour Material

 Recent Publications
1.

2.
3.
4.
5.
6.

H. Hashimoto, T. Fujii, M. Nakanishi, Y. Kusano, Y. Ikeda, J. Takada, Mater. Chem. Phys.
2012, 136, 1156–1161.
H. Hashimoto, T. Fujii, S. Kohara, H. Asaoka, Y. Kusano, Y. Ikeda, M. Nakanishi, Y.
Benino, T. Nanba, J. Takada, Mater. Chem. Phys. 2012, 137, 571–575.
H. Hashimoto, H. Asaoka, T. Nakano, Y. Kusano, H. Ishihara, Y. Ikeda, M. Nakanishi, T.
Fujii, T. Yokoyama, N. Horiishi, T. Nanba, J. Takada, Dyes and Pigments 2012, 95, 639–
643.
Y. Nishina*, H. Hashimoto*, N. Kimura, N. Miyata, T. Fujii, B. Ohtani, J. Takada, RSC
Advances 2012, 2, 6420–6423. *These authors are equally contributed to this work.
T. Suzuki, H. Hashimoto, N. Matsumoto, M. Furutani, H. Kunoh, J. Takada, Appl. Environ.
Microbiol. 2011, 77, 2877–2881.
H. Hashimoto, S. Yokoyama, H. Asaoka, Y. Kusano, Y. Ikeda, M. Seno, J. Takada, T.
Fujii, M. Nakanishi, R. Murakami, J. Magn. Magn. Mater. 2007, 310, 2405–2407.

Effective Utilization of Elements and its Chemical Applications

L-3
Structural Analysis of Nanometric Amorphous Iron
Oxide Produced by Iron-oxidizing Bacterium,

Leptothrix ochracea
Hideki Hashimoto,a Hiroshi Asaoka,a Tomoko Suzuki,a Hiromichi Ishihara,a Hitoshi
Kunoh,a Yoshihiro Kusano,b Yasunori Ikeda,c Masaharu Seno,a Makoto Nakanishi,aTatsuo Fujii,a Mikio Takano,d and Jun Takadaa, eaGraduate School of Natural Science and Technology, Okayama University,

Okayama 700-8530, JapanbDepartment of Applied Arts and Design, Kurashiki University of Science and the Arts,

Kurashiki, Okayama 712-8505, Japan
cResearch Institute for Production Development, Sakyo-ku, Kyoto, 606-0805, JapandInstitute for Integrated Cell-Material Sciences, Kyoto University, Sakyo-ku,

Kyoto 606-8501, Japan
eJST, CREST, Okayama 700-8530, Japan

A variety of iron oxides are produced by iron-oxidizing bacteria living in natural
aquatic environment. Leptothrix ochracea produces an extracellular iron oxide having
unique tubular shape of ~1 m in diameter (Figure 1). In addition to this kind ofmorphological uniqueness, its compositional and structural features are very intriguing. We
have regarded this microbial ceramics as a novel functional material, which we call “LBIOX” (BIOX: biogenous iron oxide). Here we will exhibit the compositional andstructural characteristics which are vitally important for future material scientificdevelopments. The present L-BIOX microtubules were obtained from an enrichment
culture tank using groundwater as the Fe source. The outer surface of the tubular wall ismade of fibrillar particles, about 20 nm wide and 50-100 nm long, while the inner surface
is made of globular particles of 20–120 nm in diameter. The EDX spectroscopy showedthat not only Fe and O but also Si and P are contained considerably, at an atomic ratio of
Fe: Si: P = 73: 22: 5. The XRD pattern is similar to that of 2-line ferrihydrite but, unlike
ferrihydrite, L-BIOX is completely amorphous; the Fourier-transformed HAADF-STEM
image showed a halo pattern without any spot, expelling a possibility of nano-scaled
structural ordering.

Figure 1. Typical SEM image of iron oxide microtubule produced byan iron-oxidizing bacterium, Leptothrix ochracea.

6

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3rd CCS-CSJ, Young Chemists Forum

Nanfeng Zheng
Professor of State Key Laboratory of Physical Chemistry of Solid Surfaces
Xiamen University
Address: 422 Siming South Road, Xiamen, Fujian 361005, P. R. China
Tel: (+86)-592-2186821
Fax: (+86)-592-2183047
E-mail: nfzheng@xmu.edu.cn

 Educational Background

1998 B. Sc., Xiamen University, China
2005 Ph. D., Inorganic Chemistry, Inorganic Chemistry, University of California –Riverside,(supervisor: Prof. Pingyun Feng) Professional Career

2005. 8-2007. 7



2007. 82010. 3-

Postdoctoral Research Associate, Department of Chemistry andBiochemistry, University of California – Santa Barbara,with Professor Galen D. Stucky
Professor of Xiamen University
ChangJiang Chair Professor, Ministry of Education, China

 Research Interests
The research interests of Zheng’s group focus on functional nanostructures for catalysis and bioapplications, and nanoclusters with well-defined structures. The ultimate goal is to gain deeper
understanding of the synthesis, chemical reactivity and also applications of nanostructures at themolecular level. Most of current research efforts of the group are directed to 1) controlled synthesis ofnoble metal nanocrystals with well-defined exposed surface; 2) tuning metal-inorganic and metalorganic interfaces for catalysis; 3) fabricating hollow mesoporous nanoreactors to enhance the stabilityof nanoparticulate catalysts; 4) photothermal cancer therapy using nanomaterials.

 Recent Publications
1.
2.
3.
4.
5.
6.
7.
8.
9.

“Small-adsorbate Assisted Shape Control of Pd and Pt Nanocrystals” Mei Chen, Binghui Wu, Jing Yang,
Nanfeng Zheng, Adv. Mater. 2012, 24, 862–879.
“ Selective Hydrogenation of α,β-Unsaturated Aldehydes Catalyzed by Amine-capped PlatinumCobalt
Nanocrystals” Binghui Wu, Huaqi Huang, Jing Yang, Nanfeng Zheng, Gang Fu, Angew. Chem. Int. Ed.
2012, 51, 3440-3443.
“Carbon Monoxide-assisted Synthesis of Single-crystalline Pd Tetrapod Nanocrystals through Hydride
Formation” Yan Dai, Yueming Tan, Nanfeng Zheng, Gang Fu , J. Am. Chem. Soc. 2012, 134, 7073–7080.
“Hollow Mesoporous Aluminosilica Spheres with Perpendicular Pore Channels as Catalytic
Nanoreactors” Xiaoliang Fang, Zhaohui Liu, Ming-Feng Hsieh, Mei Chen, Pengxin Liu, Cheng Chen,
Nanfeng Zheng, ACS Nano 2012, 6, 4434–4444.
“GraphenePlatinum Nanoparticles-ionic Liquid Composite Catalyst for Methanol-tolerant Oxygen
Reduction Reaction’’ Yueming Tan, Chaofa Xu, Guangxu Chen, Nanfeng Zheng, Qingji Xie, Energy
Environ. Sci. 2012, 5, 6923–6927.
“Freestanding Palladium Nanosheets with Plasmonic and Catalytic Properties” Xiaoqing Huang,
Shaoheng Tang, Xiaoliang Mu, Yan Dai, Guangxu Chen, Zhiyou Zhou, Fangxiong Ruan, Zhilin Yang,
Nanfeng Zheng*, Nat. Nanotech. 2011, 6, 28-32.
“Etching Growth under Surface Confinement: An Effective Strategy to Prepare Mesocrystalline Pd
Nanocorolla” Xiaoqing Huang, Shaoheng Tang, Jing Yang, Yueming Tan, Nanfeng Zheng, J. Am. Chem.
Soc. 2011, 133, 15946–15949“Enhancing the Photothermal Stability of Plasmonic Metal Nanoplates by a Core-Shell Architecture”
Xiaoqing Huang, Shaoheng Tang, Biju Liu, Bin Ren, Nanfeng Zheng Adv. Mater. 2011, 23, 3420-3425.
“Amine-Assisted Synthesis of Concave Polyhedral Platinum Nanocrystals Having {411} High-Index
Facets” Xiaoqing Huang, Zipeng Zhao, Jingmin Fan, Yueming Tan, Nanfeng Zheng, J. Am. Chem. Soc.
2011, 133, 4718–4721.

Effective Utilization of Elements and its Chemical Applications

L-4
Multilevel Structure Control of Metal Nanocrystals for
Catalysis and Bioapplications
Nanfeng Zheng
State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry,
Xiamen University, 422 Siming South Road, Xiamen, Fujian 361005, P. R. China
nfzheng@xmu.edu.cn
Much of our research effort has been directed towards the development of effective methods
to control the surface, interfacial and also hierarchical structures of inorganic nanomaterials. In
this presentation, I will provide an overview of our recent research in the following three areas: 1)
the controlled synthesis of Pt/Pd nanocrystals with well-defined surface structures using small
adsorbates (e.g., CO, halides, organic amines) that preferentially adsorb on specific Pt/Pd surface;2) the effects of surface structure and interfacial structure of noble metal nanocrystals on theircatalysis and bioapplications; 3) the design and fabrication of hollow mesoporous structures. I
will first discuss how small adsorbates can be used to control the surface structure of Pd/Pt
nanocrystals. For example, halides strongly adsorb on Pd {100} and thus promote the selective
production of Pd nanocubes and Pd nanowires with {100} exposed facets. CO molecules behave
differently in the controlled synthesis of Pd and Pt nanostructures. CO prefers to adsorb on Pd{111} surface to facilitate the growth of ultrathin Pd nanosheets and tetrapod/tetrahedral
nanocrystals having {111} as the main exposure surface. But for Pt, the preferential adsorption of
CO on Pt {100} induces the formation of Pt nanocubes. The strong adsorption of amines on Pt
stepped sites help the formation of high-index {411} faceted Pt nanocrystals displaying an
excellent electrocatalytic activity. Besides the surface structure control and their applications of
the shape-controlled metal nanocrystals, the control over the interfacial and hierarchical structureof metal nanocrystals for the optimization of their catalysis and bio-properties will be presented in
the talk.

8

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3rd CCS-CSJ, Young Chemists Forum

Hayato Tsuji
Associate Professor of Chemistry
Department of Chemistry, School of Science,
The University of Tokyo
Address: 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Tel & Fax: (+81)-3-5841-4367
E-mail: tsuji@chem.s.u-tokyo.ac.jp

 Educational Background




P
h
o
t
o
g
r
a
p
h
(

1998 B. Sc., Kyoto University(supervisor: Prof. Tamio Hayashi)
1998 M. Sc., Graduate School of Science, Kyoto University(supervisor: Prof. Tamio Hayashi)
2001 Doctor of Engineering, Graduate School of Engineering, Kyoto University(supervisor: Prof. Kohei Tamao)

 Professional Career





2001
2002
2006
2011

JSPS Fellowship (PD)Assistant professor, Kyoto University
Associate professor, The University of Tokyo
JST-PRESTO Researcher Research Interests
1. Synthesis of -conjugated molecules using organometallic reagent.
2.

Photophysical and electronic functionality.

 Awards




2009
2010
2010



2011

Banyu Chemistry Award
Incentive Award in Synthetic Organic Chemistry
The Young Scientists’ Prize, The Commendation for Science and Technology by
the Minister of Education, Culture, Sports, Science and Technology
Thieme Chemistry Journal Award Recent Publications
1.
2.

3.
4.

5.
6.

"New Dyes for Dye-sensitized Solar Cells Featuring a Carbon-bridged Phenylenevinylene Linker" Zhu,
X.; Tsuji, H.; Yella, A.; Chauvin, A.-S.; Grätzel, M.; Nakamura, E. Chem. Commun. 2013, 49, 582.
"Naphtho[2,1-b:6,5-b']difuran: a Versatile Motif Available for Solution-processed Single-crystal Organic
Field-effect Transistors with High Hole Mobility" Mitsui, C.; Soeda, J.; Miwa, K.; Tsuji, H.; Takeya, J.;
Nakamura, E. J. Am. Chem. Soc. 2012, 134, 5448.
"Synthesis of Tetrasubstituted Alkenes by Stereo- and Regioselective Stannyllithiation of
Diarylacetylenes" Tsuji, H.; Ueda, Y.; Ilies, L.; Nakamura, E. J. Am. Chem. Soc. 2010, 132, 11854.
"Modular Synthesis of 1H-Indenes, Dihydro-s-Indacene, and Diindenoindacene– A Carbon-bridged pPhenylenevinylene Congener" Zhu, X.; Mitsui, C.; Tsuji, H.; Nakamura, E. J. Am. Chem. Soc. 2009, 131,
13596.
"Bis(carbazolyl)benzodifuran: A High-mobility Ambipolar Material for Homojunction Organic Lightemitting Diode Devices" H. Tsuji, C. Mitsui, Y. Sato, E. Nakamura, Adv. Mater. 2009, 21, 3776.
"Synthesis and Properties of 2,3,6,7-Tetraarylbenzo[1,2-b:4,5-b’]difurans as Hole-Transporting Material"
Tsuji, H.; Mitsui, C.; Ilies, L.; Sato, Y.; Nakamura, E. J. Am. Chem. Soc. 2007, 129, 11902.

Effective Utilization of Elements and its Chemical Applications

L-5
Novel Carbon Materials toward Efficient Photovoltaics– Carbon-bridged Phenylenevinylenes andTheir Application to Dye-sensitized Solar Cells
Hayato Tsujia,baDepartment of Chemistry, School of Science, The University of Tokyo, Hongo,

Bunkyo-ku, Tokyo 113-0033, Japan
bJST-PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japantsuji@chem.s.u-tokyo.ac.jp
Dye-sensitized solar cells (DSSCs) have achieved a power conversion efficiency (PCE) of ~12%
using ruthenium-based dye and are one of the most promising practical photovoltaic devices. Fromthe viewpoint of cost, availability, and toxicity problems of rare metal-based dyes, however, use of
metal-free organic dyes has become to attract attention as alternatives. We have been interested indeveloping new planar -conjugated systems, and recently found that carbon-bridged
phenylenevinylene (COPV) compounds are unique in several aspects among commonly used electron systems. In this symposium, I present synthesis and properties of donor-COPV1-acceptor
type molecules (Dye-1 to Dye-3, Figure 1) as well as their application to DSSCs to demonstrate theirvaluable roles to achieve high PCE values for metal-free organic dyes.

Figure 1. COPV1-based dyes (Dye-1 to Dye-3) and reference compounds (Ref-1 to Ref-3) examined inthis study.

The PCE values increased progressively from 5.51% (Dye-1), to 6.18% (Dye-2) and to 7.12%(Dye-3), which are 22%, 36% and 43% higher than those obtained for the reference cells using theunbridged conterparts. Dye-3 gave the highest Jsc value of 11.60 mA/cm2, whereas Dye-1 and Dye-2
afforded 9.84 mA/cm2 and 10.78 mA/cm2, respectively. This order is in good agreement with that of
the absorption maxima. The Voc values for Dye-1, -2 and -3 systematically increased from 0.745 V(Dye-1), to 0.778 (Dye-2) and to 0.791 (Dye-3), while this is not the case for the reference dyes. As
a result, the Voc value for Dye-3 is higher than that for Ref-1 by 0.11 V. The Voc value of 0.791 V isremarkably high, given the fact that it is limited by the difference between the oxidation potential ofiodide/triiodide and the Fermi level of TiO2, which is approximately 0.9 V. In addition, the fill factor(FF) of the cells using Dye-1 to Dye-3 changes from 0.742, to 0.741 and to 0.763, respectively,
values that are much higher than those of 0.68 to 0.70 for the reference cells. An even higher Voc ofclose to 0.9 V was achieved using a Co(II/III)-based electrolyte, without substantial decrease in otherparameters, resulting in the PCE value of 7.54%.

10

11

3rd CCS-CSJ, Young Chemists Forum

Wen-Xiong Zhang
Associate Professor
College of Chemistry, Peking University
Address: Beijing 100871, P. R. China
Tel : (+86)-10-6275-8294
Fax: (+86)-10-6275-1708
E-mail: wx_zhang@pku.edu.cn

 Educational Background

1992-1996
1996-2000



1999-2002

20022004

20042007

B. Sc., Hunan Normal University,
M. Sc., Guangxi Normal University(supervisor: Prof. Wenbang Huang)
Ph.D, Nankai University(supervisor: Prof. Li-Cheng Song)
Postdoctoral Fellow, Peking University(supervisor: Prof. Zhenfeng Xi)
Postdoctoral Fellow, Riken, Japan(supervisor: Prof. Zhaomin Hou)

 Professional Career


2007-

Professor, Peking University

 Research Interests
Structural characterization of active reaction intermediates in metal-mediated or -catalyzed
organic synthesis and small molecule activation of novel organo rare earth metal compounds.

 Recent Publications
1.

2.

3.

4.

5.

“Regioselective Ring Expansion of 2,4-Diiminoazetidines via Cleavage of C–N and C(sp3)–H
bonds: Efficient Construction of 2,3-Dihydropyrimidinesulfonamides” Wang, Y.; Chi, Y.;
Zhang, W. -X.;* Xi, Z.* J. Am. Chem. Soc. 2012, 134, 29262929.
“Procedure-controlled Selective Synthesis of 5-Acyl-2-iminothiazolines and their Selenium
and Tellurium Derivatives by Convergent Tandem Annulation” Wang, Y.; Zhang, W. -X.;*
Wang, Z.; Xi, Z.* Angew. Chem. Int. Ed. 2011, 50, 81228126.
“Zirconocene and Si-tethered Diynes: A Happy Match Directed towards Organometallic
Chemistry and Organic Synthesis” Zhang, W. -X.; Zhang, S.; Xi, Z.* Acc. Chem. Res. 2011, 44,541551.
“Ln4(CH2)4-Cubane-type
Rare-earth
Methylidene
Complexes
Consistingof“(C5Me4SiMe3)LnCH2” Units (Ln = Tm, Lu)” Zhang, W. -X.; Wang, Z.; Nishiura, M.; Xi, Z.;*
Hou, Z. J. Am. Chem. Soc. 2011, 133, 57125715.
“Efficient One-pot Synthesis of 2,3-Dihydropyrimidinthiones via Multicomponent Coupling ofTerminal Alkynes, Elemental Sulfur and Carbodiimides” Wang, Z.; Wang, Y.; Zhang, W. X.;* Hou, Z.; Xi, Z.* J. Am. Chem. Soc. 2009, 131, 15108–15109.

Effective Utilization of Elements and its Chemical Applications

L-6
Mechanism-directed Organicand Organometallic Chemistry of Carbodiimides
Wen-Xiong Zhang
College of Chemistry, Peking University, Beijing 100871, P. R. China
wx_zhang@pku.edu.cn
For more than 130 years, carbodiimides (RN=C=NR) have proved versatile reagents since
the carbodiimides was first correctly formulated and characterized by Weith. Carbodiimide
chemistry mainly included the use as condensing agents in the preparation of nucleotides andpeptides, heterocycle synthesis, cycloaddition reactions, biological modification, and etc. For
organometallic chemists, carbodiimides were used widely to synthesize amidinate/guanidinate
ancillary ligands for stabilization of various metal complexes owing to the well establishednucleophilic addition process of organometallic reagents to carbodiimides. Scheme 1summarized our recent development on the metal-promoted carbodiimide chemistry.1-4 To gain
information on these processes, mechanistic studies were carried out by the isolation andcharacterization of the important reaction intermediates.

Scheme 1.
References[1] (a) Xu, L.; Wang, Z.; Zhang, W. -X.;* Xi, Z.* Inorg. Chem. 2012, 51, 11941. (b) Zhao, F.; Wang, Y.;
Zhang, W. -X.;* Xi, Z.* Org. Biomol. Chem. 2012, 10, 6266. (c) Li, D.; Guang, J.; Zhang, W. -X.;*
Wang, Y.; Xi, Z.* Org. Biomol. Chem. 2010, 8, 1816. (d) Zhang, W. -X.;* Li, D.; Wang, Z.; Xi, Z.*
Organometallics 2009, 28, 882. (e) Li, D.; Wang, Y.; Zhang, W. -X.;* Zhang S.; Guang, J.; Xi, Z.*
Organometallics 2011, 30, 5278.
[2] Wang, Z.; Wang, Y.; Zhang, W. -X.;* Hou, Z.; Xi, Z.* J. Am. Chem. Soc. 2009, 131, 15108.
[3] Wang, Y.; Zhang, W. -X.;* Wang, Z.; Xi, Z.* Angew. Chem. Int. Ed. 2011, 50, 8122.
[4] Wang, Y.; Chi, Y.; Zhang, W. -X.;* Xi, Z.* J. Am. Chem. Soc. 2012, 134, 2926.

12

13

3rd CCS-CSJ, Young Chemists Forum

Ryotaro Arita
Associate Professor
Department of Applied Physics, School of Engineering,
The University of Tokyo
Address: 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
Tel & Fax: (+81)-3-5841-6809
E-mail: arita@ap.t.u-tokyo.ac.jp

 Educational Background


1995



1997



2000

B. Sc., The University of Tokyo(supervisor: Prof. Hideo Aoki)
M. Sc., Graduate School of Science, The University of Tokyo(supervisor: Prof. Hideo Aoki)
Doctor of Science, Graduate School of Science, The University of Tokyo(supervisor: Prof. Hideo Aoki)

 Professional Career






1999
2000
2006
2008
2011

JSPS Fellowship (DC2)
Assistant Professor, The University of Tokyo
Research Scientist, RIKEN
Assoicate Professor, The University of Tokyo
JST-PRESTO Researcher Research Interests
1. Theoretical materials design of strongly correlated electron systems.
2. Development of new methods for electronic structure calculation.
 Awards




2006
2011
2012

JDZB Science Award, The Society of Friends of the Japanese-German Center Berlin
Young Scientist Award of the Physical Society of JapanThe Young Scientists’ Prize, The Commendation for Science and Technology by
the Minister of Education, Culture, Sports, Science and Technology Recent Publications
1.
2.
3.
4.
5.
6.
7.

"Magneto-orbital Effect without SpinOrbit Interactions in a Noncentrosymmetric Zeolitetemplated Carbon Structure" Koretsune, T.;Arita, R.; Aoki, H. Phys. Rev. B 2012, 86, 125207.
"Ab initio Derivation of Electronic Low-energy Models for C60 and Aromatic Compounds"
Nomura, Y.; Nakamura, K.; Arita, R Phys. Rev. B 2012, 85, 155452.
"Ab initio Derivation of Correlated Superatom Model for Potassium Loaded Zeolite" Nohara, Y.;
Nakamura, K.; Arita, R J. Phys. Soc. Jpn. 2011, 80, 124705.
"Spin-density-functional Study of the Organic Polymer Dimethylaminopyrrole: A Realization of
the Organic Periodic Anderson Model" Suwa, Y.; Arita, R.; Kuroki, K; Aoki, H. Phys. Rev. B 2010,82, 235127.
"Spin-density-functional Study of Magnetism in Potassium-loaded Zeolite A" Nohara, Y.;
Nakamura, K.; Arita, R. Phys. Rev. B 2009, 80, 220410(R).
"First-principles Electronic Structures of Solid Picene" Kosugi, T.; Miyake, T.; Ishibashi, S.; Arita,
R; Aoki, H. J. Phys. Soc. Jpn. 2009, 78, 113704.
"Ab initio Derivation of Low-energy Model for Alkali-cluster-loaded Sodalites" Nakamura, K.;
Koretsune, T.; Arita, R. Phys. Rev. B 2009, 80, 174420.

Effective Utilization of Elements and its Chemical Applications

L-7
Magneto-orbital Effect without SpinOrbit Interactions in a
Noncentrosymmetric Zeolite-templated Carbon Structure
Takashi Koretsune,a Ryotaro Arita,b,c and Hideo Aokid
aDepartment of Physics, Tokyo Institute of Technology, Oh-okayama,

Meguro-ku, Tokyo 152-8551, JapanbDepartment of Applied Physics, School of Engineering, The University of Tokyo,

Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
cJST-PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, JapandDepartment of Physics, School of Science, The University of Tokyo, Hongo,

Bunkyo-ku, Tokyo 113-0033, Japanarita@ap.t.u-tokyo.ac.jp

A peculiar manifestation of orbital angular momentum is proposed for a zeolitetemplated carbon system, C36H9. The structure, being a network of nanoflakes in the
shape of a “pinwheel,” lacks inversion symmetry. While the unit cell is large, theelectronic structure obtained with a first-principles density-functional theory and captured
as an effective tight-binding model in terms of maximally localized Wannier functions,exhibits an unusual feature that the valence band top comes from two chiral states having
orbital magnetic momenta of ±1. The noncentrosymmetric lattice structure then makes
the band dispersion asymmetric, as reminiscent of, but totally different from, spin-orbit
systems. The unusual feature is predicted to imply a current-induced orbital magnetism
when holes are doped.

Figure 1.
(a) Crystal structure of the zeolite-templated carbon. Solid line represents
a unit cell, which contains eight hydrocarbon C36H9 patches [with 288 carbon (darker
spheres) and 72 hydrogen atoms (lighter)] with different orientations. (b) A C36H9 patchwith its three nearest neighbor patches, which form a three-winged “pinwheel” with athreefold axis. (c) Maximally localized Wannier function for the top valence bands.

14

15

3rd CCS-CSJ, Young Chemists Forum

Shou-Fei Zhu
Associate Professor of Chemistry
State Key Laboratory and Institute of Elemento-Organic Chemistry,
Nankai University,
Address: 94 Weijin Road, Tianjin 300071, P. R. China
Tel: (+86)-22-2350-4087
Fax: (+86)-22-2350-6177
E-mail: sfzhu@nankai.edu.cn

 Educational Background2000 B. Sc., Nankai University(Advisor: Prof. Shou-He Xiang)
2005 Ph. D., Nankai University(Advisor: Prof. Qi-Lin Zhou)

 Professional Career

2005. 7-2008. 12
2008. 12-present
2012. 3-2013. 3

Lecture, Nankai University
Associate Professor, Nankai University
Postdoctoral Fellow, the University of Tokyo(Advisor: Prof. Eiichi Nakamura) Research Interests
SFZ's research interests focus on transition-metal catalysis, particularly on the development of chiralligands and catalysts as well as new asymmetric reactions. His current research interests involve:
1) Transition-metal-catalyzed asymmetric carbene transfer reactions.
2) Transition-metal/organo cooperative catalysis. 3) Iron catalysis.

 Awards







2004 Hong Kong Qiu-Shi Award for Graduate Students
2007 Tianjin Natural Science Award (the First-Rank)
2010 New Century Excellent Talents Project (Ministry of Education of China)
2012 The Science Funds for Excellent Youth(National Natural Science Foundation of China)
2012 The Top-notch Personnel Supporting Project for Youth of China
2012 Young Chemist Award of Chinese Chemical Society Recent Publications
1.
2.
3.
4.
5.
6.

"Enantioselective Transition-metal-catalyzed Heteroatom-hydrogen Bonds Insertion Reactions" ShouFei Zhu, Qi-Lin Zhou, Acc. Chem. Res. 2012, 45, 1365–1377.
"Well-defined Binuclear Chiral Spiro Copper Catalysts for Enantioselective N–H insertion" Shou-Fei
Zhu, Bin Xu, Guo-Peng Wang, Qi-Lin Zhou, J. Am. Chem. Soc. 2012, 134, 436–442.
"Enantioselective Hydrogenation of α-substituted Acrylic Acids Catalyzed by Iridium Complexes with
Chiral Spiro Aminophosphine Ligands" Shou-Fei Zhu, Yan-Bo Yu, Shen Li, Li-Xin Wang, Qi-Lin
Zhou, Angew. Chem. Int. Ed. 2012, 51, 8872–8875.
"Asymmetric N–H Insertion Reaction Cooperatively Catalyzed by Rhodium and Chiral Spiro
Phosphoric Acids" Bin Xu, Shou-Fei Zhu, Xiu-Lan Xie, Jun-Jie Shen, Qi-Lin Zhou, Angew. Chem. Int.
Ed. 2011, 50, 11483–11486.
"Enantioselective Iron-catalysed O–H Bond Insertions" Shou-Fei Zhu, Yan Cai, Hong-Xiang Mao, JianHua Xie, Qi-Lin Zhou, Nat. Chem. 2010, 2, 546–551.
"Enantioselective Copper-catalyzed Intramolecular OH Insertion: An Efficient Approach to Chiral 2Carboxy Cyclic Ethers" Shou-Fei Zhu, Xiao-Guang Song, Yu Li, Yan Cai, Qi-Lin Zhou, J. Am. Chem.
Soc. 2010, 132, 16374–16376.

Effective Utilization of Elements and its Chemical Applications

L-8
Iron-catalyzed Carbene Transfer Reactions
Shou-Fei Zhu
State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University,
94 Weijin Road, Tianjin 300071, P. R. China
sfzhu@nankai.edu.cn

Transition metal catalysis plays a crucial role in modern chemistry. However, theimportant reactions are predominantly catalyzed by precious metals nowadays. The readyavailability, low price, and environmentally benign character of iron imply that it is an
ideal alternative to precious metals in catalysis. Recent growth in the number of ironcatalyzed reactions reported reflects an increasing demand for sustainable chemistry.
Although tremendous efforts have been devoted into this field in the past decade, the ironcatalysis is still in its infancy comparing to well-established precious metal catalysis. The
iron catalysis is suffering many challenges, such as limited reaction types, low efficiency,
as well as poor selectivity. The development of new iron catalysts and iron-catalyzed neworganic transformations are the original impetus for advancing the iron catalysis.
Carbene transfer reactions have been versatile and powerful tools in organic
synthesis; however, iron-catalyzed carbene transfer reactions are much underdeveloped.
We report here the preliminary results of iron-catalyzed carbene transfer reactions,
including O–H bond insertion reactions of alcohols and water, formal C–H bond insertionof indoles, and others. Good to excellent level of enantioselectivities with broad substratescopes were obtained by fine tune of the chiral iron catalysts. Iron catalysts are superior
to other transition metal catalysts in the above reactions, which demonstrate that the ironcatalysts are good candidates for asymmetric carbene transformations.

16

17

3rd CCS-CSJ, Young Chemists Forum

Aiwen Lei
Executive Director of Green Catalysis Institute
Professor of the College of Chemistry & Molecular Sciences
Wuhan University
Address: Wuhan, Hubei, P. R. China 430072
Tel & Fax: (+86)-27-68754672
E-mail: aiwenlei@chem.whu.edu.cn

 Educational Background

1999-2000 Graduate Studies, Shanghai Institute of Organic Chemistry,
CAS, China (SIOC)
2000-2003 Postdoctoral Fellow, Department of Chemistry,
The Pennsylvania State University (supervisor: Prof. Xumu Zhang)
2003-2005 Research Associate, Department of Chemistry, Stanford University(supervisor: Prof. James, P. Collman)

 Research Interests




-

Small molecule (such as O , N O, H O , NH , ClO , etc.) activation with an emphasis on applying
2

2

2

2

3

2

such molecules in efficient synthetic methods
Developing highly selective and efficient transition-metal-catalyzed CC, and CHeteroatom bondformation in syntheses
Mechanistic and active intermediate studies of chlorite dismutase, cytochrome P450, andperoxidase.

 Awards











2011 Eli Lilly Asian Scientific Excellence Award
2011 Lectureship Awardee of Asian International Symposium for Outstanding Young Scientists
2010 National Science Fund for Distinguished Young Scholars, China, 20102009 CAPA (Chinese-American Chemistry & Chemical Biology Professors Association)
Distinguished Faculty Award, 20092008 Chinese Chemistry Society－John Wiley Young Chemist Award
2008 Royal Society Chemistry Journal Grant
2008 Synthesis & Synlett Journal Award
2007 Wuxi Pharmtech Biological & Organic Creative Award
2007- Luojia Scholarship Professor (Wuhan University)
2006 Outstanding Young Scientist of Hubei Province Recent Publications
1.
2.
3.
4.
5.
6.
7.
8.
9.

A. Lei. etc. Nature Comm. (2012) DOI: 10.1038/ncomms2196
A. Lei. etc. Angew. Chem. Int. Ed. (2012) DOI: 10.1002/anie.201206518
A. Lei. etc. Angew. Chem. Int. Ed. 51, 9547 (2012)
A. Lei. etc. Angew. Chem. Int. Ed. 51, 5662 (2012)
A. Lei. etc. J. Am. Chem. Soc. 134, 5766 (2012)
A. Lei. etc. Angew. Chem. Int. Ed. 51, 5204 (2012)
A. Lei. etc. Angew. Chem. Int. Ed. 51, 4666 (2012)
A. Lei. etc. Angew. Chem. Int. Ed. 51, 3638 (2012)
A. Lei. etc. Chem Sci, 3, 1211(2012)18

Effective Utilization of Elements and its Chemical Applications

L-9
Oxidative Coupling: Chemistry between Two “Nucleophiles”
Aiwen Lei
College of Chemistry and Molecular Sciences, Wuhan University,
Hubei, 430072, P. R. China
aiwenlei@chem.whu.edu.cn

Our research focuses on developing novel and efficient bond-formation methods
catalyzed by transition metals. Currently, we are interested in the oxidative coupling,which avoids difficult oxidative addition step and makes bonds between two
nucleophiles. As an important character of our research, in-depth understanding
toward the reactions is the other focus. Recently, we revealed a second
transmetallation reaction, which could occur in the Pd-catalyzed coupling reaction as
a fundamental step. In addition, kinetic studies in our laboratory quantitatively
disclosed the rate of reductive elimination of Csp2NiCsp2.

Oxidative Coupling

Mechanistic & Kinetic Investigation

SnBu3 + R 2(sp3)

2nd generation:

ZnX

desyl chloride

3

generation:

R1

[Pd]

R2

+

R2

H

H
R1

N
R

O

R1

H OR 2+ CO +

H
+

O
+

R

CO

R'

OMe

R1

Air
[Pd]

R2

R1

H

+

R2

R3
H

-1

200

400

600

800

1000

-1

k0 C = 0.032 M s -1
k- 10 C = 0.017 M-1s-1
o

-1.4
-1.5
-1.6

1200

0

time (s)NiCl 2. 6H2O, CuI
TMEDA
Air or O2

500

1000 1500
t/ s

2000

2500

R2

R1

Air

DMF

New Concept: Second Transmetallation

COOR 2

PdCl2(PPh3)2

[Pd]
[O]

R1

O

R1

R2

SecondTransmetallation

O

L

R

R'
O
R3
R1

O

[Pd]

Ar1I + Ar 2ZnCl

N
RO

Ag 2CO3, KOAc

Oo

R 1-R2OO-4

ko bs = 6.54 x 10 M s
0-1

k10 C = 0.10 M s
o

0.08

0.04

-1

-1

o

k obs = 1.49 x 10 -4 M s-1

0.12

-1

k20 C = 0.32 M s-1.3

Ar COOR2

Pd/P-olefinO2 balloon

H OR2

R

First-order kinetic suggests
TM as the rate-limiting step

p-MeO PhZ nCl
p-ClPhZ nCl

0.16

[Pd]

R1H + R2H

H

Zero-order kinetic suggests
RE as the rate-limiting stepR2(sp 3)Odesyl chloride

ArB(OR1)2 + CO + R 2OH
rd

R1

R 1-R2

R3In + CO + MeOH
+ H

Ar-Ar

desyl chloride: RCl[Pd]

R1M + R2H

R 1ZnCl[Ni]

ArZnCl

R 1-R2

R1M + R2M

R1

Nu1-Nu2ln[PhZnCl]

1st generation:

catalyst
oxidant+ Nu2[desyl chloride] (M)

Nu1

R2

L

Pd

L
L

Ar 1-Ar2 + Ar 2-Ar 2

Ar2
Pd
Ar1



Ar1-ZnCl

2

Ar

L

Zn

L

Cl

Pd

Ar 2
Ar 2

Ar 2
Ar 1
Reductive

LElimination

L

Pd

Ar2
Ar1


L
L

Pd + Ar 1-Ar2

19

3rd CCS-CSJ, Young Chemists Forum

Qilong Shen
Professor
Key Laboratory of Organofluorine Chemistry
Shanghai Institute of Organic Chemistry, CAS
Address: 345 Lingling Road, Shanghai 200032, P. R. China
Tel : (+86)-21-54925197
E-mail: shenql@sioc.ac.cn

 Educational Background

1992-1996
1996-1999

2000-2002

 2002-2007

B.S. Nanjing University
M.S. Shanghai Institute of Organic Chemistry, CAS(supervisor: Prof. Long Lu)
M.S. University of Massachusetts, Dartmouth(supervisor: Prof. Gerald B Hammond)
Ph.D. Yale University(supervisor: Prof. John F Hartwig)

 Professional Career

2007-2010

Post-doctoral researcher, Department of Chemistry,
University of Illinois Urbana-Champaign
2010- present Professor, Shanghai Institute of Organic Chemsitry,
CAS 2001 JSPS Fellowship (PD) Research Interests
1.
2.
3.

Transition metal-catalyzed fluorination and fluoroalkylation of arene, alkene and alkane
substrates.
Fluoroalkyl-substituted phosphine ligands as CO mimics for asymmetric reactions
New methods for the synthesis of fluorinated polymers.

 Awards

2013

Thieme Chemistry Journal Award Recent Publications
1.
2.
3.

“An Electrophilic Hypervalent Iodine Reagent for Trifluoromethane-sulfanylation” Shao, X.X.; Wang, X.-Q.; Yang, T.; Lu, L.; Shen, Q. Angew. Chem. Int. Ed. Accepted.
“Copper-mediated Aerobic Fluoroalkylation of Arylboronic Acids with Fluoroalkyl Iodides at
Room Temperature” Qi Q.; Shen, Q.; Lu, L. J. Am. Chem. Soc. 2012, 134, 6548.
“Highly Selective Trifluoromethylation of 1,3-Disubstituted Arenes through Iridiumcatalyzed Arene Borylation” Liu, T.; Shao, X.; Wu, Y.; Shen, Q. Angew. Chem. Int. Ed. 2012,
51, 540.

Effective Utilization of Elements and its Chemical Applications

L-10
From Trifluoromethylation to Trifluoromethylthiolation:
Development of New Trifluoromethylthiolated
Hypervalent Iodine Reagent
Qilong Shen
Key Laboratory of Organofluorine Chemistry,
Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
345 Lingling Road, Shanghai, 200032 P. R. China
shenql@sioc.ac.cn
It is well established that the replacement of a hydrogen atom with fluorine in organic compounds brings
about major biological and chemical changes. Among many fluorinated functional groups, thetrifluoromethyl group (CF3-) and trifluoromethylthio group (CF3S-) are two of the most lipophilic
substituents. It is well known that incorporation of trifluoromethyl or trifluoromethylthio group into small
molecules greatly enhances its ability to cross lipid membranes and in vivo absorption rate. In addition, theirhigh electronegativity significantly improves the small molecule’s stability in acidic environments. Thus,
both trifluoromethyl and trifluoromethylthio group have been of special attention from pharmaceutical andagrochemical industry for theirs use\ in isosetere-based drug design. Although several strategies employing
transition-metal catalysts emerged for the preparation of trifluoromethyl- or trifluoromethylthio-substituted
arenes in the past several years, the development of general catalytic methods for the incorporation of these
two groups under mild conditions remains a challenge for synthetic organic chemists.
In 2011, we reported a copper-catalyzed protocol for trifluoromethylation of aryl and alkenylboronic acids
with trifluoromethylated hypervalent iodine reagent (Togni’s reagent). The reaction proceeded in good to
excellent yields for a range of different substrates including heteroarylboronic acids and substrates with avariety of functional groups under mild reaction conditions. In addition, we further developed a sequential
iridiumcatalyzed C-H activation borylation and copper-catalyzed trifluoromethylation of arenes with avariety of functional groups. The advantage of this tandem procedure was demonstrated by application in a
number of biologically active molecules. Based on these results, we envisioned that atrifluoromethylthiolated hypervalent iodine reagent would be a powerful electrophilic reagent for the
introduction of trifluoromethylthio group. Herein, we present the invention of such a reagent and its reactions
with a variety of nucleophiles such as -ketoesters, aldehydes, amides, aryl or vinyl boronic acids or alkynes
under mild conditions.
B(OH)2R
1 equiv

R
H

I+

K2CO3 (2.0 equiv)
Diglyme35 oC, 14 h

CF3
R

R

5 mol% CuTc
10 mol% Phen

B2Pin2/ 80 oC/ 24 h

LiOH H2O (2.0 Equiv)
Togni's reagent
CH2Cl2/ 45 oC, 3 h

R

R'

O

B(OH)2up to 75%
alkyne

SCF3

CF3

SCF3

ArB(OH)2

up to 95%

SCF3

(1)

50-95% yield

0.2 mol% [Ir(COD)OMe]2
0.4 mol% dtbpy

SCF3

R''

5 mol % CuI
10 mol % L1O

1.2 equiv

R'

R'

F3C

up to 92%

F3CS

I

O

-ketoesters
up to 98%

aldehydes
up to 86%

n

O

SCF3

H
R
O

enolate20%, 50:1dr

N
CF3S

CO2R

Ph

O
O

(2)

20

21

3rd CCS-CSJ, Young Chemists Forum

Takeshi Fujita
Associate Professor of Engineering
Advanced Institute for Materials Research, Tohoku University
Address: 2-1-1 Katahira, Aoba-ku, Sendai, Miyagi 980-8577, Japan
Tel & Fax: (+81)-22-217-5990
E-mail: tfujita@wpi-aimr.tohoku.ac.jp

 Educational Background

1998 B. Sc., Kyushu University(supervisor: Prof. Minoru Nemoto)2000 M. Sc., Graduate School of Engineering, Kyushu University(supervisor: Prof. Minoru Nemoto)2003 Doctor of Engineering, Graduate School of Engineering, Kyushu University(supervisor: Prof. Zenji Horita) Professional Career






2003
2003
2005
2010
2011

Assistant Professor, Kyushu University
JSPS Postdoctal Fellowship for Research Abroad, Arizona State University
Assistant Professor, Tohoku University
Associate Professor, Tohoku University
JST-PRESTO Researcher Research Interests
1.
2.

Transmission electron microscopy
Advanced functional materials (nanoporous metals metallic glass) Awards
 2007 JIM Micrograph Award 2009 JIM Micrograph Award Recent Publications
1.

2.
3.
4.
5.
6.

“Atomic Origins of the High Catalytic Activity of Nanoporous Gold” T. Fujita, P. F. Guan, K.
McKenna, X. Y. Lang, A. Hirata, L. Zhang, T. Tokunaga, S. Arai, Y. Yamamoto, N. Tanaka,
Y. Ishikawa, N. Asao, Y. Yamamoto, J. Erlebacher, M. W. Chen, Nat. Mater. 2012, 11, 775780.
“Nanoporous Metal/Oxide Hybrid Electrodes for Electrochemical Supercapacitors” X. Y. Lang,
A. Hirata, T. Fujita, M. W. Chen, Nat. Nanotechnol. 2011, 6, 232-236.
“Oxygen Reduction in Nanoporous Metal–Ionic Liquid Composite Electrocatalysts” J. Snyder,T. Fujita, M. W. Chen, J. Erlebacher, Nat. Mater. 2010, 9, 904-907.
“Atomic-scale Heterogeneity of a Multicomponent Bulk Metallic Glass with Excellent Glass
Forming Ability” T. Fujita, K. Konno, W. Zhang, V. Kumar, M. Matsuura, A. Inoue, T. Sakurai,
M. W. Chen, Phys. Rev. Lett. 2009, 103, 075502.
“Unusually Small Electrical Resistance of Three-dimensional Nanoporous Gold in External
Magnetic Fields” T. Fujita, H. Okada, K. Koyama, K. Watanabe, S. Maekawa, M. W. Chen,
Phys. Rev. Lett. 2008, 101, 166601.
“Three-dimensional Morphology of Nanoporous Gold” T. Fujita, L. H. Qian, K. Inoke, J.
Erlebacher, M. W. Chen, Appl. Phys. Lett. 2008, 92, 251902.

Effective Utilization of Elements and its Chemical Applications

L-11
Catalytic Origins of Nanoporous Metal
Takeshi Fujitaa,baAdvanced Institute for Materials Research, Tohoku University, Katahira,Aoba-ku, Sendai, Miyagi 980-8577, Japan
bJST-PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japantfujita@wpi-aimr.tohoku.ac.jp
It is well known that gold is the only metal that has endothermic oxygen
chemisorption energy. In principle, it does not bind oxygen at all and thus is inert
toward oxidation reactions. For this reason, the discovery that gold nanoparticles are acatalyst for carbon monoxide (CO) oxidation stimulates extensive researchenthusiasms and considerable debate. Because catalytically active gold nanoparticles
are usually supported on high surface area oxides, their catalytic performance may beaffected by the supports, which has limited the understanding of the intrinsic catalytic
activity of gold.
Interestingly, significant catalytic activity can be retained in dealloyed nanoporous
gold (NPG) even when their feature lengths are larger than 30 nm. Here we reportatomic insights of the NPG catalysis, characterized by Cs-corrected transmission
electron microscopy (TEM) and environmental TEM. A high density of atomic steps
and kinks are observed on the curved surfaces of NPG, comparable to 3–5 nm
nanoparticles, which are stabilized by hyperboloid-like gold ligaments. In situ TEM
observations provide compelling evidence that the surface defects are active sites forthe catalytic oxidation of CO and residual Ag stabilizes the atomic steps by
suppressing {111} faceting kinetics.

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3rd CCS-CSJ, Young Chemists Forum

Katsuro Hayashi
Associate Professor of Materials Science
Materials and Structures Laboratory, Tokyo Institute of Technology
Address: 4295, Nagatsuta, Yokohama 226-8503, Japan
Tel & Fax: (+81)-45-924-5337
E-mail: k-hayashi@lucid.msl.titech.ac.jp

 Educational Background

1995 B. Sc., The University of Tokyo
1997 M. Sc., Graduate School of Engineering,
The University of Tokyo
2000 Ph. D. (Eng.), Graduate School of Engineering, The University of Tokyo(supervisor: Prof. Taketo Sakuma)

 Professional Career

1997 JSPS Fellowship (DC1)2000 Postdoctoral Researcher, Hosono Transparent Electro-Active Materials Project,
ERATO, JST
2004 Assistant Professor, Frontier Collaborative Research Center, Tokyo Institute of Technology
2006 Associate Professor, Materials and Structures Laboratory, Tokyo Institute of Technology

 Research Interests
1.
2.

Electrical and chemical properties of metal-oxide materials
Electrochemical devices using solid electrolytes

 Awards2006 Young Scientist Award, First International Symposium on Transparent Conducting Oxides(Crete, Greece)
2008 Young Scientist Award, MEXT, Japanese Government
2009 Third Prize, German Innovation Award Gottfried Wagner Prize 20082009 Challenging Research Award, Tokyo Institute of Technology Recent Publications
1.
2.
3.
4.
5.

6.

“Intense Atomic Oxygen Emission from Incandescent Zirconia” K. Hayashi, T. Chiba, J. Li, M.
Hirano, H. Hosono, J. Phys. Chem. C, 2009, 113 9436.
“Heavy Doping of H− Ion in 12CaO·7Al2O3” K. Hayashi, J. Solid State Chem. 2011, 184, 1428
“Kinetics of Electron Decay in Hydride Ion-Doped Mayenite” K. Hayashi, J. Phys. Chem. C,
2011, 115, 11003.
“New Functionalities in Ubiquitous Oxides” H. Hosono, K. Hayashi, T. Kamiya, T. Atou, T.
Susaki, Sci. Technol. Adv. Mater. 2011, 12, 34303.
“Solid-State Source of Atomic Oxygen for Low-Temperature Oxidation Processes:
Application to Pulsed Laser Deposition of TiO2:N films” D. Ojima, T. Chiba, K. Shima, H.
Hiramatsu, H. Hosono, K. Hayashi, Rev. Sci. Instrum. 2012, 83, 23903.
“Thermionic Electron Emission from a Mayenite Electride-Metallic Titanium Composite
Cathode” T. Yoshizumi, K. Hayashi, Appl. Phys. Exp. 2013, 6, 15802.

Effective Utilization of Elements and its Chemical Applications

L-12
Refractory Oxides as Novel Electronics and Ionics Materials
Katsuro Hayashi
Center for Secure Materials, Materials and Structures Laboratory,
Tokyo Institute of Technology, 4259 Nagatsuta, Yokohama, Kanagawa 226-8503, Japan
Typical constitution elements of refractory materials are O, Si, Al, Ca, Mg, Na, Ti, and Zr, whichalmost agree with the best abundant elements in the Clark’s natural abundance. Principal role required forthese materials is withstanding severe thermochemical conditions, and many costs cannot be paid forthem; they are made of naturally stable and abundant resources i.e. rocks and soils. Although electronic
functionality has not been much expected in the refractory materials, a combination of the excellent
durability with electronic and/or ionic properties potentially creates novel functionaries and applications
without using precious elements. In this symposium, a few research topics of our group according to thispolicy will be described.
Hydride ion doping in mayenites. Mayenite is a natural mineral as well as a constituent of alumina
cements. Its structural formula for the unit cell is described as [Ca24Al28O64]4+4X (C12A7), in which
former part corresponds to a positively charged framework with cage structure and the latter is anions
incorporated in the cages (cf. Bull. Chem. Soc. Jpn. 2007, 80, 872-884).
In 2002, our group reported that the cage anions, 4X, is partially replaced with hydride (H) ions byhigh temperature treatment in hydrogen gas, and resultant H ion-doped mayenite is converted topersistently an electronic conductor by irradiation of ultraviolet light. The H ion in cage can generate
totally two electrons, which again captured in cages, by the photo-assisted reaction via its conversion to
H+ ion, and the electrons are responsible for the conductivity. Since the H ion-doped mayenite istransparent, it was expected to serve as a functional transparent oxide conductor (TCO) that potentiallysubstitutes for indium tin oxide (ITO). However, conductivity, transparency, chemical properties and highcontact resistance with metals do not meet to requirements for practical applications. Nevertheless thehigh contact resistance is connected to inherent low work function, which is advantageous for electron
emission or injection cathodes. According to thermionic emission property, its work function is as low as
2.1 eV, which is comparable with those of alkali metals.
Although mayenite lattice provide a peculiarly stable site for H ion, doping of H ion in metal oxide
generally has been considered to be very difficult. Since the H ion is a strong reducing agent, a hostoxide material needs to be durable for it. Refractory materials are good candidates. In addition, there aremany oxide-based mineral crystals that have a monovalent anion site like mayenite does. Evidences forH ion incorporation in some materials will be also presented.
High energy density battery. Revolutional battery that has an energy density higher by several times
than Li-ion batteries is demanded for electronic vehicles having a comparable range with conventional
petrol ones. One of the ultimate ways for enhancing the energy density is employment of metallic Li as
negative active material and oxygen in air as positive active material. This type of battery is termed Li-air
battery and has been studied extensively for the last decade.
We are developing a Na-substituted version for it. The cell is composed of metallic Na negativeelectrode, organic electrolyte, solid electrolyte, aqueous electrolyte, and gas permeable positive electrode.
It is demonstrated that the Na-substitution is not only the replacement with cheaper and more abundantmaterials but also beneficial for enhancing the energy density. The requirements for the solid electrolyte
are fast Na+ ion conductivity as well as chemical stability for metallic Na and strong basic solutions. We
have chosen -alumina (typical chemical composition of Na1+xMgxAl11xO17, where x ~0.6) and
NASICON (typical chemical formula of Na1+xZr2SixP3xO12, where x ~2.0) ceramic membranes for thispurpose. The cell performance achieved so far will be presented.

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3rd CCS-CSJ, Young Chemists Forum

Liang Zhao
Associate Professor
Chemistry Department, Tsinghua University
Address: Department of Chemistry, Tsinghua University,
Beijing 100084, P. R. China
Tel: (+86)-10-62797527
E-mail: zhaolchem@mail.tsinghua.edu.cn

 Educational Background






2002
2003-2007

B. Sc., the Chemistry College at Peking University
Ph. D., the Chemistry Department of Chinese University of Hong Kong(supervisor: Prof. Thomas C. W. Mak)
2007-2009 Postdoctoral studies. University of Utah(supervisor: Prof. Peter J. Stang)2009.11-now Associate Professor, Department of Chemistry, Tsinghua University
2002.8-2003.7 Research Associate, Institute of Physical Chemistry, Peking University

 Research Interests
His research work is focused on (i) synthesis of organic and organometallic macrocycles, (ii)metal cluster-centered coordination self-assembly, (iii) synthesis of high-nuclearity metalclusters and nanoparticles assisted by polydentate organic or organometallic ligands.

 Recent Publications
1.

2.

3.

4.
5.

6.

“Stabilization of a Reactive Polynuclear Silver Carbide Cluster through the Encapsulation
within Supramolecular Cage” Cai-Yan Gao, Liang Zhao*, Mei-Xiang Wang*, J. Am. Chem.
Soc. 2012, 134, 824–827.
“Designed Synthesis of Metal Cluster-Centered Pseudo-Rotaxane SupramolecularArchitectures” Cai-Yan Gao, Liang Zhao*, Mei-Xiang Wang*, J. Am. Chem. Soc. 2011,
133, 8448–8451.
“Synthesis, Structure and Metal Binding Property of Internally 1,3-Arylene-Bridged
Azacalix[6]aromatics” Yi-Xin Fang, Liang Zhao*, De-Xian Wang, Mei-Xiang Wang*, J.
Org. Chem. 2012, 77, 10073–10082.
“Designed Synthesis of a Metal Cluster-Pillared Coordination Cage” Xin He, Cai-Yan Gao,
Mei-Xiang Wang, Liang Zhao*, Chem. Commun. 2012, 48, 10877–10879.
“Structural Diversity in Coordination Self-Assembled Networks of a Multimodal Ligand
Azacalix[4]pyrazine” Jin-Cheng Wu, Liang Zhao*, De-Xian Wang, Mei-Xiang Wang*,
Inorg. Chem. 2012, 51, 3860–3867.
“Dual Templated Synthesis of Silver Acetylide Cluster-encapsulated Supramolecular
Boxes” Cai-Yan Gao, Xin He, Liang Zhao*, Mei-Xiang Wang*, Chem. Commun. 2012, 48,
8368–8370.

Effective Utilization of Elements and its Chemical Applications

L-13
Macrocycle-directed Metal Cluster-centered
Coordination Self-assembly
Liang Zhao
Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China
Coordination-driven self-assembly has proven to be a powerful means of synthesizing various discrete
supramolecular metallacycles and metallacages.1 Therein, a single metal atom featuring specific coordinationgeometry often acts as coordination centers. In contrast, discrete coordination self-assembled
metallosupramolecules involving polynuclear metal clusters as centers are scarcely reported to date. In the past
two years, we have endeavored to establish a synthetic strategy for the construction of metal cluster-involved
supramolecular architectures from zero (0D) to three dimensional (3D). A series of metal cluster-centeredsupramolecular complexes have been built by silver-acetylide clusters and macrocyclic azacalix[n]pyridine
ligands.2-5 Further mechanism studies revealed that the positive homotropic allosteric effect between
macrocyclic ligands and metal ions plays a pivotal role in the synthesis of such metal cluster-involved
ensembles. This observation facilitated the generalization of this macrocycle-enhanced metal cluster synthetic
strategy in the synthesis of metal chalcogenide and halide cluster compounds. Potential applications of thesecomplexes are being extended by us to the following research fields: (i) new metal cluster-based functional
materials, (ii) supramolecular catalysts, (iii) supramolecular polymer based on metal cluster-macrocycle
building blocks, and (iv) bio-inspired molecular recognition and enzyme mimic.

Reference
1.
2.
3.
4.
5.

Chakrabarty, R.; Mukherjee, P. S.; Stang, P. J. Chem. Rev. 2011, 111, 6810–6918.
Gao, C.-Y.; Zhao, L.*; Wang, M.-X.* J. Am. Chem. Soc. 2011, 133, 8448–8451.
Gao, C.-Y.; Zhao, L.*; Wang, M.-X.* J. Am. Chem. Soc. 2012, 134, 824–827.
Gao, C.-Y.; He, X.; Zhao, L.*; Wang, M.-X.* Chem. Commun. 2012, 48, 8368–8370.
He, X.; Gao, C.-Y.; Wang, M.-X.; Zhao, L.* Chem. Commun. 2012, 48, 10877–10879.

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3rd CCS-CSJ, Young Chemists Forum

Yoshiaki Nakamura
Associate Professor of Applied Physics
Graduate School of Engineering Science, Osaka University
Address: 1-3 Machikaneyama-cho, Toyonaka, Osaka 560-8531,
JAPAN
Tel & Fax: (+81)-6-6850-6301
E-mail: nakamura@ee.es.osaka-u.ac.jp
 Educational Background

1997 B. Eng., Department of Applied. Physics,
Graduate School of Engineering, The University of Tokyo(supervisor: Prof. Fujio Shimizu)
1999 M. Eng., Department of Applied. Physics, Graduate School of Engineering,
The University of Tokyo(supervisor: Prof. Koji Maeda)
2002 Doctor of Engineering, Department. of Applied. Physics, Graduate School of Engineering,
The University of Tokyo(supervisor: Prof. Koji Maeda)

 Professional Career

2002 Research Associate: The University of Tokyo
2008 Associate Professor: Osaka University
2011 JST-PRESTO Researcher Research Interests

Optical properties and electronic states of nanodots
Thermoelectric study on nanodots on Si substrates
Heteroepitaxy using nanodots
Resistive switching effect using oxide nanodots

 Awards2002 Young Scientist Award in 9th International Workshop on Desorption induced By Electronic
Transitions
2006 Prize for Lecture Encouragement in The Japanese Society of Applied Physics

 Recent Publications
1.
2.
3.
4.
5.
6.

"Epitaxial Growth of High Quality Ge Films on Si(001) Substrates by Nanocontact Epitaxy"
Nakamura, Y.; Murayama, A.; Ichikawa, M., Cryst. Growth Des. 2011, 11, 3301.
"Nanocontact Heteroepitaxy of Thin GaSb and AlGaSb Films on Si Substrates Using Ultrahighdensity Nanodot Seeds" Nakamura, Y.; Miwa, T.; Ichikawa, M., Nanotechnology 2011, 22, 265301.
"Self-organized Formation and Self-repair of a Two-dimensional Nanoarray of Ge Quantum Dots
Epitaxially Grown on Ultrathin SiO2-covered Si Substrates" Nakamura, Y.; Murayama, A.;
Watanabe R.; Iyoda, T.; Ichikawa, M., Nanotechnology 2010, 21, 095305.
"Self-assembled Epitaxial Growth of High Density -FeSi2 Nanodots on Si (001) and their
Spatially Resolved Optical Absorption Properties" Nakamura,Y.; Amari, S.; Naruse, N.; Mera, Y.;
Maeda, K.; Ichikawa, M., Cryst. Growth Des. 2008, 8, 3019.
"Quantum-confinement Effect in Individual Ge1−xSnx Quantum Dots on Si (111) Substrates
Covered with Ultrathin SiO2 Films Using Scanning Tunneling Spectroscopy" Nakamura, Y.;
Masada, A.; Ichikawa, M.; Appl. Phys. Lett. 2007, 91, 013109.
"Quantum Fluctuation of Tunneling Current in Individual Ge Quantum Dots Induced by a Singleelectron Transfer” Nakamura, Y.; Ichikawa, M.; Watanabe, K.; Hatsugai, Y.; Appl. Phys. Lett.
2007, 90, 153104.

Effective Utilization of Elements and its Chemical Applications

L-14
Si-based Epitaxial Nanodots for Thermoelectric Material
Yoshiaki Nakamuraa,baGraduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
bJST-PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan

nakamura@ee.es.osaka-u.ac.jp
Nanostructuring has drawn much attention in thermoelectric study because of reduction effect ofthermal conductivity,  in nanomaterials. In various nanomaterials, we focused on the stacked epitaxial Si
nanodot (ND) structures on Si substrates. Our idea is that nanometer-scale interfaces reduce drasticallyand epitaxial growth of crystals can keep electric conductivity  (Fig. 1). In this paper, we develop theformation technique of the above stacked Si ND structures using ultrathin SiO2 film technique andmeasure their thermal conductivity.
Clean Si surfaces were oxidized at 500°C at the O2 pressure of 2 × 10-4 Pa to form ultrathin (~0.3 nm)
SiO2 films. Si was then deposited to form ultrahigh density (>1012 cm-2) Si NDs epitaxially grown on Si
substrates as the following. At first stage of Si deposition, nanowindows were created in the ultrathin SiO2
films through the reaction of Si + SiO2 → 2SiO↑, and Si NDs were subsequently formed on the ultrahighdensity nanowindows. The above Si ND formation process and oxidization process were repeated tofabricate the stacked Si ND structures.
The epitaxial growth of stacked Si NDs on Si substrates was confirmed by reflection high energy
electron diffraction and cross-sectional high resolution transmission electron microscopy. Unlike thenanocomposite, all NDs had almost the same crystal orientation and homogeneously distributed withultrahigh density. We measured thermal conductivity,  of these stacked Si ND structures. In the case of 3
nm Si NDs,  is measured to be ~0.6 W/mK which is below that of Si amorphous (~1-2 W/mK). This
demonstrates the possibility of our nanostructure as a Si-based thermoelectric material with high ZT.
This work was supported by PRESTO-JST program.

Figure 1. Schematic of stacked epitaxial Si NDs and our idea for reduction and  preservation.

28

3rd CCS‐CSJ, Young Chemists ForumEffective Utilization of Elements and its Chemical Applications

Date: March 24th (SUN) 9:00‐17:10
Venue: Room S9(CO‐LEARNING HOUSE II C601)
Ritsumeikan University, Biwako‐kusatsu Campus (Shiga, Japan)
Hosted by
The(CSJ)
Society

ChemicalChinese(CCS)

Society of Japan
ChemicalPublication： March 2013
Publisher:

The Chemical Society of Japan

1‐5, Kanda‐Surugadai, Chiyoda‐ku, Tokyo 101‐8307, Japanc The Chemical Society of Japan○