WELCOME 5 COMMITTESS 7 SPONSORI NG ORGANIZATIONS … · Gustavo de Miguel (UCLM, Toledo) María...

3

CONTENT

WELCOME ........................................................................................5

COMMITTESS ...................................................................................7

SPONSORING ORGANIZATIONS AND COMPANIES ................ 9

PROGRAM ........................................................................................ 11

ABSTRACTS

School: Lectures ........................................................................................ 13

Workshop: Oral Contributions ................................................................ 23

Posters ....................................................................................................... 47

AUTHOR INDEX ............................................................................ 95

5

WELCOME

Dear Colleagues and Friends;

Welcome to Toledo, the City of the three cultures, for the First Bilateral Spanish-

Japanese school/workshop on Nanotechnology and New Materials for Environmental

Challenges.

As you already know, the SJNANO 2011 meeting consists of one day school and 2

days workshop. The school will provide for the registered students high level talks done

by experts in the field of nanomaterials using a wide range of theoretical and

experimental tools for their study, and covering a broad landscape of applications as new

energy sources, materials for energy conversion, new catalysts, water treatment, eco-

friendly materials, etc. The two days workshop consists of 20 lectures and one poster

session, where state-of-the-art research result will be presented.

I hope that the oral and poster presentation not only will provide numerous

possibilities for stimulating discussions and communications between the partners of

ongoing projects, but can trigger collaborations between different groups in the Spanish-

Japanese partnership for science and technology. In fact that is one of the aims of this

first binominal meeting. Two poster-prizes will be awarded for the two best poster

presentations by Ph.D. students (one from Japan and the other one from Spain).

You are cordially invited to join the coffee breaks, lunch meals and the

conference dinner. Hope these “supposed” relaxed times will trigger more

communication for further exciting cooperation between the groups.

I would like to thank the members of international committee, Ignacio

Atorrasagasti, C. Bauluz, C. González from the Spanish Ministry of Science and

Innovation (MICINN), Prof. Katsumi Kaneko and Mrs. Suzuka Endo from the Japanese

Science and Technology (JST) Agency, and Dr. P. A. Serena (CSIC), for the invaluable

help, support and advices. Thanks also for the members of my group, especially to M.J.

Marchena, C. Martin, B. Cohen, N. Alarcos and G. De Miguel, and of course C. Blanco

Solis for making the website.

I wish also to thank the institutions, MICINN, JST and UCLM, and the companies

Innova (Madrid) and Picoquant (Berlin) for financial support of SJNANO2011, and

Pacifico-meeting agency for their help.

So, please enjoy the meeting !

Abderrazzak DouhalToledo, September 13th , 2011

Chairman of SJNANO2011

7

LOCAL ORGANIZING COMMITEES

LOCAL ORGANIZING COMMITEE:

Abderrazzak Douhal (UCLM, Toledo)

Noemí Alarcos (UCLM, Toledo)

Boiko Cohen (UCLM, Toledo)

Gustavo de Miguel (UCLM, Toledo)

María José Marchena (UCLM, Toledo)

Cristina Martín (UCLM, Toledo)

Juan Ángel Organero (UCLM, Toledo)

INTERNATIONAL ORGANIZING COMMITEE:

Juan Bisquert Spain

Avelino Corma Spain

Abderrazzak Douhal Spain

Masatake Haruta Japan

Katsumi Kaneko Japan

Nazario Martín Spain

Pedro Serena Spain

Yoshikazu Shinohara Japan

Takashi Tatsumi Japan

Masahiro Tatsumisago Japan

9

SPONSORING

The SJnano 2011 is organized in cooperation with the University of Castilla La

Mancha (UCLM, Toledo).

The SJnano 2011 is grateful to the following institutions and companies for

participation and support:

Universidad de Castilla La Mancha

Japan Science and Technology Agency

Ministerio de Ciencia e Innovación

Consejo Superior de Investigaciones Científicas

Innova Scientific S.L.

PicoQuant GmbH

11

PROGRAM

Wednesday (14th September)

SCHOOL MONITORING DAY

09:00 Opening

09:30 L1-L2 JP1 & JP2

11:10 Coffee break Coffee break

11:40 L3-L4 JP3 & JP4

13:20 Lunch Lunch

15:30 L5-L6 JP5 & JP6

17:10 Coffee break Coffee break

17:40 L7-L8 JP7 & JP8

19:30 Reception Reception

Thursday (15th

Sept) Friday (16th Sept)

WORKSHOP

09:00 P1-P3 P12-P14

10:30 Coffee break

11:00 P4-P6 P15-P17

13:00 Lunch

15:00 P7-P9 P18-P20 + Closing

16:30 Coffee break

Free Time to Visit Toledo

17:00 P10-P11

18:00-19:30 Poster

21:00 Dinner

School: Lectures

L1

15

THEORETICAL TOOLS FOR STUDYING METALLIC NANOPARTICLES

Mercedes Boronat,1 Avelino Corma

1

1Instituto de Tecnología Química, Universidad Politécnica de Valencia – Consejo

Superior de Investigaciones Científicas, Av. De los Naranjos S/n, 46022 Valencia, Spain

E-mail: [email protected]

The research effort devoted to understand the origin of the exceptional catalytic activity

of gold established that particle size, shape, and interaction with the support are key parameters,

but the direct and specific role played by each of these factors is not completely clear. In the last

years, theoretical modelling studies have become a powerful tool providing information about

fundamental aspects of catalysis, such as identification of active sites in heterogeneous catalysts

and determination of reaction mechanisms.

The key role played by the oxide or hydroxide support and by special Au sites at the

metal-support interface in the activation and dissociation of molecular O2 has been clearly

demonstrated, but it has also been shown that gold NP smaller than ~2 nm supported on inert

materials1 can dissociate O2. The ability of small isolated gold NP to dissociate O2 and the

possibility of generating a reactive surface oxide layer has been theoretically and experimentally

demonstrated.2 It is known that the presence of oxygen atoms on gold surfaces modifies the

chemical behavior of gold, but the nature of the new sites generated and their implication in the

mechanism of gold-catalyzed reactions is not fully understood yet. In this contribution we

analyze, from a theoretical point of view, the nature of the active sites generated on small

unsupported gold NP as a function of oxygen coverage, and try to establish their role in two

reactions of fundamental and industrial interest: alcohol oxidation to aldehydes and olefin

epoxidation.

On the other hand, the high chemoselectivity reported for the Au/TiO2 catalyst in the

hydrogenation of substituted nitroaromatics with molecular H2 has been attributed to a

cooperation between the gold NP, where H2 is dissociated, and the metal/support interface,

where nitrostyrene adsorbs selectively through the nitro group.3 H2 dissociation is the rate

determining step of the reaction, and in this contribution we analyze from a theoretical point of

view the nature of the active sites involved in H2 dissociation, and the possible ways in which

Au/TiO2 catalysts can be modified in order to increase their hydrogenation activity without

modifying their high chemoselectivity.

Acknowledgements Financial support from MAT2009-14528-C02-01, PLE2009-0046 and CONSOLIDER Ingenio

2010-MULTICAT is gratefully acknowledged. We thank Red Española de Supercomputación

(RES) and Centre de Càlcul de la Universitat de València for computational resources.

References [1]. M. Turner, V. B. Golovko, O. P. H. Vaughan, P. Abdulkin, A. Berenguer-Murcia, M. S.Tikhov, B. F. G.

Johnson, R. M. Lambert, Nature 454, 981, (2008). T. Ishida, H. Watanabe, T. Bebeko, T. Akita, M. Haruta, Appl.

Catal. A: General 337, 42, (2010). H. Tsunoyama, H. Sakurai, Y. Negishi, T. Tsukuda, J. Am. Chem. Soc. 127,

9374 (2005). H. Tsunoyama, N. Ichikuni, H. Sakurai, T. Tsukuda, J. Am. Chem. Soc. 131, 7086 (2009).

[2]. L. Alves, B. Ballesteros, M. Boronat, J. R. Cabrero-Antonino, P. Concepción, A. Corma, M. A. Correa-Duarte,

E. Mendoza, J. Am. Chem. Soc. 133,10251 (2011).

[3] A. Corma, P. Serna, Science 313, 332 (2006). M. Boronat, P. Concepción, A. Corma, S. González, F. Illas, P.

Serna, J. Am. Chem. Soc. 129, 16230 (2007).

L2

16

EXPLORING THE INTIMATE INTERACTIONS IN SILICA-BASED AND

DYE:TITANIA MATERIALS USING SINGLE MOLECULE FLUORESCENCE

MICROSCOPY AND ULTRAFAST SPECTROSCOPY

Abderrazzak Douhal

Departamento de Química Física, Facultad de Ciencias Ambientales y Bioquímica, and

INAMOL, University of Castilla La Mancha, 45071 Toledo, Spain.


Confinement of molecules by other molecules plays a key role in shaping the

spectroscopy and dynamics of the trapped systems. During the last 15 years, we have reported

on studies of the excited state dynamics of several guest molecules (including drugs)

encapsulated in various nano chemical and biological hosts.[1-3] In this lecture, I will outline

the concept of three laser-based techniques to witness the photoinduced changes in the

nanomatter. I will show some of our results, and their relevance to understanding the

photobehavior of confined systems. Using ultrafast spectroscopy and single molecule

fluorescence microscopy, we were able to get a detailed picture of the global photobehaviour of

the studied nanosystems. For the guests, we studied relatively simple molecules, like iodine, as

well as complex aromatic molecular systems, involving proton, electron and energy transfers,

either coupled or not with intramolecular twisting motions. As hosts, we used cyclodextrins,

micelles, Human Serum Albumin proteins, mesoporous materials and zeolites.

The fs-ensemble studies show the confinement effect on the relaxation photodynamics

and related pathways, as well as on the formed photoproducts, of the excited guest at short time

scale, while giving the time framework of the involved processes within the nanostructures. The

ps-single molecule fluorescence microscopy clearly shows the importance of preparation

methods of the studied molecular hybrid materials, and reveals how the photobehavior and

molecular distribution is affected by the different synthesis strategies. It further demonstrates the

electronic confinement concept at single-molecule level.

Acknowledgements: This work was supported by the MICINN and JCCM through the

projects: MAT2008-01609, Consolider Ingenio 2010 (CSD2009-0050, MULTICAT) and

PCI08-5868, respectively.

References [1]. A. Douhal et al., Angew. Chem. Int. Ed. Engl. 1997, 36, 1514.

[2]. A. Douhal et al., J. Phys. Chem. A, 1998, 102, 1657.

[3]. D.P. Zhong et al. PNAS (USA) 2000, 97, 14052.

[4]. A. Douhal, Chem. Rev. 2004, 104, 1955.

[5]. A. Douhal, Acc. Chem. Res. 2004, 6, 349.

[6]. A. Douhal et al. PNAS (USA) 2005, 102, 18807.

[7]. A. Douhal, Editor, ―Cyclodextrin Materials Photochemistry, Photophysics, and Photobiology‖, Elsevier,

Amsterdam, 2006, ISBN-13: 978-0-444-52780-6.

[8]. A. Douhal et al. J. Phys. Chem. B, 2007, 111, 5487.

[9]. A. Synak et al. J. Phys. Chem. C, 2009, 113,19199. [10]. M. Gil et al. J. Phys. Chem. C, 2010, 114 (14), 6311.

[11]. M. Gil et al. J. Phys. Chem. C, 2010, 114, 9554.

[12]. B. Cohen et al., J. Am. Chem. Soc, 2010, 132 (15), 5507.

[13]. M. Gil et al., J. Phys. Chem. C, 2010, 114, 9554.

[14]. B. Cohen et al. Phys. Chem. Chem. Phys., 2011, 13(5), 1819.

[15].B. Cohen et al. J. Phys. Chem. B. 2011, 115, 7637.

[16]. M. Ziolek et al. J. Phys. Chem. C, 2011, 115, 8858.

[17]. M. Marchena et al. J. Phys. Chem. B, 2011, 115, 2424.

[18]. M. Ziolek et al. Phys. Chem. Chem. Phys., 2011, 13, 4032.

L3

17

WHAT IS THERMOELECTRIC ENERGY CONVERSION?

Yoshikazu Shinohara

Eco-energy Group, Battery Materials Unit, National Institute for Materials Science

1-2-1, Sengen, Tsukuba, Ibaraki 305-0047, Japan


Thermoelectric energy conversion is a solid-state conversion applying the phenomenon

in which thermal energy is transported in a substance by carriers. Heating and cooling are

possible simply by passing an electric current in a substance. Such a kind of cooling device is

called as a Peltier device. Conversely, the conversion makes it possible to generate electricity

simply by creating a temperature difference in a substance. This type of energy conversion is

characterized by a simple mechanism, possible low temperature applications near room

temperature, no moving part, compactness and silence. It is regarded as an environment-friendly

energy conversion technology which can be used for consumer products.

Now we have the growing energy problems and global warming issues. Thermoelectric

energy conversion can realize power generation from renewable energy such as geothermal and

solar heat, and distributed exhaust energy at low temperatures, as well as cooling and heating

without CFC. A high performance thermoelectric conversion device is desired for effective

energy utilization.

The device comprises the top and

bottom plates, electrodes, thermoelectric

materials and junctions connecting the

electrodes and thermoelectric materials, as

shown in Fig.1. The device performance is

determined mainly by that of thermoelectric

materials, which is evaluated by the

thermoelectric figure-of-merit Z (=S2/) or

dimensionless figure-of-merit ZT. The

physical meaning of Z is an energy

conversion efficiency when a 1K

temperature difference is applied to the

material. Here, S, , , and T are the

Seebeck coefficient, electrical conductivity, thermal conductivity, and absolute temperature,

respectively. To achieve high Z or ZT in thermoelectric materials, improvement of the electrical

conductivity and Seebeck coefficient and reduction of thermal conductivity are necessary.

However, a trade-off relationship exists between these properties. For example, the electrical

conductivity is proportional to the carrier concentration, while the Seebeck coefficient decreases

with increasing carrier concentration.

In the lecture, I will introduce the principal and state-of-the-art of the thermoelectric

energy conversion.

Fig.1.Schematic view of thermoelectric device

High temperature side

Low temperature side

Current

L4

18

PERSPECTIVES FOR ZEOLITE CHEMISTRY AND CATALYSIS

Takashi Tatsumi

Division of Catalytic Chemistry, Chemical Resources Laboratory,

Tokyo Institute of Technology, Yokohama 226-8503, Japan


Over the past three decades, versatile approaches to the synthesis of zeolites have been

taken, leading to discoveries of a great many new synthetic zeolites. The Structure Commission

of International Zeolite Association has approved 197 framework types as of March 2011. The

availability of a great number of these synthetic zeolites has greatly expanded the realm of shape

selectivity in catalytic transformation and sorption accumulation since the diameter of the

channels and cavities are different depending on the structure. The use of organic structure-

directing agents (SDAs) has been the primary strategy for discovering new zeolites. Because

restrictions as to the molecular size are imposed by conventional zeolites, there has been a

continued interest in the synthesis of extra-large pore zeolites that can be used for the

manufacturing of fine chemicals such as pharamaceutical intermediates, fragrance, and organic

electronic materials and as well as for conversions of heavy oil fractions. The size, geometry,

rigidity, hydrophobicity, and stability of SDAs are very important factors that dominate the

crytsallization of zeolite structures. SDAs provided with rigidity have been found to be suitable

for giving large-pore multidimensional frameworks.

However, this type of complex molecule is not simply obtained from easily available

amines. The challenge is to synthesize these zeolites with inexpensive and easily available

SDAs. Moreover, to bring these zeolites into practical use as catalysts, facile methods for

synthesizing the zeolites need to be devised. We have developed a new methodology for

converting layered zeolite precursors into crystalline microporous materials with interlayer

zeolite pores expanded [1]. To overcome the diffusion problems that badly affect the

performance of zeolite catalysts, various strategies, including a decrease in the particle size and

the creation of additional meso/macro-porosities, have been successfully pursued, and the

outcomes are summarized in an excellent review [2].

Although zeolites have long been used as solid acid catalysts, zeolites are also endowed

with the redox property by the incorporation of a variety of metals. Metals other than aluminum

can be inserted into the zeolite framework, giving a group of materials named metallosilicates.

Striking developments have been attained in the oxidation catalysis exhibited by isolated

titanium atoms incorporated into the zeolite framework. TS-1, Ti-containing MFI zeolite,

proved to be a very good catalyst for the oxidation of various organic compounds using H2O2 as

oxidant, and several industrial processes utilizing TS-1 are being operated. We have discovered

that Ti-MWW catalysts exhibit catalytic performance superior to TS-1 in a variety of liquid-

phase oxidation reactions [3].

References [1] P. Wu, J. Ruan, L. Wang, L. Wu, Y.Wang, Y. Liu, W. Fan, M. He, O. Terasaki, T. Tatsumi, J. Am. Chem. Soc.

2008, 130, 8178.

[2] Y. Tao, H. Kanoh, L. Abrams, K. Kaneko, Chem. Rev. 2006, 106, 896.

[3] P. Wu, T. Tatsumi, Catal. Surveys Asia, 2004, 8, 137.

L5

19

THE INTERMEDIATE BAND SOLAR CELL: AN ATTRACTIVE CONCEPT

TO BE DEVELOPED

A. Luque

Instituto de Energía Solar – Universidad Politécnica de Madrid

ETSIT de Telecomunicación, Ciudad Univeritaria sn, 28040 Madrid, Spain

Email: [email protected]

This work will provide an overview of the progress made to date in the research of

intermediate band solar cells (IBSC). The general structure [1] of an IBSC is sketched in Fig. 1.

It consists of an ―intermediate band material‖ sandwiched in-between two conventional

semiconductors of p and n type. The ―intermediate band material‖, that gives its name to the

solar cell, is characterised by the existence of a collection of energy levels (intermediate band,

IB) located in-between the conduction and valence bands (CB and VB). This IB divides the

semiconductor bandgap, EG, in two bandgaps EL and EH.

Figure 1. Conceptual representation of the structure and operation of an intermediate band solar cell.

The practical implementation of the IBSC requires: a) the absorption of two sub-bandgap

photons where one photon pumps an electron from the VB to the IB and a second photon pumps

an electron from IB to the conduction band CB; b) that carrier relaxation between bands occurs

at a much lower rate than carrier relaxation within bands. The overview will cover several

theoretical aspects of importance for the understanding of the operation of the IBSC at

fundamental level as well as several material systems that have proven capable of actually

implementing intermediate band solar cells (quantum dots [2] , ZnTe:O [3] and GaNxAs1-x[4]

alloys).

References [1]. A. Luque and A. Martí, Progress in Photovoltaics: Res. Appl. 9, 73–86 (2001).

[2]. E. Antolin et al. " Journal of Applied Physics, vol. 108, p. 064513, 2010.

[3]. W. Wang, A. S. Lin, and J. D. Phillips, Applied Physics Letters, vol. 95, pp. 011103-3, 2009. [4]. N. Lopez et al." Physical Review Letters, vol. 106, p. 028701, 2010.

L6

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SEMICONDUCTOR QUANTUM DOTS FOR PHOTOVOLTAIC

APPLICATIONS

Iván Mora-Seró

Photovoltaic and Optoelectronic Devices Group, Departament de Física, Universitat

Jaume I, 12071 Castelló, Spain.


With energy conversion efficiencies in continuous growth, quantum dot sensitized solar

cells (QDSCs) are currently under an increasing interest, but there is an absence of a complete

model for these devices. The design of these cells have followed the previous designs on dye

sensitized solar cells, but the charge of the light absorbing material requires a new paradigm.1

Here, we compile the latest developments in QDSCs in order to attain high efficiency, modeling

the performance. CdS, PbS, PbS/CdS, CdSe, CdS/CdSe QDs, with ZnS, capping have been

grown directly on TiO2 surface by successive ionic layer adsorption and reaction (SILAR) to

ensure high QD loading. Polysulfide electrolyte and Cu2S counterelectrodes have been used to

provide higher photocurrents and fill factors, FF. Cells with efficiencies in the range of the

highest reported have been prepared and analyzed (4.0%, 2.7% and 1.9% for CdSe, PbS/CdS

and CdS respectively). A complete model of QDSC is given, explaining the differences found

among cells depending on: absorbing material, SILAR number of cycles, TiO2 nanostructure

and surface treatments. Current limitations of QDSCs are determined and further ways to

enhance cell performance discussed.

References: [1] I. Mora-Seró, J. Bisquert, J. Phys. Chem. Lett. 2010, 1, 3046–3052

L7

21

APPLICATION POTENTIAL OF CARBON-BASED NANOPOROUS

MATERIALS TO SUSTAINABLE TECHNOLOGY

Katsumi Kaneko

Research Center for Exotic Nanocarbons, Shinshu University, Wakasato, Nagano,

380-8553, Japan


Nanoporous carbons are quite important with the relevance to storage of clean

energies such as methane and hydrogen and electrical charges due to a remarkable

nanoconfinement effect1,2

. Accordingly there are active studies on nanoporous carbons from

various aspects. For example, new trials to produce carbon films having both of micropores

and mesopores, nanoporous carbons having both of hydrophilic and hydrophobic pores, and

C60-pillared single wall carbon nanotube were carried out3,4

The adsorption mechanism of

water vapor on hydrophobic nanoporous carbons has gathered a great interest. When the

nanoscale water layer in the hydrophobic pore contains ions, a nanoscale electrolytic

solution (nanosolution) is formed 5-7

However, we do not understand sufficiently water layer

and electrolytic nanosolution in nanoscale carbon pores. Supercapacitor is one of key

devices for construction of clean energy technologies. Understanding of the electrolytic

solution layers confined in nanoscale carbon spaces should induce a further progress in the

supercapacitor technology.8,9

This presentation will introduce recent understanding on the

structure of organic electrolytic solution in slit-shaped carbon nanopores10

.

In order to promote nuclear fusion technology, we need to establish a highly efficient

separation method of D2 from H2. Also we need to develop an isotopic separation route for

developing a new waste chemistry on radioactive 14

C. Quantum sieving is a potential

technique for separation of isotopes. In this presentation, the quantum molecular sieving

effect for H2/D2 and CH4/CD4 of single-wall carbon nanotube (SWCNT), single-wall

carbon nanohorn, activated carbon fibers, zeolites, and metal-organic framework materials

will be presented11-14

.

Acknowledgements: Exotic Nanocarbons, Japan Regional Innovation Strategy program

by the Excellence, JST supports K.K. and researchers at Shinshu University, GCOE

Chiba University support PhD students of Chiba University. The researches were supported

by Grant-in-Aid (A) and JST Isotope Separation Project .

References [1] K. Urita et al. J. Am. Chem. Soc. in press.

[2] S. Hashimoto et al, J. Am. Chem. Soc. 133, 2022 (2011). [3]Y,Tao et al, Appl. Phys. Lett. 93,19311 (2008) J. Amer. Chem. Soc. (2009), 131, 904.

J. Amer. Chem. Soc. 132, 1214(2010)

[4] S. Utsumi et al. Nano Lett,9, 3694 (2009).

[5] T. Ohba, et al, Nano Lett., 5, 227(2005), J. Am. Chem. Soc. 126, 156 (2004), Mol. Phys, 111, 6207 (2007).

J. Phys. Conf. 177, 0120010 (2009). [6] T. Ohkubo, et al, J. Am. Chem. Soc. 124, 11860 (2002), Physica Scr., T115, 685 (2005)

[7] T. Ohba et al. J. Phys. Chem. C. 113, 12622 (2009)

[8] C.-M. Yang,et al. J. Am. Chem. Soc., 129, 20 (2007).

[9] A. Tanaka et al, J. Amer. Chem. Soc. 132, 2112（2010）

[10] Tanaka H, et al, J. Am. Chem. Soc. 127 7511 (2005).

[11] Y,Hattori et al, J. Phys. Chem. B 110 9764 (2006)

[12] Noguchi D, et al, J. Am. Chem. Soc. 130 6367 (2008).

[13]H. Tanaka et al, J. Low Temp. Phys. 157, 352 (2009).

[14] D. Noguchi et al, J.Phys.:Condens.Matter 22, 334207 (2010)

L8

22

ULTIMATE STRUCTURES FOR POLY-IODIDE ELECTROLYTES OF DYE

SENSITIZED SOLAR CELLS

Shozo Yanagida1,2

1 Research Center for Advanced Science and Technology, The University of Tokyo

2Emeritus Professor of Osaka University

2-1 Yamadaoka, Suita-shi, Osaka 565-0871 JAPAN


Poly-iodide I

-/Im

- electrolytes (Im

-: m=3~7) play an essential role in DSC, showing

excellent charge diffusivity in bulk phase of DSC devices. At favorable concentration of I-

/Im- in DSC (I

- =0.60 M, I2=0.03 M), the charge diffusion takes place through electronic

diffusion mechanism, providing excellent performance for quasi-solid-state DSC like

gelled-electrolyte-based2 and ionic liquid crystal electrolyte-based DSC

3. The electronic

diffusivity is cleared by determination of charge transport of the I-/Im

- electrolytes using

microelectrode technique.1

Literature search reveals that tetramethylammonium poly-iodide (CH3)4N+Im

- (Im

-,

m=3, 5, 9) crystals show p-type semiconducting properties, and that the electrical resistivity

ranging from 107 to 10

10 Ω cm at room temperature, and the activation energy (1.3~2.3 eV)

for electronic conduction decreases with the increasing number of iodine atoms in Im-. The

dramatically enhanced conductivity of I5- and anisotropy of the conductance to the direction

of the iodine atom nets were reported. 4

The conductance was discussed in view of the

reported X-ray crystallography data, which indicate that I5- in [(CH3)4N

+]I5

- is packed in a

dense layered structure of

approximately square nets

containing five iodine atoms.

These facts and

computational analyses of Im-

(m=1, 3, 5, 7, 9) based on the

density functional theory give

their HOMO/LUMO

structure and energetic,

suggesting contribution of I5-

to electron diffusivity and to

redox reactions of I- and I3

- at

oxidized dye-molecules and

platinum or carbon on

cathode electrodes,

respectively.

Acknowledgment: Kind advice of Mr. Noritaka Uchida of Wavefunction, Inc. Japan

Branch Office.

References [1]. R. Kawano, M. Watanabe, Chem. Commun., 2003, 330–331.

[2]. W. Kubo, K. Murakoshi, T. Kitamura, S. Yoshida, M. Haruki, K. Hanabusa, H. Shirai, Y. Wada, S.

Yanagida, J. Phys. Chem., B 2001, 105, 12809 [3]. N. Yamanaka, R. Kawanao, W. Kubo, N. Masaki, T. Kitamura, Y. Wada, M. Watanabe, S. Yanagida, J.

Phys. Chem., B 2007, 111, 4763.

[4]. S. Kawai, R. Kiriyama, M. Uchida, S. Kusabayashi, H. Mikawa, Bull. Chem. Soc. Jap., 1965, 37, 799.

Workshop: Oral Contributions

OC1

25

NANO ISSUES IN THERMOELETRIC MATERIALS

Yoshikazu Shinohara,1 Yukihiro.Isoda,

1 Marisol S. Martín-González

2

1 Eco-energy Group, Battery Materials Unit, National Institute for Materials Science

1-2-1, Sengen, Tsukuba, Ibaraki 305-0047, Japan 2 Thermoelectrics group, IMM-Instituto de Microelectrónica de Madrid (CNM-CSIC)

Isaac Newton 8, PTM, E-28760 Tres Cantos, Madrid, Spain


Research and development into thermoelectric materials was intensified by the arms race

between the USA and USSR in the 1950s. At the time, many telluride compounds, including Bi2Te3

and PbTe, as well as SiGe, were found, and the fundamentals of the study of thermoelectric

materials were established. After the end of the cold war, research into consumer applications

advanced mainly using Bi2Te3.

Now we have the global warming issues by green house gases emission. When input energy

in our business activities is used more effectively, the amount of emitted green house gases will be

reduced. Since approximately three quarters of the input energy is exhausted just as waste heat,

thermoelectric energy conversion has been paid attention to as one of technologies that can recover

the exhausted heat energy.

Bi2Te3 shows the dimensionless figure-of-merit ZT (=S2/) of ~1.2 at near room

temperature. Here, S, , , and T are the Seebeck coefficient, electrical conductivity, thermal

conductivity, and absolute temperature, respectively. This value at near room temperature has not

exceeded by other materials. Social need for thermoelectric materials, however, is ZT of more than

2. We must overcome the gap between the present material performance and social need to

contribute to the global warming issues.

Nanotechnologies have been applied to improve the ZT value of thermoelectric materials

after Hicks and Dresselhaus‘ report in 1993[1]. Thin film structures by MBE, nano-composite

structures by sintering and nanowire structures were researched. These structures are understood to

be useful to reduce thermal conductivity. There are still the following problems left;

1) Most of nano-researches on thermoelectric materials were only model experiments to

demonstrate the expected nano-effect.

2) Reduction of thermal conductivity has a limited affect on improvement of the ZT

value.

3) Enhancement of Seebeck coefficient has not achieved clearly by nano-structures.

4) Social need can be answered to by overcoming the trade-off relation between

Seebeck coefficient and electrical conductivity as well as reduction of thermal conductivity.

In the presentation, I will show the state-of-the-art of thermoelectric materials including the

nano issues and our bilateral project.

References [1]. Hicks, L. D. and Dresselhaus, M. S. Effect of quantum-well structures on the thermoelectric figure of merit. Phys. Rev. B 1993, 47, 12727–12731.

OC2

26

BI2TE3 NANOWIRES ARRAYS BY ELECTRODEPOSITION

M.S. Martín-González, O. Caballero-Calero, J. Martín-Pérez, C.V. Manzano

1Nano-engineering thermoelectrics devices group.

IMM-Instituto de Microelectronica de Madrid (CNM CSIC). c/ Issac Newton 8, PTM

28760 Tres Cantos (Madrid) Spain.


The growing social alarm over increasing energy cost and global warming related to fossil

fuel sources has motivated the search for cleaner, more sustainable energy sources. Among the

different feasible technologies, thermoelectric (TE) devices have received attention as these solid-

state devices can generate electricity by harvesting waste thermal energy, thereby improving the

efficiency of a system. The many advantages of TE devices include solid-state operation, no noise,

zero-emissions, vast scalability, no maintenance and a long operating lifetime. The efficiency of TE

materials is directly related to a dimensionless figure of merit (ZT). In order to compete with

conventional refrigerators, a ZT=3 should be obtained. Although, a device with ZT>2 will be also

important in other applications. Due to their limited energy conversion efficiencies (i.e. ZT is ≈1),

thermoelectric devices currently are only present in niche applications.

However, there is a renewed interest in the field of thermoelectrics due to quantum size

effects, which provide additional ways to enhance energy conversion efficiencies in nanostructured

materials. For example, a ZT up to 2.5 was achieved by synthesizing two-dimensional

Sb2Te3/Bi2Te3 superlattice thin films through a chemical vapor deposition (CVD) process,

exceeding previous limits of ≈1 for bulk counterparts; theoretical calculations predict that even

higher ZTs can be achieved in one-dimensional nanowires.

In this work we present the advances we have performed in implementing the

electrodeposition of films and nanowires arrays of Bi2Te3 (the most well known thermoelectric

material) at IMM. We will also explain the influence of the different electrodeposition parameters in

the quality of the obtained films, the growth of porous alumina as a template to prepare the

nanowires, and the results obtained so far.

Acknowledgements: Authors would like to thanks the MICINN for financial support from

―FOMENTO DE LA COOPERACIÓN CIENTÍFICA INTERNACIONAL (FCCI) 2009.

Modalidad ACI PLAN E (JAPON ) Ref.: PLE2009-0073‖

References [1]. M.S. Martín-González, A.L. Prieto, R. Gronsky, T. Sands, and A.M. Stacy ―Insights into the Electrodeposition

Mechanisms of Bi2Te3‖ J. Electrochem. Soc., 2002, 149, C546-C554 [2]. A.L. Prieto, M.S. Sander, M.S. Martín-González, R. Gronsky, T. Sands, and A.M. Stacy ―Electrodeposition of

Ordered Bi2Te3 Nanowire Arrays‖ J. Am. Chem. Soc., 2001, 123, 7160

OC3

27

MOLECULAR STATES AND REACTIVITY OF METHANE ON SINGLE

WALL CARBON NANOTUBILITES

Katsumi Kaneko,1 Sachie Hashimoto,

2 Shuwen Wang,

2 Toshihiko Fujimori,

1

Tsutomu Itoh,1Tomonori Ohba,

2 Hirofumi Kanoh,

2

1Research Center for Exotic Nanocarbons, Shinshu University, Wakasato, Nagano, 380-8553, Japan

2Department of Chemistry, Graduate School of Science, Chiba University, Yayoi-cho,

Inage-ku, Chiba 263-8522, Japan


Single-wall carbon nanotubilites such as single-wall carbon nanotube (SWCNT) and single-wall

carbon nanohorn (SWCNH) have intensive application potentials to separation and storage of gases, new

reaction fields, electrodes, and new electronic devices. Hence, surface chemical functions of those single-wall

carbon nanotubilites should be elucidated for construction of new sustainable techniques. Carbon nanotubilites

have nanopore spaces which have much stronger interaction potential well for molecules than the slit-shaped

carbon nanopore spaces. Accordingly, we need to find interfacial function of the single wall carbon nanopore-

spaces.1 SWCNHs are prepared without any catalysts. A SWCNH particle has a tube of 2-3 nm in diameter

and the nanoscale windows can be donated by partial oxidation. Furthermore, infra-red light transparent the

wall of SWCNH. Therefore, the rotational vibrational spectrum of methane was measured with the aid of an

FT-IR spectrometer (JASCO, FT/IR-550) over the temperature range of 105 K to 140 K. Also Ni, Co, Fe, Cu

and their mixed nanoparticles-dispersed SWNNH were prepared to obtain an excellent catalyst for

decomposition of methane into carbon nanotube and hydrogen using temperature programmed reaction

method up to 1173 K.2 Ni-nanoparticles on alumina were also prepared for comparison.

Difference IR spectral changes for the 3 asymmetric stretching mode band of adsorbed CH4 on the

open-SWCNHs with increasing temperature from 105 to 140 K at P / P0=0.05 were measured. The gas phase

spectrum had characteristic rotational structures of the P and R branches. The difference IR spectrum of

adsorbed methane at 140 K shows P and R branches. However, these rotational structures become obscure

below 130 K, remaining in the explicit Q branch. An assembled structure of the adsorbed methane should

differ from that in the bulk liquid phase because of the lack of envelope curves of P and R branches as

expected for the bulk liquid. This behavior indicates that methane molecules lose their rotational freedom even

above 111 K of the boiling temperature in the nanopore spaces.2

Nano Ni particles-dispersed SWCNH showed a high decomposition reactivity of methane into

carbon nanotube and hydrogen. The decomposition starts at 670 K. However, the decomposition

temperature of Ni-Co nanoparticles-dispersed SWCNH is 630 K, being the lowest. In case of Ni

nanoparticles dispersed alumina, the decomposition starts at 770 K. It is noteworthy that even SWCNH

contributes to the high decomposition reactivity of methane.

Acknowledgements: This work was supported by Japan Science and Technology Agency Strategic

Japanese-Spanish Cooperative Program: Nanotechnologies and New Materials for Environmental Challenges.

Exotic Nanocarbons, Japan Regional Innovation Strategy program by the Excellence, JST supports K.K., T.T.,

and T.F. GCOE Chiba University supported PhD students of Chiba University.

References [1] Y. Aoki, K. Urita, D. Noguchi, T. Itoh, H. Kanoh,T. Ohba, M. Yudasaka, S. Iijima, K. Kaneko, Chem. Phys. Lett.

2009, 482, 269.

[2] M. Yamamoto, T. Itoh, H. Sakamoto, T. Fujimori, K. Urita, Y. Hattori, T. Ohba, H. Kagita, H. Kanoh, S.

Niimura, K. Hata, K. Takeuchi, M. Endo, F. Rodrígues-Reinoso, K. Kaneko, Adsorption, 2011, 17, 643.

[3] S. Hashimoto, T. Fujimori, H. Tanaka, K. Urita, T. Ohba, H. Kanoh, T. Itoh, M. Asai, H. Sakamoto, S. Niimura,

M. Endo, F. Rodoriguez-Reinoso, K. Kaneko, J. Amer. Chem. Soc.2011, 133, 2022. (2011).

OC4

28

NANOSTRUCTURED CARBON MONOLITHS FOR STORAGE AND

CONVERSION OF METHANE

Joaquín Silvestre-Albero, Manuel Martínez-Escandell, Antonio Sepúlveda Escribano,

Francisco Rodríguez-Reinoso

Laboratorio de Materiales Avanzados. Instituto Universitario de Materiales de Alicante -

Departamento de Química Inorgánica, Universidad de Alicante, Aptdo. 99, E-03080

Alicante, Spain


The main task of our research group in this joint project is the synthesis of activated carbon

monoliths with highly developed microporosity able to adsorb large amounts of methane and, if

possible, the synthesis of similar monoliths but with a slightly larger pore size (2-3 nm) in order to

stabilize methane hydrate within this porosity to enhance the storage of methane. An additional task

was the synthesis of highly dispersed heterogeneous catalysts based on these porous carbons for the

Japanese group to study the production of hydrogen and single wall carbon nanotubes from

methane.

Although several precursors have been used for the synthesis of the porous carbons, the best

results have been obtained with petroleum residues when subjected to chemical activation with

KOH; additionally, solid monoliths can be obtained by just conforming under pressure at a given

stage of the synthesis process. Carbons with surface area above 3000 m2/g and pore volume above

1.25 cm3/g have been obtained, with a very high gravimetric methane capacity; however, since the

bulk density of the monoliths is relative low (less than 0.45 g/cm3) the volumetric capacity (the one

of interest for the practical storage of methane) is not as large as expected (maximum values are at

around 150 V/V). The synthesis procedure was slightly modified in order to get carbons with very

high adsorption capacity but with the maximum in pore size distribution displaced to larger pore

dimension, around 3 nm, to favor the methane hydrate formation. Carbons of lignocellulosic origin

have also been prepared, in this case using chemical activation with ZnCl2 or H3PO4 in combination

with CaCl2; monoliths were obtained without the use of any binder. We were able to obtain

activated carbon with a very well developed mesoporosity, combined with a well-defined

microporosity.

On the other hand, a second issue the project deals with the design of carbon supported

catalysts for the decomposition of methane to yield hydrogen and nanotubes. In this first part of the

project we have studied the effect of the carbon support (activated carbon, expanded graphite or

graphitized carbon black) in the behavior on supported nickel catalysts. The best performance has

been obtained with the activated carbon supported catalyst, which is related to both the textural

properties of the support and to the size of the nickel particles.

Acknowledgements: Financial support from Ministerio de Ciencia e Innovación, Spain, (Project

PLE2009/0052) is gratefully acknowledged.

OC5

29

ORGANIC SDA-FREE SYNTHESIS OF ZEOLITES

Takashi Tatsumi, Toshiyuki Yokoi, Hiroyuki Imai

Division of Catalytic Chemistry, Chemical Resources Laboratory,

Tokyo Institute of Technology, Yokohama 226-8503, Japan


While organic structure-directing agents (OSDAs) are highly competent in affording new

and interesting zeolite structures, their cost may be too high for them to be used as commercial

catalysts and adsorbents. The challenge is to find ways to prepare these zeolites with cheaper

OSDAs or fewer amounts of OSDAs. The removal of OSDAs requires combustion that destroys

this expensive component. Furthermore, the associated heat generation in combination with the

formed water can be detrimental to the zeolite structure.

OSDA-saving or -free synthesis of zeolites has attracted much attention because such

approach can not only decrease the production steps and costs but also contribute to economical and

environmentally benign synthesis of advanced materials. There are numerous examples of OSDA-

free syntheses of zeolites such as A, X, Y, L, mordenite, ferrierite, and ZSM-5. Recently, Xiao and

his co-workers succeeded in the synthesis of beta zeolite by the addition of calcined beta seeds to

the starting aluminosilicate gel in the absence of any OSDAs [1].

We have focused our attention on the improvement in the synthesis of the RTH-type zeolite.

The RTH structure consists of the cages with the openings of 8MR and has two-dimensional

channels. Unfortunately, only two examples on the RTH-type zeolites were reported. One is a

borosilicate zeolite, ―RUB-13‖. It can be synthesized by using the mixture of OSDAs of 1,2,2,6,6-

pentamethylpiperidine (PMP) and ethylenediamine (EDA) [2]. The other is ―SSZ-50‖, which is an

aluminosilicate zeolite and will be useful as a solid-acid catalyst. Unfortunately, the synthesis of

SSZ-50 [3] requires the special OSDA, N-ethyl-N-methyl-5,7,7-trimethylazoniumbicyclo[4.1.1]-

octane cation, which is obtained through multiple and elaborate organic synthesis processes.

The use of such OSDAs could significantly limit the industrial use of RTH-type zeolites as

catalysts or adsorbents, and the drastic reduction in their amounts has been desired. After intensive

investigations, we succeeded in preparing the RTH-type zeolites without using any OSDAs [4].

The key points are the addition of sodium hydroxide and the molar composition of water as well as

calcined [B]-RUB-13 crystals as seeds. Thus prepared RTH-type zeolites synthesized without any

organic-templates are named ―TTZ-1‖ (Tokyo Tech. Zeolite) series. A pure phase of the RTH-type

borosilicate was hydrothermally synthesized in the absence of any OSDAs, the optimum molar

composition of the reactants being 1 SiO2 : 0.25 H3BO3 : 0.2 NaOH : 200 H2O (seed 2 wt%). We

have also been able to introduce Al into the RTH framework. We have found that these RTH-type

zeolites show remarkable catalytic performance in the methanol-to-olefins reaction.

On-going research is being made on the OSDA-free synthesis of zeolites of other topologies

such as TTZ-2 and -3 by utilizing the directing action of seeds.

References [1] B. Xie, J. Song, L. Ren, Y. Ji, J. Li, F. –S. Xiao, Chem. Mater. 2008, 20, 4533.

[2] S. Vortmann, B. Marler, H. Gies, P. Daniels, Microporous Mater. 1995, 4, 111.

[3] G. D. Lee, S. I. Zones, J. Solid State Chem. 2002, 167, 289. [4] T. Yokoi, M. Yoshioka, H. Imai, T. Tatsumi, Angew. Chem. Int. Ed, 2009, 48, 9884.

OC6

30

SYNTHESIS OF ZEOLITES USING PHOSPHOROUS-CONTAINING ORGANIC

STRUCTURE AGENTS.

Fernando Rey, Manuel Hernández-Rodríguez, Raquel Simancas

Instituto de Tecnología Química (UPV-CSIC). Avda. de los Naranjos s/n. 46022-Valencia.

Spain


The development of novel zeolites is mostly driven by the organic synthesis of new and

more complex tetraalkylammonium cations, which function as structure directing agent (SDA)

during zeolite crystallisation and remains occluded filling the void spaces of the zeolites. Upon

removal of the tetraalkylammonium cations, the characteristic porosity of the zeolites and the active

sites located in their structures are accessible to reactants. Then, it is of major interest to develop

new organic cations able to act as structure directing agents and which could help in controlling the

accessibility and/or the nature of zeolitic active sites. We will show that the employ of P-containing

–SDAs provides important benefits from the synthetic point of view and also allows controlling the

adsorption and acid properties of Al-containing zeolites.

This is particularly important for small pore zeolites, since 8-ring windows do not permit the

diffusion of phosphate anions and therefore, secondary treatments for softening of zeolite acidity

are not possible. This effect will be shown for the particularly important conversion of methanol to

light olefins (ethylene and propylene).

The use of P-containing SDAs also opens new possibilities for studying the role of organic

cations during crystallisation of zeolites and to locate them inside the zeolite pores by means of

Solid State NMR and X-Ray Diffraction techniques.

Finally, some new possibilities for unseen SDAs in synthesising new of microporous

catalysts or nanotechnological devices using this approach will be outlined and possibilities for their

advanced characterisation.

Acknowledgements: The authors acknowledge Spanish Government (projects MAT2009-14528-

C02-01 and PLE2009-0054) for financial support. R.S. and M.H.R. thank to UPV and MICINN for

Predoctoral fellowships, respectively.

OC7

31

DEVELOPMENT OF NEW ELECTROLYTE AND ELECTRODE MATERIALS

FOR ALL-SOLID-STATE THIN FILM LITHIUM BATTERIES THROUGH

SOLUTION PROCESS

Kiyoharu Tadanaga,1 Akitoshi Hayashi,

1 Masahiro Tatsumisago

1

Mario Aparicio,2 Alicia Durán,

2 Yolanda Castro

2, Francisco Muñoz

2

1Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture

University, Sakai, Osaka 599-8531, Japan 2 Instituto de Cerámica y Vidrio, Consejo Superior de Investigaciones Científicas, Madrid,

Spain 28049


Power supply or energy storage devices are an extremely important element in realizing

next-generation sheet devices, as it needs to be formed as a small, thin-film device. In the case of

the conventional secondary cells, organic liquid electrolytes are usually used, and there are still

safety concerns, such as leakage of liquid electrolyte and the likelihood of fires caused by a short-

circuit occurring between electrodes. Thus, thin-film lithium secondary battery supported on a

substrate must consist of all-solid state materials. For the fabrication of thin film batteries, physical

vapor processes, such as sputtering and PVD process, have been used. On the other hand, large area

and good quality, or nano-structured thin films can be prepared using solution processes. In the

solution processes, chemical compositions of thin films can be controlled, and rather thick films are

easily obtained. Thus, the solution process is very attractive for the development of thin film

batteries.

Our project attempts to develop new electrolyte and electrode materials for all-solid-state

thin film lithium batteries using solution processes, as a clean and efficient energy production and

storage device. Safe, thin-film lithium secondary cells which are free from such hazards as liquid

leakage and/or fires will be developed by employing electrolytes prepared from inorganic or

inorganic-organic hybrid solid-state materials by using solution processes.

In the initial stage of the project, thin films of LiMn2O4 electrode and Li2O-P2O5 solid

electrolyte were prepared by a sol-gel process and so-called the ―mist CVD process‖. In the mist

CVD process, aqueous solution of starting materials is ultrasonically atomized to form mist

particles with a size of about 3 m, and the mists are transferred by a carrier gas to the substrate to

form thin films. This process proceeds at atmospheric conditions, and aqueous solutions can be used

for the source. Thus, this process possesses advantages of safety, cost-effectiveness, light load to the

environment, and multiplicity of applying to a lot of materials.

Dense LiMn2O4 thin films with a thickness of about 750 nm were obtained with the

deposition of about 30 min in the mist CVD process, and these thin films were confirmed to work as

the positive electrode by the cyclic voltammetry and charge-discharge measurements. We also

confirmed that dense films of Li2O-P2O5 electrolyte with a thickness of about 5 m were prepared

by the mist CVD process, and ionic conductivity of the film with Li/P=1.5 was about 3 x 10-9

Scm-1

at room temperature.

OC8

32

LI4TI5O12 ELECTRODES AND HYBRID ORGANIC-INORGANIC

ELECTROLYTES THIN-FILMS FOR LITHIUM-ION MICROBATTERIES

John F. Vélez, Miguel Gómez, Yolanda Castro, Francisco Muñoz, Alicia Durán, Jadra

Mosa, M. Aparicio

Instituto de Cerámica y Vidrio (CSIC), Madrid, Spain 28049


Research in all-solid-state microbatteries arises to facilitate miniaturization, create more

flexibility for the design of stand-alone microelectronic devices and enhance the applicability in

(medical) implants due to the avoided leakage risks because of the substitution of liquid electrolytes

by solid electrolytes.

The first objective in the present work was the synthesis and characterization of thin-film

Li4Ti5O12 electrodes using a dipping sol-gel process. This oxide has a spinel structure, which has the

advantage that it undergoes only very minor volumetric changes (< 0.2%) upon cycling. Li-ion

intercalation occurs via a two-phase coexistence process, resulting in a very stable discharge voltage

between 1.5 and 1.6 V. One layer sol-gel coatings with thickness around 170 nm have been

prepared on glass, silicon and Au-coated quartz substrates using titanium isopropoxide and lithium

acetate as precursors. Low-angle X-ray analysis of coatings treated at temperatures between 500

and 800°C shows the presence of diffraction peaks at all temperatures. This is one of the advantages

of the sol-gel method: the possibility of producing compounds at lower temperatures compared with

other processing methods. However, only it is possible to obtain pure Li4Ti5O12 when an excess of

lithium precursor is incorporated. Cyclic voltammetry in a mixed solvent of ethylene carbonate and

diethyl carbonate containing 1.0 mol dm-3

LiPF6 show the two typical redox peaks around 1.55 V

vs. Li/Li+ for cathodic and anodic scans. Discharge and charge tests were performed at 10 µA in the

same electrolyte. Curves in both steps were very flat and their working potentials were also around

1.55 V vs. Li/Li+. Capacity at room temperature is very stable and close to the theoretical value of

610 mA h cm-3

.

The second objective was the synthesis and characterization of sol-gel thin-film hybrid

organic-inorganic electrolytes based on two different compositional systems: silica – methacrylate

and silica – epoxy. Starting precursors were lithium acetate (LiAc), tetraethylorthosilicate (TEOS),

methacryloxypropyl trimethoxysilane (MPS), hydroxyethyl methacrylate (HEMA) and

glycidoxypropyl trimethoxysilane (GPTMS). The hybrid nature of these materials makes it possible

to obtain homogeneous defect-free coatings with a wide range of thicknesses, from hundreds of

nanometers to several microns. The ionic conductivity determined by Electrochemical Impedance

Spectroscopy (EIS) reached valuesof 10-6

S/cm. Although these values are far from those obtained

with liquid electrolytes (10-3

S/cm), the extremely low thickness obtained with this methodology

partially compensates for the difference in conductivity.

Acknowledgements: This work has been supported by the Spanish Science and Innovation

Ministry under project PLE2009-0074 from National Program for I+D internationalising (ACI-

PLAN E). The funding comes from the Fondo Especial del Estado para la Dinamización de la

Economía y el Empleo (Plan E).

OC10

33

NOVEL GOLD CATALYSTS FOR GREEN CHEMISTRY AND EFFICIENT

ENERGY CONVERSION

Masatake Haruta,1 Takashi Takei,

1 Ayako Taketoshi,

1 Tamao Ishida

2

1Department of Applied Chemistry, Graduate School of Urban Environmental Sciences,

Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan 2Present address: Department of Chemistry, Faculty of Science, Kyushu University, 6-10-1

Hakozaki, Higashiku, Fukuoka 812-8581, Japan


This research project aims at creating a variety of gold catalysts for green chemistry and

efficient energy conversion through joint work with Professor Corma‘s group of the Polytechnic

University of Valencia (PUV). The major research targets are simpler organic syntheses, biomass-

derived chemical syntheses, and high efficiency energy conversion.

Supported gold nanoparticles (NPs) prepared by Tokyo Metropolitan University (TMU)

were tested for liquid phase organic reactions mainly in PUV. In the hydrogenation of 3-

nitrostyrene, Au/WO3 was found to be superior to the best gold catalyst (Au/TiO2) both in

conversion and selectivity to 3-aminostyrene. In the hydrogenation of chrotonaldehyde, Ir/TiO2 and

Au/TiO2 enhance the hydrogenation of C=O bond producing preferentially crotylalcohol (valuable

compound), while Pd and Pt catalysts preferred C=C bond hydrogenation. During the course of

catalyst survey, MnO2 showed high catalytic activity without gold NPs for the synthesis of

azobenzene from aniline and molecular oxygen.

Ethanol is produced in a large quantity by the fermentation of sugar canes and corn starch,

its transformation to acetaldehyde is encouraged to replace petroleum gas (ethylene) with renewable

resources. Gold NPs deposited on MnO2 or CeO2 could completely oxidize ethanol at temperatures

below 130 ℃, presenting better candidates for fuel cell anodes. Gold NPs deposited on MoO3

(strongly acidic), V2O5, or La2O3 (basic) produced acetaldehyde with selectivities above 90% [1].

The effect of support materials and the size of gold are interesting topics for further spectroscopic

and kinetic investigation.

Methanol is one of key chemical intermediates which can store and liberate hydrogen. If it

can be decomposed into H2 and CO by utilizing low-temperature waste heat, the enthalpy of the gas

mixture is increased by 17 %. This reaction was catalyzed efficiently nearly to equilibrium

conversion by gold NPs deposited on CeO2 or ZrO2 at temperatures below 200℃．

A big challenge in this project is to create powerful anode catalysts for fuel cells using

glucose as a fuel, because it can potentially provide 24 electrons per 1 molecule. Gold NPs were

deposited on carbon materials which were electron conducting. By pretreating carbon supports with

H2O2 or acidic aqueous solution, oxidation to produce formic acid was partly assisted. Gold NPs on

ketchen black combined with Fenton oxidation by use of supported Fe2O3 appreciably promoted

deep oxidation to formic acid.

Several lines of approach conducted jointly are opening a new area of gold chemistry and

novel heterogeneous catalysts.

References [1]. T. Takei, N. Iguchi, M. Haruta, New J. Chem. 2011, DOI: 10.1039/C1NJ20297A.

OC10

34

SUPPOSRTED GOLD NANOPARTICLES AS HETEROGENEOUS CATALYSTS

FOR AEROBIC OXIDATIONS AND SELECTIVE HYDROGENATIONS

Raquel Juarez,1 Tamao Ishida,

2 Hermenegildo Garcia,

1 Masatake Haruta,

2 and

Avelino Corma1

1Insituto de Tecnología Química CSIC-UPV, Av. De los Naranjos, Universidad Politécnica

de Valencia, 46022 Valencia, Spain 2Chemistry Department, Metropolitan University of Tokyo, Japan


Since the seminal discovery that gold nanoparticles exhibit a remarkable catalytic activity

for the selective, low temperature CO oxidation [1], there has been a considerable interest in

exploiting the unique activity of gold nanoparticles compared to that of other noble metals [2].

Besides CO oxidation, supported gold nanoparticles have been found extremely active for aerobic

oxidation of alcohols and other C-heteroatom functionalities as well as the selective hydrogenation

of nitro groups [3]. For many of these reactions, it has been found that for samples with the same

gold loading and the same gold particle size, the nature of the support can play a key role in the

catalysis. One example of in which the catalytic activity and selectivity of supported gold

nanoparticles depends largely on the support is the case of gold supported on nanoparticulate ceria.

In this case, it has been found that the activity of the catalyst depends on the ceria support particle

size and this fact has been interpreted considering that as the particle size decreases, oxygen

vacancies and lattice defects are gradually created in the ceria nanoparticles. These lattice defects

are suitable for interaction with oxygen as it is indicated in Scheme 1 for the case of alcohol

oxidation.

O2- vacancy

Au

Au+n

Ce(IV)

O2-

O

O

OH

R´R

HO2

R

O

R´

H2O

O

RR´

H

O2- vacancy

Au

Au+n

Ce(IV)

O2-

O2- vacancy

Au

Au+n

Ce(IV)

O2-

O

O

OH

R´R

HO2

R

O

R´

H2O

O

RR´

H

In the context of a joint Spanish-Japanese project, our research groups have been

collaborating by preparing a large series of supported gold nanoparticles in various metal oxide

supports obtained by various methods and checking their active ity for a series of tests reactions that

are of industrial relevance and that for which there is considerable information available. In

particular, we have studied the oxidation of 1-phenylethanol, selective hydrogenation of

nitrostyrene to aminostyrene and the methoxycarbonylation of aromatic amines using dimethyl

carbonate. The results obtained will be commented compared to the current most-competitive

catalyst.

Acknowledgements: The Spanish-Japanese joint initiative is thanked for partial funding of this research.

References [1]M. Haruta, T. Kobayashi, H. Sano and N. Yamada, Chemistry Letters, 2 (1987) 405.

[2]M. Haruta, Nature, 437 (2005) 1098.

[3]A. Corma and H. Garcia, Chemical Society Reviews, 37 (2008) 2096.

Scheme 1. Mechanistic proposal to rationalize

the influence of the ceria support and the

creation of oxygen lattice defects on the catalytic

activity of ceria supported gold nanoparticles

OC11

35

FULLERENE-BASED ORGANIC SOLAR CELLS

Nazario Martín

aOrganic Chemistry Department, Chemistry Faculty, Universidad Complutense de Madrid,

E-28040 Madrid, Spain, [email protected]. Fax: (+34) 91-394-4103; Tel: (+34) 91-

394-4227 bIMDEA-Nanociencia, Facultad de Ciencias, Ciudad Universitaria de

Cantoblanco, Módulo C-IX, 3a planta, 28049, Madrid, Spain

Energy is currently the most important problem facing mankind. The energy received from

Sun, calculated as 120 000TW (5% ultraviolet; 43% visible and 52% infrared), surpasses that

consumed on the planet over a year by several thousand times.1 Therefore, photovoltaic energy is

regarded as an important, clean and unexhausted renewable energy.

Photovoltaic (PV) solar cells are currently a hot topic in science, and since the first silicon-

based device prepared by Chapin in 1954 exhibiting an efficiency around 6%,2 different

semiconducting materials (inorganic, organic, molecular, polymeric, hybrids, quantum dots, etc.)

have been used for transforming sun light into chemical energy. Among them, photo- and electro-

active organic materials are promising due to key advantages, such as the possibility of processing

directly from solution, thus affording lighter, cheaper and flexible all-organic PV devices.

The design of new organic functional molecules able to harvest sun light and efficiently

undergo photon to current energy conversion processes is at the forefront of chemical challenges. In

this presentation, the fundamental contribution of chemistry to the multidisciplinary field of organic

photovoltaics is presented in a systematic way through the variety of organic compounds

synthesized to be successfully used in photovoltaic devices.3 Particular attention is devoted to the

advances produced in this field in our research group involving fullerenes and endofullerenes.4

Figure 1. Carbon nanostructures have played an important role in the preparation of efficient organic solar cells.

References [1] (a) N. Armaroli and V. Balzani, Angew. Chem., Int. Ed., 2007, 46, 52; (b) For further information about solar

energy, see the International Energy Agency Photovoltaic Power Systems Program at: www.iea-pvps.org. [2] D. M. Chapin, C. S. Fuller and G. L. Pearson, J. Appl. Chem., 1954, 25, 676.

[3] For a recent review: J. L. Delgado, P.-A. Bouit, S. Filippone, M. A. Herranz, N. Martín, Chem. Commun., 2010, 46,

4853–4865.

[4] a) Y. Takano, M. A. Herranz, N. Martin, S. G. Radhakrishnan, D. M. Guldi, T. Tsuchiya, S. Nagase, T. Akasaka, J.

Am. Chem. Soc. 2010, 132, 8048; c) D. M. Guldi, L. Feng, S. G. Radhakrishnan, H. Nikawa, M. Yamada, N. Mizorogi,

T. Tsuchiya, T. Akasaka, S. Nagase, M. A. Herranz, N. Martin, J. Am. Chem. Soc. 2010, 132, 9078

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36

GROWTH AND APPLICATION OF THREE-DIMENSIONAL QUANTUM DOT

SUPERLATTICE FOR HIGH-EFFICIENCY SOLAR CELLS

Toshiyuki Kaizu,1 Yoshitaka Okada

1

1Research Center for Advanced Science and Technology, The University of Tokyo

Tokyo 153-8904, Japan


Effciency enhancements exceeding the Shockley-Queisser limit of a

single junction solar cell [1] are possible in an intermediate band solar cell (IBSC) [2], which

incorporates a three-dimensional quantum dot (QD) superlattice in the active region of a pn junction

cell. The presence of IB leads to generation of a net electron-hole pair when 2 below-bandgap

photons are absorbed, i.e. one photon pumps an electron from the valence band (VB) to IB, while a

second photon pumps an electron from the IB to conduction band (CB). These electron-hole pairs

add to those produced by band-to-band transitions with photons above the bandgap energy that

excite electrons directly from VB to CB.

Experimental challenges to demonstrate IBSCs first require

fabrication of a close-packed three-dimensional QD superlattice. The second stage is to realize

ideally half-filled IB states to maximize photocurrent generation by two-step photon absorption,

which is the central operation principle of IBSC [3]. We have reported our first QD solar cell with

30 multi-stacked InAs/AlGaInAs QD layers fabricated on InP (311)B substrate by using strain

compensation technique [4]. Here the compressive strain locally induced around QDs is

compensated by tensile strain produced by the spacer layer. As a consequence, the size dispersion of

InAs QDs has significantly improved to ~ 12%. In recent studies, the strain-compensation technique

has been applied to demonstrate multi-stacked QDSCs with InAs/GaNAs material system [5-6].

Here an InAs QD layer with 2.0 monolayers (MLs) thickness and 20 nm-thick GaN0.01As0.99 strain-

compensating layer (SCL) are consecutively grown in pair up to 50 ~ 100 layers. The average QD

diameter, height, size uniformity in diameter, and in-plane density are 29.6 nm, 5.4 nm, 10.2 %, and

51010

cm-2

, respectively.

Acknowledgements: We would like to gratefully acknowledge Profs. A. Luque and A. Martí of

Universidad Politécnica de Madrid for their valuable comments and discussion. The Strategic

International Cooperative Program by Japan Science and technology Agency (JST) is also

acknowledged.

References [1] W. Shockley and H. J. Queisser, J. Appl. Phys. 32 (1961) 510.

[2] A. Luque and A. Martí, Phys. Rev. Lett. 78 (1997) 5014.

[3] A. Martí, L. Cuadra, and A. Luque, IEEE Trans. Electron Devices 48 (2001) 2394.

[4] Y. Okada et al, Proc. of 20th European Photovoltaic Solar Energy Conference, Barcelona (June 2005) 1AO.7.6.

[5] R. Oshima, A. Takata, and Y. Okada, Appl. Phys. Lett. 93 (2008) 083111.

[6] Y. Okada, R. Oshima and A. Takata, J. Appl. Phys. 106 (2009) 024306.

OC13

37

HIGH DENSITY QUANTUM DOT ARRAY FOR INTERMEDIATE BAND SOLAR

CELL

Antonio Luque

Instituto de Energía Solar, Universidad Politecnica de Madrid, 28040 Madrid, Spain


The intermediate band solar cell1 has been proposed as a concept able to substantially enhance the

efficiency limit of an ordinary single junction solar cell. If a band permitted for electrons is inserted within the

forbidden band of a semiconductor then a novel path for photo generation is open: electron hole pairs may be

formed by the successive absorption of two sub bandgap photons using the intermediate band (IB) as a stepping

stone. While the increase of the photovoltaic (PV) current is not a big achievement —it suffices to reduce the

badgap— the achievement of this extra current at high voltage is the key of the IB concept. In ordinary cells the

voltage is limited by the bandgap so that reducing it would also reduce the bandgap. In the intermediate band solar

cell the high voltage is produced when the IB is permitted to have a Quasi Fermi Level (QFL) different from those

of the Conduction Band (CB) and the Valence Band (VB). For it the cell must be properly isolated from the

external contacts, which is achieved by putting the IB material between two n- and p-type ordinary

semiconductors2. Efficiency thermodynamic limit of 63% is obtained for the IB solar cell

1 vs. the 40% obtained

3

for ordinary single junction solar cells. Detailed information about the IB solar cells can be found elsewhere4.

IB solar cells may be implemented by nanotechnology5. In particular the IB can be formed by the bound states of

quantum dots of a lower gap semiconductor located inside a wider bandgap host semiconductor. The first

practical realization was made with InAs QDs in a GaAs matrix6. Other groups have prepared similar devices

7-11.

Highest efficiency so far has been 18%10

. In reality present QD IB solar cells present a negligible increase of the

photocurrent and a substantial reduction of the voltage so that they always present less efficiency than test

structures of the same host semiconductor without QDs.

As matter of fact one of the reasons of this reduced efficiency is that the InAs/GaAs system is very

inappropriate. The increased thermodynamic efficiency limit is achieved for a bandgap of about 2 eV and a

position of the IB band at 0.7 e.V from the CB whereas in the InAs/GaAs system has a total bandgap of 1.42 eV

at room temperature and the position of the IB is at about 0.25-0.30 eV form the GaAs CB. Calculations12

show

that for these bandgaps the one-sun efficiency (the one referred to in all the cited publications) cannot exceed that

of the cell without IB although the case might be different under concentrated sunlight. However, this materials

system has permitted to experimentally prove the operational principles of this concept, namely the two photon

mechanism13

and the three QFL splitting14

and its direct consequence, the achievement of voltage very close to the

GaAs badgap15

. Unfortunately this has only been possible to detect13

or achieve15

at very low temperature when

the thermal escape has been suppressed.

The reduction of voltage of present QD IB solar cells is partly due to the reduction of minority carrier

lifetime introduced through the dislocations created by the stresses. This has been amended by stress reduction of

spacer increase and is not a major problem today. In part it is also due to the reduction of the bandgap due to the

invasion of the bandgap by the heavy hole states12,16

that form a quasi continuous. and by the formation of a

wetting later that acts as a quantum well12

. According to this, it is unfair use single gap cell without QDs with the

cell with QDs in the same host material. Changing the bandgap of the host material this problem is solved. Yet the

OC13

38

increase of current is very small and this is due by an inherent low absorption of the QDs for interband transitions.

We think that the CB wavefunctions have an envelope with S symmetry16

while this symmetry is absent in the

VB wavefunctions. The consequence is that the wavefunctions overlap poorly. We don‘t know yet the solution to

this problem, besides, of course, a photon management strategy to enhance the absorption.

References

1 A. Luque and A. Martí, Physical Review Letters 78, 5014–5017 (1997).

2 A. Luque and A. Martí, Progress in Photovoltaics: Res. Appl. 9, 73–86 (2001).

3 W. Shockley and H. J. Queisser, Journal of Applied Physics 32, 510-519 (1961).

4 A. Luque and A. Marti, Advanced Materials 22, 160-174 (2009).

5 A. Martí, L. Cuadra, and A. Luque, in Proc. 28th IEEE Photovoltaics Specialists

Conference (IEEE, New York, 2000), p. 940-943. 6

A. Luque, A. Martí, C. Stanley, N. López, L. Cuadra, D. Zhou, and A. Mc-Kee,

Journal of Applied Physics 96, 903–909 (2004). 7

S. M. Hubbard, C. D. Cress, C. G. Bailey, R. P. Raffaelle, S. G. Bailey, and D. M.

Wilt, Applied Physics Letters 92, 123512 (2008). 8

V. Popescu, G. Bester, M. C. Hanna, A. G. Norman, and A. Zunger, Physical Review

B 78, 205321 (2008). 9

R. Oshima, A. Takata, and Y. Okada, Applied Physics Letters 93, 083111 (2008). 10

S. A. Blokhin, A. V. Sakharov, A. M. Nadtochy, A. S. Pauysov, M. V. Maximov, N.

N. Ledentsov, A. R. Kovsh, S. S. Mikhrin, V. M. Lantratov, S. A. Mintairov, N. A.

Kaluzhniy, and M. Z. Shvarts, Semiconductors 43, 514–518 (2009). 11

D. Alonso-Alvarez, A. G. Taboada, J. M. Ripalda, B. Alen, Y. Gonzalez, L.

Gonzalez, J. M. Garcia, F. Briones, A. Marti, A. Luque, A. M. Sanchez, and S. I.

Molina, Applied Physics Letters 93, 123114 (2008). 12

A. Marti, E. Antolin, E. Canovas, N. Lopez, P. G. Linares, A. Luque, C. R. Stanley,

and C. D. Farmer, Thin Solid Films 516, 6716-6722 (2008). 13

A. Marti, E. Antolin, C. R. Stanley, C. D. Farmer, N. Lopez, P. Diaz, E. Canovas, P.

G. Linares, and A. Luque, Physical Review Letters 97, 247701-4 (2006). 14

A. Luque, A. Marti, N. Lopez, E. Antolin, E. Canovas, C. Stanley, C. Farmer, L. J.

Caballero, L. Cuadra, and J. L. Balenzategui, Applied Physics Letters 87, 083505-3

(2005). 15

E. Antolín, A. Martí, P. G. Linares, I. Ramiro, E. Hernández, C. D. Farmer, C. R.

Stanley, and A. Luque, in Proc.25 Photovoltaic Specialists Conference (IEEE,

Honolulu, 2010). 16

A. Luque, A. Marti, E. Antolín, P. G. Linares, I. Tobías, I. Ramiro, and E.

Hernandez, Solar Energy Materials & Solar Cells, to be published (2011).

OC14

39

TRANSPARENT CONDUCTIVE OXIDE-LESS DYE SENSITIZED SOLAR CELLS

CONSISTING OF FLEXIBLE NANOPOROUS TITANIA SHEET

-FLEXIBLE, CYLINDER, FIBER, AND HYBRID DYE-SENSITIZED SOLAR

CELLS-

Yuhei Ogomi,1 Shyam S. Pandey,

1 Yoshihiro Yamaguchi

2, Shuzi Hayase

1

1Kyushu Institute of Technology, 2-4 Hibikino,

Wakamasuku, Kitakyushu, 808-0196 Japan 2Nippon Steel Chemical Company Limited, 46-80, Nakabaru, Sakinohama, Tobata,

Kitakyushu, 804-8503 Japan


We present dye-sensitized solar cells consisting of flexible nanoporous titania sheets (TiO

sheet). The TiO was fabricated by coating a titania paste on a protected metal mesh sheet or glass

sheet.

1.Transparent conductive oxide-less DSCs (TCO-less DSC)1: We have also reported a

flexible DSC consisting of plastic sheet//TiO sheet/gel electrolyte sheet/Pt/Ti sheet and the

efficiency was 4.7 %. The efficiency of the TCO-less flexible DSC increased to 6.1 % by using a

TiO layer which was fabricated only on a top side of a protected porous metal sheet, where both of

top and bottom sides of the protected metal sheet had been previously covered by porous titania

layers.

2.TCO-less cylinder and fiber DSCs2,3

: TCO-less cylinder DSCs was fabricated by using

a round shaped flexible nanoporous titania sheet which was inserted into a glass tube. It is expected

that encapsulation becomes easy. 5.6 % efficiency is reported together with optical simulation.

Fiber DSCs consisting of the round shaped porous tiania sheet are also reported.

3.Hybrid DSC4,5

: Cocktail DSCs on which two dyes are randomly adsorbed on a titania

layer has been reported to cover wide ranges of wavelengths. However, because of unfavorable

interactions between two dyes, high efficiency has not been reported. We propose a DSC structure

consisting of two titania layers which is independently stained by two dyes, where electrons are

injected from both of titania layers. The DSC consists of glass/TCO/porous titania layer stained by

dye A (top electrode)/porous titania layer fabricated on a glass mesh sheet (bottom electrode)/gel

electrolyte sheet/Pt/Ti sheet. The top and bottom electrodes were contacted electronically by

pressing them. We proved that electrons were collected from both of top and bottom electrode by

using model two dyes. In addition, we report electron injection from two dyes which are bonded

with Metal-O-metal linkages.

These DSCs with flexible nanoporous titania sheet are expected to open new application

fields.

References [1]. Y. Yoshida, S. S. Pandey, K. Uzaki, S. Hayase, M. Kono, and Y Yamaguchi, Appl. Phys. Lett., 94, 093301 (2009).

[2]. J. Usagawa, S. S. Pandey, S. Hayase, M. Kono, and Y. Yamaguchi, Appl. Phys. Express, 2, 062203 (2009),

[3]. J. Usagawa, M. Kaya, S. S. Pandey and S. Hayase, Journal of Photonics for Energy, 1, 01110-1 (2011).

[4]. F. Inakazu, Y. Noma, Y. Ogomi and S. Hayase, Appl. Phys. Lett., 92, 093304 (2008).

[5]. K. Sadamasu, T. Inoue, Y. Ogomi, S. S. Pandey, and S. Hayase, Appl. Phys. Express, 4, 022301 (2011).

OC15

40

PHOTOPHYSICAL BEHAVIOR OF A RED ABSORBING SQUARAINE

SENSITIZER IN SOLUTION, SOLID STATE AND WITH TIO2

NANOPARTICLE THIN FILMS

A. Douhal,

1 G. de Miguel

1, M. Ziolek

1, M, Zitnan

1, M. J. Marchena

1, K. Abe

2, Y.

Ogomi2, S. S. Pandey

2 and S. Hayase

2

1Department of Physical Chemistry, Facultad del Medio Ambiente, University of Castilla-La

Mancha, Toledo, Spain 45071 2Kyushu Institute of Technology, 2-4 Hibikino, Wakamatsu, Kitakyushu, Japan


Femto- to millisecond dynamics of three types of squaraines (SQs) [1] molecules in solution, deposited onto quartz substrates and embedded in TiO2 nanoparticle thin films [2] were investigated by the

time-correlated single photon counting technique (TCSPC), femtosecond (fs) transient absorption

spectroscopy and nanosecond flash photolysis. In solution, the major deactivation pathway is a twisting

process with a potential energy barrier which is related to a growing of the dipole moment of the SQ due an intramolecular charge transfer reaction. In the solid state samples, strong exciton-exciton interaction in the

films provokes the formation of H- and J-aggregates. Deactivation kinetics of these species turned out to be

non-exponential with a power-dependence of the transient absorption signal, which indicates a singlet-singlet annihilation process to account for the rapid deactivation of the excited state of the aggregates. Absorption

spectra of the SQs embedded into TiO2 nanoparticles thin films show the presence of large amounts of

aggregates together with the monomer species. Quantum yield of the electron injection from the excited state of the SQ to the conduction band of the TiO2 is reduced in this sample due to the competition with the

singlet-singlet annihilation process. To reduce this undesired deactivation mechanism, a co-adsorption of the

SQs with chenodeoxycholic acid (CDCA) additive was carried out, lowering the aggregation in these

samples and therefore increasing the efficiency of the injection. Finally, the complete solar cell was prepared by adding the I

-/I3

- electrolyte and the Pt counterelectrode.

Figure 1. Femtosecond transient absorption (left) and nanosecond flash photolysis (right) decays of SQ 41 in TiO2 thin films with and without

the CDCA additive and with the I-/I3- electrolyte, representing the charge separation and recombination, respectively

Acknowledgements: This work was supported by the MICINN through projects MAT2008-01609 and

PLE-2009-0015. G. M. thanks the Ministerio de Ciencia e Innovación for a ―Juan de la Cierva‖ postdoctoral

fellowship

References [1] L. Beverina, P. Salice, Eur. J. Org. Chem. 2010, 1207.

[2] H. Choi, I. Raabe, D. Kim, F. Teocoli, C. Kim, K. J.-H. SongYum, J. Ko, M. D. Nazeeruddin, M. Grätzel, Chem. Eur. J., 2010, 16, 1193.

0 2 4 6 8 10 12 14

0.00

0.25

0.50

0.75

1.00 TiO2

TiO2 + CDCA

TiO2 + CDCA + I

-/I

3

-

A

/ a

.u.

Time / ps

SQ 41

exc

= 640 nm

0 1 2 3 4 5

0.00

0.25

0.50

0.75

1.00 SQ 41

exc

= 640 nm

TiO2

TiO2 + CDCA

TiO2 + CDCA + I

-/I

3

-

A

/ a

.u.

Time / s

OC16

41

QUANTUM DOT-SENSITIZED SOLAR CELLS BASED ON DIFFEERET MORPHOLOGIES OF TiO2 ELECTRODES TOGETHER WITH

PHOTOEXCITED CARRIER DYNAMICS

Taro Toyoda,1 Qing Shen

1,2

1Department of Engineering Science, Faculty of Informatics and Engineering, The University of

Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585, Japan 2 PRESTO, Japan Science and Technology Agency, 4-1-8 Honcho,

Kawaguchi, Saitama 332-0012, Japan E-mail: [email protected]

Semiconductor quantum dots (QDs) could be provided as a sensitizer for the sensitized solar cells [1,

2] due to its adjustable energy gaps, large intrinsic dipole moment, and large extinction coefficient.

Moreover, QD-sensitized solar cell has a capability of producing multiple exciton generation (MEG) [3]. We

demonstrate CdSe QD-sensitized solar cells based on different kinds of nanostructured TiO2 electrodes with

(1) conventional assembly of nanoparticles, (2) nanotubes [4], and (3) inverse opal structure (photonic

crystal) [2,5]. CdSe QDs were adsorbed on the nanostructured TiO2 electrodes by chemical bath deposition

[2,6]. Finally, the surface of electrodes were passivated by ZnS coating [7]. Sandwich structure solar cells

were prepared by using the Cu2S counter electrode [8]. Polysulfide solution was used as a regenerative redox

couple. Optical absorption characterization was carried out with photoacoustic (PA) spectroscopy [9,10].

Incident photon to current conversion efficiency (IPCE) and photovoltaic properties were investigated.

Photosensitization by CdSe QDs could be observed in the visible region. The maximum IPCE value of 75%

and the maximum photovoltaic conversion efficiency of 3.5% can be obtained. These values are relatively

high for semiconductor QD-sensitized solar cells. Photoexcited carrier dynamics is characterized with the

improved transient grating (TG) technique [11-13]. TG measurements show the fast (hole) and slow

(electron) relaxation processes with lifetimes of a few picosecond and a few tens to hundred picoseconds,

respectively. There are correlations between the lifetimes of photoexcited carrier dynamics and the

photovoltaic properties.

References [1] Q. Shen, D. Arae, and T. Toyoda, J. Photochem. Photobiol. A: Chem. 2004, 164, 75.

[2] L. J. Diguna, Q. Shen, J. Kobayashi, and T. Toyoda, Appl. Phys. Lett. 2007, 91, 023116.

[3] A. J. Nozik, Physica E 14, 115 (2002).

[4] Q. Shen, K. Katayama, T. Sawada, M. Yamaguchi, and T. Toyoda, Jpn. J. Appl. Phys. 2006,

45, 5569.

[5] L. Diguna, M. Murakami, A. Sato, Y. Kumagai, T. Ishihara, N. Kobayashi, Q. Shen, and

T. Toyoda, Jpn. J. Appl. Phys. 2006, 45, 5563.

[6] S. Gorer and G. Hodes, J. Phys. Chem. 1994, 98, 5338.

[7] Q. Shen, J. Kobayashi, L. J. Diguna, and T. Toyoda, J. Appl. Phys. 2008, 103, 084304.

[8] G. Hodes, J. Manassen, and D. Cahen, J. Electrochem. Soc. 1980, 127, 544.

[9] A. Rosencwaig and A. Gersho, J. Appl. Phys. 1977, 47, 64.

[10] T. Toyoda, S. Tsugawa, and Q. Shen, J. Appl. Phys. 2009, 105, 034314.

[11] Q. Shen, K. Katayama, M. Yamaguchi, T. Sawada, and T. Toyoda, Thin Solid Films 2005,

486, 15.

[12] Q. Shen, M. Yanai, K. Katayama, T. Sawada, and T. Toyoda, Chem. Phys. Lett. 2007, 442, 89.

[13] Q. Shen, Y. Ayuzawa, K. Katayama, T. Sawada, and T. Toyoda, Appl. Phys. Lett. 2010, 97, 263113

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42

CHARACTERISTICS OF ELECTRONIC PROCESSES AND MATERIALS OF

DYE-SENSITIZED SOLAR CELLS

Juan Bisquert

Photovoltaic and Optoelectronic Devices Group, Departament de Física, Universitat

Jaume I, 12071 Castelló, Spain


Understanding and improving the performance and stability of dye-sensitized solar cells

(DSC) requires to combine the microscopic models for the basic electronic processes governing the

solar cell operation (injection, transport, recombination, extraction) with macroscopic models that

are suited for complete device measurement. Based on large experience on DSC characterization by

Impedance Spectroscopy (IS), we are now interested to provide detailed understanding of the factors

determining the cell performance. I discuss here the relation between recombination resistance and

capacitance of the cell measured by IS, with the j-V curve both in the dark and under (1 sun)

illumination. We can provide a detailed energetic map that shows the limitation to injection

(photocurrent) and split of Fermi levels (photovoltage). Based on this approach, I discuss the recent

trends of progress and innovations such as the redox couples with more positive potential, or

alternative nanostructures. We mention some advances of the understanding of quantum dot-

sensitized solar cells and organic solar cells, using similar methods of analysis.

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43

MATERIALS DEVELOPMENT FOR AQUEOUS LITHIUM/AIR

RECHARGEABLE BATTERIES

Nobuyuki Imanishi, Tao Zhang, Hirokazu Ohkuma, Atsuhi Hirano,

Yasuo Takeda, Osamu Yamamoto

Department of Chemistry, Faculy of Engineering, Mie University,

1577 Kurimamachiyacho, Tsu, Mie, Japan 514-8507


Under the Strategic Japanese-Spanish Cooperative Program between JST and MICINN, our

group including three Japanese universities have started the collaboration research with two Spanish

universities. The title of the subject is ―New Perovskite Materials as Components of

Electrochemical Devices for Energy Generation‖. The scope of the work is to study innovative

materials as components of electrochemical devices for cleaner and more efficient energy

production, in particular solid oxide fuel cells and Li/air batteries. We focus on the perovskite

materials and attempt to optimize the performance of the electrochemical devices by selecting the

materials with the best electrical and catalytic properties. In my presentation, the possibilities and

challenges about Li/air batteries are introduced, of which related research works were mainly

conducted at Mie University.

Lithium/air rechargeable batteries attract much attention due to their potential applications in

electric vehicles. The high theoretical energy density of 11,140 Wh kg-1

excluding O2 for lithium/air

rechargeable batteries is comparable to that calculated for gasoline/air. Two types of lithium/air

battery systems have been studied, namely, non-aqueous electrolyte system1 and aqueous electrolyte

systems. Our group focuses on the latter system and has promoted the development of water-stable

lithium electrodes (WSLE), which can be used in aqueous electrolytes. WSLE is composed of a

lithium-metal active layer, a polymer membrane buffer layer of poly (ethylene oxide) (PEO) with

LiN(SO2CF3)2 (LiTFSI) salt, and a water-stable glass ceramics layer, Li1.35Ti1.75Al0.25P2.7Si0.3O12

(LTAP)2. The most important features required for a WSLE are low electrode resistance and no

dendrite formation at high current density.

The proposed lithium/air aqueous battery is constructed of a water stable lithium anode, a

LiCl saturated aqueous solution3, and a carbon/air electrode, where the perovskite-type oxide,

La0.8Sr0.2Co0.2Fe0.8O(LSCF), was used as the catalyst for oxygen reduction and evolution. The cell

showed a stable cell performance under air for a long period. The open-circuit voltage of the

carbon/LSCF-type electrode shows a little lower than that of the carbon-Pt electrode. There are

many choices for the catalyst, which have been studied as air cathode in the field of SOFC, but it

should have a bi-functional activity for oxygen reduction and oxygen evolution. The perovskite

oxide air electrode shows lower polarizations for the oxygen reduction and evolution than those of

the platinum electrode.

References [1]. A.Debart, A.J.Paterson, J.Bao, P.G.Bruce, Angew. Chem. Int. Ed., 47, 4521 (2008).

[2].T.Zhang, N.Imansihi, S.Hasegawa, A.Hirano, J.Xie, Y.Takeda, O.Yamamoto, N.Sammes, J.Electrochem. Soc., 155,

A965 (2008).

[3]. Y.Shimonishi, T.Zhang, N.Imanishi, D.Im, D.J.Lee, A.Hirano, Y.Takeda, O.Yamamoto, N.Sammes, J. Power

Sources, 196, 5128-5132 (2011).

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44

NEW PEROVSKITE MATERIALS AS COMPONENTS OF ELECTROCHEMICAL

DEVICES FOR ENERGY GENERATION

Susana García Martín,1 Miguel Ángel Alario Franco,

1 Emilio Morán Miguélez,

1 Juan

Peña Martínez,1 Subakti,

1 Daniel Muñoz Gil,

1 Alejandro Gómez Pérez,

1 Flaviano

García Alvarado,2 Ulises Amador Elizondo

2

1Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad

Complutense, 28040-Madrid, Spain 2Departamento de Química, Universidad San Pablo-CEU, Urb. Monte Príncipe, 28668-

Boadilla del Monte, Madrid, Spain


The excellent cathodic behaviour for solid oxide fuel cells of the oxide of composition

Ba0.5Sr0.5Co0.8Fe0.2O3-δ [1] has developed an enormous interest in the study of double-perovskite

materials. Moreover, some perovskites as for instance BaGdMn2O6-δ and BaGdCo2O6-δ present

layered-type ordering of the cations, which seems to favour the oxygen anion diffusion throughout

the structure [2]. These two facts have originated an increasing interest on materials based on

layered perovskites as cathodes for intermediate temperature-operating solid oxide fuel cells (IT-

SOFC). The electrical properties and electrochemical performance of BaGdCo2O5+δ have recently

been reported [3]. The low area specific resistance of this material on Ce0.8Gd0.2O2-δ electrolyte at

different temperatures indicates that it is acceptable as a cathode for IT-SOFC applications. Other

studies on double perovskites such as PrBaCo2O5+δ [4] and SmBaCo2O5+δ [5], have also

demonstrated a high cathodic performance of these oxides at intermediate temperature ranges.

The aim of our project is to study new materials of the systems A1-xA‘xB1- yB‘yO6-z (A=Sr,

Ba; A‘= rare earth elements; B, B‘= transition metals) with perovskite structure and the ordered

phases of Ba as cathodes for fuel cells and Lithium/air batteries. The work consists of the synthesis

of the oxides, study of their crystal structure and microstructure, study of their electrical and

electrochemical properties and performance of the materials on both electrochemical devices.

We present in here the main results of the work carried out during the first eight months of

the project and the near future perspectives on our research.

Acknowledgements: Authors thank the Spanish MICINN for funding Projects PIB2010JP-00181

and MAT2010-19837-C06 and CAM for Project MATERYENER-2, P2009/PPQ-1629.

References [1]. Z. Shao, S. M. Haile, Nature 2004, 431, 170.

[2]. A. A. Taskin et al. Progress in Solid State Chemistry 2007, 35, 481.

[3]. A.Tarancón et al. Mater. Chem. 2007, 17, 3175.

[4]. G. Kim et al J. Mater. Chem. 2007, 17, 2500.

[5]. Q. Zhou, He, T. Ji, Y. J. Power Sources 2008,185, 754.

OC20

45

NANOMATERIALS APPLICATIONS IN (BIO)SENSING PLATFORMS

Arben Merkoçi

ICREA & Nanobioelectronics and Biosensors Group, Institut Català de Nanotecnologia

Barcelona, Spain


The need for fast, low cost and efficient in-field testing of analytes with interest for

environmental monitoring or safety and security issues has increased enormously in the last few

years. In this context biosensor technology represents an interesting alternative for the development

of such devices that should in addition show user-friendly capacity. Between different biosensing

alternatives the nanotechnology and nanomaterial oriented biosensors represent very attractive

bioanalytical tools. The design for such a purpose of nanomaterials based biosystems with special

optical and electrochemical properties is bringing significant advantages. Heavy metals, pesticides

as well as proteins and even cells detections methodologies with interest for various applications

and based on nanomaterials (i.e. nonoparticles, nanochannels, graphene structures etc.) will be

described. The developed devices are based on the use of special platforms which allows their

future applications and extension in several fields. In addition these nanomaterials based

bioanalytical systems are being offered as excellent screening alternatives to sophisticate and high

cost equipments that require well prepared professionals for their use, including data treatment,

prior obtaining of final results with interest for further decisions taken in analysis/screening

scenarios.

Acknowledgements: We acknowledge MEC (Madrid) for the projects PLE2009-0050 and

MAT2008–03079.

References [1] A. Merkoçi, ―Nanoparticles-based strategies for DNA, protein and cell sensors‖, Biosensors and Bioelectronics 26

(2010) 1164–1177 [3] A. de la Escosura-Muñiz, C. Parolo, A. Merkoçi, ―Immunosensing using nanoparticles‖, Materials Today, 13 (2010)

24-34.

[2] G. Aragay, J. Pons, A. Merkoçi, Chemical Review, ―Recent Trends in Macro, Micro and Nanomaterials Based Tools

and Strategies for Heavy Metals Detection‖ 111 (2011), 3433-3458.

Posters

P1

49

ALL-SOLID-STATE LITHIUM SECONDARY BATTERIES USING LiCoO2

POSITIVE ELECTRODE AND Li2S-P2S5 SOLID ELECTROLYTES

Atsushi Sakuda, Akitoshi Hayashi, Kiyoharu Tadanaga, Masahiro Tatsumisago

Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture

University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan


Development of all-solid-state batteries using nonflammable inorganic solid electrolytes is

anticipated to improve the safety of batteries. To improve electrochemical performance of the all-

solid-state batteries, the formation of an effective electrode-electrolyte interface is important.

In the present study, LiCoO2 positive electrode particles were coated with Li2S–P2S5 solid

electrolytes (SEs) using pulsed laser deposition (PLD) to form favorable electrode-electrolyte

contacts; the electrochemical performance of the all-solid-state cells using the coated LiCoO2 was

investigated.

The SE thin film of 80Li2S·20P2S5 (mol%) was fabricated using PLD with a KrF excimer

laser ( = 248 nm, LPXPro, Lambda Physik). The SE film showed high lithium-ion conductivity of

about 10-4

S cm-1

at room temperature [1]. A target holder was attached to the upper side of the

PLD vacuum chamber, and a vibrating sample holder

was placed at the lower side. This PLD system allowed

the formation of an SE layer on the electrode particles.

During deposition of the SE, the electrode particles

were fluidized by a vibration system (VIB–FB, Nara

Machinery Co., Ltd.) to form a uniform SE layer on the

electrode particles [2]. To avoid exposure to air, an Ar-

filled glove box was connected to the vacuum chamber

for deposition.

Figure 1 shows the charge-discharge curves of

all-solid-state cells using LiCoO2 particles coated with

Li2S-P2S5 films. Those of all-solid-state cells usually

studied, which use the mixture of LiCoO2 and Li2S-

P2S5 particles as an electrode layer, are also shown for

comparison. The all-solid-state cells using LiCoO2

coated with Li2S-P2S5 films were charged and

discharged, and exhibited larger capacity than the cells

with the mixture of LiCoO2 and Li2S-P2S5 particles. A

favorable contact between electrode and electrolyte,

and effective lithium-ion conducting paths to the

electrode particles are formed by the Li2S-P2S5

coatings.

References [1]. A. Sakuda et al., J. Am. Ceram. Soc., 2010, 93, 765.

[2]. A. Sakuda et al., J. Power Sources, 2011, 196, 6735.

Fig. 1 Charge-discharge curves of all-solid-

state cells using LiCoO2 particles with Li2S-

P2S5 particles and coatings.

P2

50

THERMAL DIFFUSIVITY MEASUREMENTS OF POLIANILINE AND

POLIANILINE/NANOCLAY COMPOSITES

B. Abad1, P. Díaz-Chao,

1 A. Almarza

2, D. Amantia

2, S. Vázquez-Campos

2, F. Briones,

1

M. Martín González1

1 IMM-Instituto de Microelectrónica de Madrid (CNM CSIC), Isaac Newton 8, PTM,

E-28760 Tres Cantos, Madrid, Spain 2 Centro Tecnológico LEITAT C/ de la Innovació, 2 08225 Terrassa (Barcelona)


Nowadays one of the main society challenges is to obtain cleaner sources of energy.

Thermoelectric materials, which are able to convert heat into electricity and vice-versa, are one of

the candidates. Cost-Effective energy harvesting from temperature gradients requires thermoelectric

materials with high electrical conductivities and Seebeck coefficient, but low thermal conductivity.

Conducting polymer can fulfill these conditions if doped appropriately.

One of the most promising polymers is Polyaniline. In this work the thermal diffusivity of the

polyaniline and polyaniline with nanoclays has been studied, using a new experimental set-up at

IMM developed under NANOTERMA project. The novel system is based on the steady-state

method and it is used in order to obtain the thermal diffusivity of the polymers and their

nanocomposites, see figure 1.

Fig. 1 Experimental system built under the NANOTHERMA project

The thermal diffusivity is directly related with the thermal conductivity by this

expression . With the new experimental set-up, we are able to measure thermal diffusivity,

but we need to measure the specific heat to obtain the thermal conductivity. It is already made in

collaboration with technological center LEITAT by Differential Scanning Calorimetry (DSC).

Acknowledgements: Authors would like to thanks the MICINN for financial support from

―FOMENTO DE LA COOPERACIÓN CIENTÍFICA INTERNACIONAL (FCCI) 2009.

Modalidad ACI PLAN E (JAPON ) Ref.: PLE2009-0073‖

References

[1] J. R. Szczech, J. M. Higgins and S. Jin, J. Mater. Chem., 2011, 21, 4037–4055

P3

51

NEW SYNTHESIS OF PURE SILICA AND GE-CONTAINING SSZ-73 ZEOLITES

M. Hernández-Rodríguez, J. A. Vidal-Moya, J. L. Jordá, G. Sastre, T. Blasco, F. Rey

Instituto de Tecnología Química (UPV-CSIC)

Avda. De los Naranjos s/n, 46022-Valencia, Spain


Zeolite SSZ-73 (SAS) has been synthesized previously by Zones‘ group at Chevron [1] using a

highly selective Organic Structure Directing Agent as pure silica zeolite. Its synthesis as pure phase was

rather difficult because crystallization of RUB-13 (RTH) competes with SSZ-73 because different isomers of

the same OSDA direct the synthesis to these two phases [1,2]. Then, the synthesis of pure SSZ-73 relays on the purity of the OSDA, which is far for been trivial. Here, we report a convenient method for preparation of

pure SSZ-73 zeolite as pure silica and as Germania-silica materials. Also, the preferential occupation of Ge

of sites located at eight-ring has been demonstrated by means of X-Ray diffraction and Multi-Nuclei Solid State MAS-NMR spectroscopy.

In this work, SSZ-73 zeolites were obtained from synthesis gels having the following chemical

composition: x SiO2 : (1-x) GeO2 : 0.5 OSDA : 0.5 HF : 7 H2O, where x was varied from 1 to 0.667 (Si/Ge =

∞ - 2) and OSDA is the tri-tert-butyl-methyl-phosphonium hydroxide. The temperature and time of crystallization was varied in a very broad range.

Table 1 provides the Si/Ge ratio employed and the final chemical of the zeolites SSZ-73. There, it is

evident that the final products posses nearly the same Si/Ge ratios than the original crystallization media. Also, the Phosphorous contents in all the preparations of SSZ-73 is one OSDA in each cavity of SSZ-73

structure, being the same value than that obtained in previous zeolites SSZ-73 [1]. The crystallinity and

purity of the zeolites SSZ-73 was very high as deduced from their corresponding X-Ray diffraction patterns

shown in Figure 1.

The Rietveld analyses of the corresponding patterns permit to calculate the Germanium occupation

of the two crystallographic sites and the unit cell parameters of the SSZ-73 structure. The calculated Unit Cell volumes of the SSZ-73 samples do not follow any clear dependence with the Germanium content,

suggesting that there is a preferential sitting of Germanium in one of the two crystallographic sites. This has

been confirmed from the Rietveld analyses of the X-Ray patterns. Indeed, only T1 is occupied by Ge at low Germanium content, while T2 sites starts to be occupied at Germanium contents above 3.2 Ge atoms/U.C.

References [1]. D. S. Wragg et al., Chem. Mater. 19 (2007) 3924-3932.

[2]. C. Kim et al., Micropor. Mesopor. Mater. 116 (2008) 227–232.

Table 1. Chemical compositions of Zeolites SSZ-73

Sample (Si/Ge)gel (Si/Ge)solid P (mol/U.C.)

3.5Ge-SAS 3.5 3.5 1.96

5Ge-SAS 5 4.6 1.99

10Ge-SAS 10 9.1 2.02

15Ge-SAS 15 13.2 2.01

Si-SAS ∞ ∞ 1.98

Figure 1. XRD patterns of zeolites SSZ-73

P4

52

CATALYTIC METHANE DECOMPOSITION OVER CARBON SUPPORTED

NICKEL CATALYSTS

Robison Buitrago, Juan Carlos Serrano-Ruiz, Antonio Sepúlveda-Escribano,

Francisco Rodríguez-Reinoso

Laboratorio de Materiales Avanzados. Instituto Universitario de Materiales de Alicante -

Departamento de Química Inorgánica, Universidad de Alicante, Aptdo. 99, E-03080

Alicante, Spain


The catalytic decomposition of methane, CH4 C + H2 is an attractive reaction for COx-

free production of hydrogen, and it is even more interesting if carbon is obtained in the form of high

added value materials as carbon nanotubes and/or nanohorns [1].

This communication reports a study on the effect of the carbon support in Ni/C catalysts on

its catalytic behavior in methane decomposition. To this end an activated carbon, an expanded

graphite and a graphitized carbon black where impregnated with an alcoholic solution of

Ni(NO3)2·6H2O (Sigma-Aldrich 99.999% purity) with the appropriated concentration to obtain a 10

wt.% Ni.

The catalysts were tested under temperature-programmed conditions, from room

temperature to 1273 K, and under isothermal conditions at 693 K, with a gas stream of methane

diluted in helium. The gas exiting the reactor was monitored by on line mass spectroscopy, and the

catalysts were analyzed after reaction by TEM.

The obtained results showed that the activated carbon supported catalysts presented the best

performance, with a maximum of methane decomposition rate at 693 K. Fig. 1 shows the results

obtained in the temperature-programmed decomposition reaction with this catalyst, as well as the

TEM micrograph obtained after the reaction experiment, where the carbon nanotubes formed can be

are clearly seen.

400 500 600 700 800 900 1000 1100 1200 1300

Hydrogen

Methane

Temperature, K

Fig. 1. a) Methane decomposition performance of the Ni catalyst supported on activated carbon. b) TEM

image of the catalyst after the methane decomposition reaction at 693 K.

Acknowledgements: Financial support from Ministerio de Ciencia e Innovación, Spain (Project

PLE2009/0052) is gratefully acknowledged. R.B. thanks UA, CAM and Unión Fenosa for his

predoctoral grant (UF2007-X9159987F).

References [1]. Yongdan Li, et al. Catalysis Today. 2011, 162, 1-48.

P5

53

FUNCTIONAL HYBRIDS BASED ON ORGANOCATALYTIC BUILDERS INTO

MESOPOROUS FRAMEWORKS

Enrica Gianotti,1,2

Urbano Díaz,1 Avelino Corma

1

1Instituto de Tecnología Química (UPV-CSIC), Universidad Politécnica de Valencia,

Consejo Superior de Investigaciones Científicas, Valencia, Spain 46022 2Department of Chemistry IFM and NIS-Centre of Excellence, University of Turin, 10125 Turin,

Italy. E-mail: [email protected]

The heterogenisation of organic molecules though their insertion into the network of inorganic

matrixes has allowed to obtain organic-inorganic hybrid materials that cover a wide range of

applications in different areas as optics, electronics, energy, environment, biology, medicine,

catalysis [1]. In the field of heterogeneous catalysis, the organic-inorganic hybrids offer the

advantage to merge the properties of inorganic materials (high mechanical, thermal and structural

stability) and of organic moieties (flexibility and functionality). Moreover, the nature of the active

sites that can be introduced in the inorganic catalysts is limited, whilst the organic molecules can be

functionalised to catalyse a larger variety of reactions but suffer from their inability to be recycled.

In this view, the production of new organic-inorganic materials may overcome these drawbacks

allowing the structural insertion of the specific catalytic functions through the organic moieties,

while the inorganic part allows heterogenizing the catalyst and increasing the stability. In this way,

it should possible to design multifunctional materials [2]. In this contribution, the organic-inorganic

mesoporous materials have been produced using a NH4F-catalysed sol-gel process, at neutral pH

and low temperatures, that avoids the use of structural directing agents (SDAs) [3]. Proton sponges

have been used as the organic builder of the hybrids, while the inorganic part corresponds to silica

tetrahedra. The proton sponges are diamines with neighboring atoms at short distance and aromatic

frames, such as naphthalene and phenanthrene and exhibit high unusual basicity. The 1,8-

bis(dimethylamino)naphthalene (DMAN) [4], the archetype of proton sponge, with pKa=12.1 and

1,8-bis(tetramethylguanidino) naphthalene (TMGN) [5], a new organosuperbase, with pKa= 25.1,

have been heterogenized in a non-ordered mesoporous

silica.

The synthesised hybrids were studied as base

catalysts in Knoevenagel condensation. Several

recycling tests were also performed to evaluate the

catalyst deactivation and reusability. Additionally,

further experiments are carrying out to merge acid/base

active sites into the framework of mesoporous

materials.

References [1] Sànchez, C. et al., C.R. Chimie 2010, 13, 3.

[2] Wight, A.P., Davis, M.E., Chem Rev. 2002, 102, 3589. [3] Gianotti, E., Diaz, U., Coluccia, S., Corma, A., 2011, 13, 11702.

[4] Alder, R.W., Bowman, P.S., Steele, W.R.S., Winterman, D.R., Chem. Commun. 1968, 723.

[5] Raab, V., Kipke, J., Gschwind, R.M., Sundermyer, J., Chem. Eur. J. 2002, 8, 1682.

NN

NMe2 NMe2

NMe2NMe2 NMe2Me2N

DMAN TMGN

P6

54

ANALYSIS OF THE PHOTOLUMINESCENCE OF Zn1-X CdXO NANOWIRES

UNDER THERMAL ANNEALING

M. López-Ponce1, A. Hierro

1, J. M. Ulloa

1, P. Lefebvre

1*, G. Tabares

1, E. Muñoz

1,

K. Yamamoto1, A. Nakamura

2, J. Temmyo

2

1ISOM and Departamento de Ingeniería Electrónica U.P.M.,

Ciudad Universitaria s/n, 28040 Madrid, Spain 2Research Institute of Electronics, Shizuoka University,

3-5-1 Johoku, Hamamatsu, Shizuoka 432-8011, Japan

*present address: Laboratoire Charles Coulomb-CNRS-Université Montpellier, France


ZnO is a semiconductor material which has been studied intensively in the last decade for

optoelectronics applications. Its high energy direct bandgap (3.37 eV), large exciton binding energy

(60 meV) and the possibility to bandgap engineer by alloying with Mg and Cd, make this material a

strong competitor for this type of applications. Besides, it is relatively ease to obtain nanostructures

with ZnO and nowadays this could lead to attractive applications such as gas sensors which can

benefit from the large surface to volume ratio [1].

In this work, we have studied the photoluminescence response of ZnxCd1-xO-based

nanowires as-grown and thermally annealed, under vacuum and air conditions. The ZnxCd1-xO-

based nanowires were grown by MOCVD on a sapphire substrate, and are 1-3 µm in length and

100-200 nm in diameter. Four samples with different Cd contents (x=0, 14, 27 and 45) have been

analyzed.

Photoluminescence spectra were measured at room temperature of as-grown samples under

vacuum and in air conditions. An increase of the PL intensity has been observed when the

nanowires are measured under vacuum. This enhancement of the PL is related to the presence of a

depletion region that is formed at the surface as a result of surface states. When the nanowires are

exposed to air, O2 and H2O molecules are adsorbed at the surface trapping free electrons and

increasing this depletion region. Under vacuum conditions, these adsorption processes are avoided,

reducing the depletion region and increasing the PL intensity. This sensitivity to the presence of

gases depends on the Cd concentration, and is likely linked to the background residual electron

concentration of the nanowires, which affects the depletion region and thus the PL intensity.

Thermally annealing the nanowires allows one to obtain an increase of the PL intensity and a

reduction of its FWHM, likely related to a reduction of point defects within the nanowire. Increasing

the annealing temperature leads to a splitting of the ZnCdO PL emission into two bands,

corresponding to CdO and ZnO, but with no apparent degradation of the PL intensity or of the

nanowire structure as observed by SEM. The mechanisms responsible for this emission splitting will

be discussed.

References [1] Ü. Özgür et al., ―A comprehesive review of ZnO materials and devices‖, Journal of Applied Physics, vol.98, pp.

041301, August 2005.

P7

55

CARRIER DENSITY AND INTERFACIAL KINETICS IN MESOPOROUS TIO2

DURING WATER SPLITTING DETERMINED BY IMPEDANCE

SPECTROSCOPY

Sixto Giménez, Halina Dunn, Pau Ródenas-Motos, Francisco Fabregat-Santiago, Eva

María Barea, Roberto Trevisán, Antonio Guerreo, Juan Bisquert

Grup de dispositius Fotovoltaics i Optoelectrònics, Departament de Física, Universitat

Jaume I, 12071 Castelló, Spain


Water splitting at a semiconductor/solution interface with the only input of sunlight to

generate Hydrogen is one of the most attractive strategies to produce and store chemical energy

[1,2]. In the present study we have investigated carrier dynamics and interfacial kinetics of water

splitting with mesoporous TiO2. We have monitored the electron dynamics by electrochemical

impedance spectroscopy in order to indirectly extract information about hole dynamics. The

applicability of the transmission line model for mesoporous semiconductors has been validated to

identify chemical capacitance, transport resistance and charge transfer resistance in this system by

testing samples of different thicknesses and under different experimental conditions (in the dark,

under illumination and with/without hole scavengers in the solution). We found that both transport

resistance and chemical capacitance scale well with sample thickness, while charge transfer

resistance scales with thickness when the FTO substrate is not exposed to the solution. Otherwise,

there is a competition between charge transfer through TiO2 and through the FTO substrate. Under

illumination, the electron density is dominated by photogenerated carriers at biases below the open

circuit potential, whereas at higher bias, the applied potential determines the electron density. As

expected, the addition of hole scavengers greatly improves both photostability and photocurrent for

TiO2. This improvement can be correlated to the decrease of charge transfer resistance.

Acknowledgements: The authors acknowledge the support of from Ministerio de Cíencia e

Innovación under Project HOPE CSD2007-00007 and the Ramon y Cajal program and Generalitat

Valenciana under Project PROMETEO/2009/058.

References [1]. A. Fujishima, K. Honda, Nature 1972, 238, 37.

[2] M.G. Walter, E.L. Warren, J.R. McKone, S.W. Boettcher, Q.X. Mi, E.A. Santori, N.S. Lewis, Chemical Reviews,

2010, 110, 6446.

P8

56

FEMTO- TO MILISECOND DYNAMICS OF SQUARAINE MOLECULES

EMBEDDED IN TIO2 NANOPARTICLES THIN FILMS

G. de Miguel

1, M. Ziolek

1, M, Zitnan

1, M. J. Marchena

1, K. Abe

2, Y. Ogomi

2, S. S.

Pandey2, S. Hayase

2 and A. Douhal

1

1Department of Physical Chemistry, Facultad del Medio Ambiente, University of Castilla-La

Mancha, Toledo, Spain 45071 2Kyushu Institute of Technology, 2-4 Hibikino, Wakamatsu, Kitakyushu, Japan


Photodynamic of three types of squaraines (SQs) [1] molecules deposited onto quartz

substrates and embedded in TiO2 nanoparticle thin films [2] have been studied by means of steady-

state and time-resolved absorption techniques with the aim of a better understanding of their excited

state properties. In pure SQs thin films, the formation of two species at the excited state, monomer

and H- or J-aggregates was proved. Non-exponential fit of the experimental time profiles together

with the power-dependence of the transient absorption signal makes us to propose a singlet-singlet

annihilation process to account for the rapid deactivation of the aggregate excited state. In SQs

embedded in TiO2 nanoparticles thin films, we only detected the formation of H-aggregates and

monomer species. However, co-adsorption of the chenodeoxycholic acid (CDCA) additive

eliminates considerably the aggregation. Femtosecond transient absorption measurements revealed

competition between the charge injection and the annihilation process in the samples without the

CDCA, which reduces the efficiency of the system. However, in the samples with CDCA, charge

injection is quantitative. On the other hand, rate constant for charge recombination turned out to be

one order of magnitude higher for the samples with CDCA, which leads to slower recombination in

the samples exhibiting the aggregates.

Figure 1. Femtosecond transient absorption (left) and nanosecond flash photolysis (right) decays of the three SQs in

TiO2 thin films with the CDCA additive, representing the charge injection and recombination, respectively.

Acknowledgements: This work was supported by the MICINN through project MAT2008-01609

and PLE-2009-0015. G. M. thanks the Ministerio de Ciencia e Innovación for a ―Juan de la Cierva‖

postdoctoral fellowship

References [1] L. Beverina, P. Salice, Eur. J. Org. Chem. 2010, 1207.

[2] H. Choi, I. Raabe, D. Kim, F. Teocoli, C. Kim, K. J.-H. SongYum, J. Ko, M. D. Nazeeruddin, M. Grätzel, Chem.

Eur. J., 2010, 16, 1193.

0 10 20 30 40 50

0.00

0.25

0.50

0.75

1.00

SQ 26

SQ 4

SQ 41

A

/ a

.u.

Time / ps

SQs in TiO2 + CDCA

exc

= 660 nm

0.0 0.5 1.0 1.5 2.0

0.00

0.25

0.50

0.75

1.00 SQ 4

SQ 26

SQ 41

A

/ a

.u.

Time / s

SQ + TiO2 + CDCA

exc

= 660 nm

P9

57

NANOMATERIALS BASED STRATEGIES FOR HEAVY METALS DETECTION

Gemma Aragay,1 Josefina Pons,

2 Arben Merkoçi

1,3

1Nanobioelectronics and Biosensors Group, Institut Català de Nanotecnologia ICN-CIN2,

Bellaterra, Catalunya, Spain 2Universitat Autònoma de Barcelona, Bellaterra, Catalunya, Spain

3ICREA, Barcelona,Catalunya, Spain


Pollution from heavy metals is a major concern throughout the world due to the high toxicity

for the environment and the human health these represent. This fact has led to the development of

many proofs of concepts laboratory systems and technologies focused on the heavy metals detection

in different fields including food safety, clinical analysis and environmental industry. Providing new

tools and tactics for heavy metals sensing is essential to ensure a high quality of citizen‘s life.

Considering the high demand for pollution control our research has been focused on the

development of different strategies for heavy metals detection using either electrochemical or

optical strategies.1

Electrochemical methods, and particularly square wave anodic stripping voltammetry

(SWASV), offer several advantages related with cost, simplicity and low detection limits. In

addition to the mentioned advantages, the miniaturization of the system by using screen-printed

electrodes (SPE) is possible. Different studies performed for heavy metals detection (Cd2+

, Pb2+

,

Cu2+

and Hg2+

) in water using either mercury-coated or carbon nanoparticles-based SPE including

the analytical performance parameters, SPE ‗s lifetime studies, temperature effects and some studies

about the different heavy metals deposition profiles among others will be presented.2,3

Optical techniques have also been applied for heavy metals detection based on light

absorption and light emitting techniques. On one hand, the use of gold nanoparticles combined with

the use of N-alkylaminopyrazole ligands as specific receptors has been used for the colorimetric

detection even at naked eye of heavy metals down to 10 ppb of Hg2+

.4 Gold nanorods are also being

used in a similar system achieving lower detection limits. This work is still under study in our

laboratories.

On the other hand, the use of free N-alkylaminopyrazole ligands for heavy metals detection

based on fluorescence techniques has also been achieved down to 0.1 ppb of Hg2+

.5

Acknowledgements: The authors would like to acknowledge MEC (Madrid) for the projects

PLE2009-0050 and MAT2008–03079. G.A. thanks Generalitat de Catalunya for the predoctoral

fellowship (FI 2009).

References

[1]. G. Aragay, J. Pons, A. Merkoçi Chem. Rev. 2011, 111, 3433–3458.

[2]. G. Aragay, A. Puig-Font, M. Cadevall, A. Merkoçi J. Phys. Chem. C, 2010, 114, 9049-9055.

[3]. G. Aragay, J. Pons, A. Merkoçi J. Chem. Mat. 2011, 21, 4326-4331.

[4]. G. Aragay, J. Pons, J. Ros, A. Merkoçi Langmuir, 2010, 26, 10165-10170.

[5]. G.Aragay, H. Montón, J. Pons, M. Font-Bardía, A. Merkoçi, work submitted.

P10

58

NEW PEROVSKITES IN THE LA-SR-NI-TI –O AS ELECTRODES FOR SOLID

OXIDE FUEL CELLS AND LITHIUM AIR BATTERIES: STRUCTURAL,

ELECTRICAL AND ELECTROCHEMICAL CHARACTERISATION

J. C. Pérez-Flores1, C. Ritter

2, D. Pérez-Coll

3, G. C. Mather

3, J. Canales-Vázquez

4,

M. Gálvez4, F. García-Alvarado

1, U. Amador

1

1 San Pablo CEU University, Chemistry Department, Urb. Montepríncipe, Boadilla del

Monte, E-28668 – Madrid (Spain) 2

Institut Laue-Langevin, BP 156-38042 Grenoble Cedex 9(France)

3 Instituto de Cerámica y Vidrio-CSIC, Campus Cantoblanco, C/Kelsen 5, E-28049- Madrid

(Spain) 4Instituto de Investigación de Energías Renovables –UCLM, Campus Universitario s/n, E-

02071 – Albacete (Spain)

The effect of doping La2NiTiO6 with Sr, on the structure and the properties of the resulting

La2-xSrxNiTiO6- (0 ≤ x ≤ 0.5) solid solutions will be presented. Structural characterization was

performed by X-ray diffraction (XRD) and neutron powder diffraction (NPD). Chemical titration

and thermo-gravimetric analysis (TGA) in different atmospheres were used to determine the cationic

oxidation states. Finally, impedance spectroscopy was used to characterize the electrical properties

of the materials [1].

The La2-xSrxNiTiO6- series presents a double perovskite structure with a 2apx2apx2ap cell

and a change in symmetry from monoclinic (P21/n) for low Sr contents (x ≤ 0.1) to orthorhombic

(Pnma) for x > 0.1.

Two charge compensating mechanisms operate as La3+

ions are substituted by Sr2+

: a)

oxidation of Ni2+

to Ni3+

and b) creation of oxygen vacancies. Both have been experimentally

observed in La2-xSrxNiTiO6-. Chemical titration and thermal analysis indicated that they operate to

a different extent since only a small (but significant) part of nickel is oxidized to a trivalent state.

Thus, oxygen vacancy creation is the main charge-compensating mechanism in these compounds, as

confirmed by neutron diffraction. The electrical properties of the La2-xSrxNiTiO6- materials in air

show an important concentration of p-type charge carriers with lower Ea as dopant concentration

increases.

Presently, we are investigating the electrochemical activity of this high oxygen deficient

perovskite in order to assess its possible use as the catalytic component of solid oxide fuel cell and

lithium air battery electrodes.

Acknowledgements: We thank Ministerio de Ciencia e Innovación and Comunidad de Madrid for

funding the projects MAT2007-64486-C07-01, PIB2010JP-00181 and S2009/PPQ-1626

respectively.

References [1]. J. C. Pérez-Flores, C. Ritter, D. Pérez-Coll, G. C. Mather, F. García-Alvarado, U. Amador, J. Mater. Chem., DOI:10.1039/C1JM11975C.

P11

59

PREPARATION OF HIGH-PERFORMANCE BISMUTH TELLURIDE FILMS BY

ELECTRODEPOSITION.

Olga Caballero-Calero,1 Pablo Díaz Chao,

1 Begoña Abad,

1 Marisol Martín-González

1

1IMM-Instituto de Microelectrónica de Madrid (CNM CSIC) Isaac Newton 8, PTM,

E-28760 Tres Cantos, Madrid, Spain


Bismuth telluride films were synthesized by electrodeposition techniques. A conventional

three-electrode cell, with Ag/AgCl (saturated KCl) as reference electrode, platinum counter

electrode, and silicon coated with chromium and gold as working electrode, was used. Films were

grown from a nitric acid bath [1], and characterized using SEM, XRD, energy dispersive X-Ray

(EDX). Also their transport properties (Seebeck coefficient, S, and electrical resistivity, ρ) were

measured.

The main goal of our research was to optimize those bismuth telluride films in order to

increase their thermoelectric performance for energy harvesting applications. Our first approach was

to modify the growth parameters until the films presented a preferential crystallographic orientation

with their c-axis parallel to the surface of the electrode, that is, [1 1 0], which is the most favorable

configuration for having the highest thermoelectric performance.

In order to further optimize the structure and morphology of the films, the addition of

sodium lignosulfonate, as proposed by Kuleshova et al. [2], was studied. In our case, we varied the

concentrations of the surfactant, the applied voltages and the type of working electrodes in the

electrodeposition process. SEM micrographs showed that those films presented morphology much

denser than in the case of films without additives, and EDX analysis showed no influence of the

additive in the composition of the films. As a conclusion of this study, we obtained the most

optimized bismuth telluride films from a morphological, structural, and a thermoelectrical point of

view: those prepared with 0.09 g/l of additive at -0.04 V of constant potential applied, which

exhibited a strong crystallographic orientation along the [1 1 0] axis, as we were looking for, along

with an increase of almost 100% in the Power Factor (S2/ρ), compared to those grown without

additives, which means an important increase of its efficiency as thermoelectric material.

Acknowledgements: The authors would like to acknowledge financial support from a joint

project with Japan: NANOTHERMA (FCCI), ERC StG NanoTEC 240497. O.C.C. wants to

acknowledge CSIC for JAE-Doc.

References [1]. M. S. Martín-González, A. L. Prieto, R. Gronsky, T. Sands, A. M. Stacy, J. Electrochem. Soc. 2002, C546-C554.

[2]. J. Kuleshova, E. Koukharenko, X. Li, N. Frety, I. S. Nandhakumar, J. Tudor, S. P. Beeby, N. M. White, Langmuir 2007, 22 16980-16985.

P12

60

SYNTHESIS AND CHARACTERIZATION OF ELECTRODEPOSITED ZnO

FILMS

C. V. Manzano1, O. Caballero-Calero

1, P. Díaz-Chao

1, M. S. Martín-González

1

1 IMM-Instituto de Microelectrónica de Madrid (CNM-CSIC), Isaac Newton 8, PTM,



In recent years, Zinc Oxide (ZnO) has been of great interest because it is a material with

remarkable and varied properties. Due to its wide band gap (3.36 eV) it is transparent in the visible

range. It has large exciton energy (60 meV). Those characteristics provide an efficient emission in

the ultraviolet and visible ranges, even at room temperature. Moreover, when doped with Al, it

presents a large thermopower factor at high temperatures when compared to other metal oxides [1].

In this study, ZnO films have been grown by constant and pulsed electrochemical

deposition. Electrodeposition of ZnO was performed using a standard three-electrode cell. ZnO

films at constant potential were grown using two different OH- sources: nitrate and peroxide in order

to obtain a comparative study between those films. While, ZnO films at pulsed potential were grown

in 0.1 M zinc nitrate aqueous solutions, the oxidation potential was maintained at + 0.9 V and the

reduction potential was changed from – 1.5 V to - 0.5 V versus Ag/AgCl decreasing in 0.2 V from

film to film.

The morphology, structural and optical characterization of the films were investigated

depending on the solution used and the applied potential. Scanning Electron Microscopy pictures

show different morphologies in each case. X-Ray Diffraction confirms that the films are pure ZnO

oriented along the (0002) direction. ZnO films have been studied by photoluminescence to identify

the emission of defects in the visible range. A consistent model that explains the emissions for the

different electrodeposited ZnO films is proposed. We have associated the green and yellow

emissions to a transition from the donor OH- to the acceptor zinc vacancies (VZn-) and to interstitial

oxygen (Oi0), respectively. The orange-red emission is probably due to transitions from the

conducting band to Oi- and OZn

0 defects and the infrared emission to transition from these Oi

-/2- and

OZn0/-

defects to the valence band [2].

Seebeck coefficient and electrical resistivity of the best films deposited under the different

conditions (different solutions, pulses and the applied potential). It can be concluded that the

Seebeck increases with temperature for all films except for the film grown at pulsed potential. And,

the resistivity increases with the temperature in all cases. The resistivity of the films grown at pulsed

potential is higher that the resistivity of the films grown at constant potential. The resistivity of the

films grown in peroxide solution is higher that the resistivity of the films grown in nitrate solution.

Acknowledgements: Authors would like to acknowledge partially financial support form:

NANOTHERMA (FCCI), MICINN project MAT2008-06330 and ERC StG NanoTEC 240497 and C.V.M.

wants to acknowledge CSIC for JAE pre-doc, and O.C.C. wants to acknowledge CSIC for JAE-doc.

References [1] T. Tsubota, M. Ohtaki, K. Eguchi, and H. Arai, Journal of Materials Chemistry 7, 85 (1997).

[2] C. V. Manzano, D. Alegre, O. Caballero-Calero, B. Alén, M. S. Martín-González J. Appl. Phys (in press).

P13

61

SYNTHESIS OF INTERLAYER EXPANDED FER-TYPE ZEOLITE

USING ORGANIC SILICON COMPOUNDS

Hiroyuki Imai, Jacques Plévert, Toshiyuki Yokoi, Junko N. Kondo, Takashi Tatsumi

Chemical Resources Laboratory, Tokyo Institute of Technology,

Yokohama, Japan 226-8503


Zeolites originating from two-dimensional (2D) lamellar precursors, e.g. MCM-22 (MWW),

ferrierite (FER), and CDS-1 (CDO) are well known, and their three-dimensional (3D) structures are

constructed via topotactic dehydroxylation between the layers in lamellar precursors. The

modification of the layered zeolitic precursors by pillaring and delamination has been reported. A

new method for enlarging pores of the zeolites was reported, in which diethoxydimethylsilane

(Me2Si(OEt)2) was inserted between the layers of the lamellar precursors of MWW, FER, CDO, and

MCM-47 to expand their interlayers [1]. Furthermore, it was reported that this interlayer silylation

method led to the formation of the new pore channels in the interlayer expanded FER [2].

In this study, we chose the ferrierite lamellar precursor, and synthesized interlayer-expanded

FER-type zeolites by insertion of monomeric Si sources having various types of organic groups

including methyl, ethyl and phenyl groups into the interlayer of the precursor. Based on the obtained

data, we discuss the properties of the resulting samples compared with the 3D crystalline FER-type

zeolite.

Figure 1 shows the XRD patterns of PREFER and silylated

samples. For the silylated samples, the layer-related diffractions

appeared in different angles from those of PREFER; furthermore,

these diffractions did not shift and appeared in lower angles than

those of 3D FER even after calcination. The amount of the

silylating agents strongly influenced the structure of the samples.

The insertion of the silylating agents with 0.1 of the ratio R [R =

(Si in silylating agent / Si in zeolitic precursor)] led to the peak at

7.6 attributed to the (002) plane (d-spacing: 11.69 Å). However,

increasing the amount of the agents up to R = 0.5 resulted in the

shift of the peak appearing at 6.2, which means that the interlayer

space was further expanded (d-spacing: 14.12 Å) compared with

that of the silylated sample above. It can be presumed that the

silylating agent molecules condensed mutually to form the species

having the bond such as Si-O-Si, and the species were inserted

into the interlayer. When Ph2SiCl2 was used as a silylating agent,

the peak attributed to the (002) plane appeared at 7.6, even after

the amount of the agents was increased up to R = 0.5. It is

probably due to that bulkiness of phenyl group inhibited the

condensation of Ph2SiCl2 molecules.

References [1] P. Wu et al., J. Am. Chem. Soc. 2008, 130, 8178.

[2] J. Ruan et al., Chem. Mater. 2009, 21, 2904.

10 20 30

2q / degree (Cu-Ka)

Inte

nsi

ty /

a.u

.

Me2Si(OEt)2, R = 0.1

x 1/5

x 1/25

x 1/2

PREFER

(00

2)

x 1/5Me2Si(OEt)2, R = 0.5

Et2Si(OEt)2, R = 0.1

Et2Si(OEt)2, R = 0.5

Ph2SiCl2, R = 0.1

Ph2SiCl2, R = 0.5

Figure 1. XRD patterns of

PREFER and silylated samples.

P14

62

METHANE ADSORPTION ON ACTIVATED CARBON PREPARED FROM

MESOPHASE PITCH

Mirian Elizabeth Casco, Manuel Martínez-Escandell, Miguel Molina Sabio, Francisco

Rodríguez-Reinoso

Laboratorio de Materiales Avanzados (LMA). Departamento de Química Inorgánica, Universidad

de Alicante.03080 Alicante.


The use of mesophase pitch as a precursor material has a great versatility when designing

activated carbons with specific textural properties. The operation variables of the heat treatment as

well as the kind of petroleum residue determine the characteristics of the mesophase pitch and the

activated carbons that can be produced with them [1.2]. This work uses three mesophase pitches

with different optical texture (size and mesophase content) to obtain activated carbons with a high

methane storage capacity.

Three different petroleum pitches were obtained using two different petroleum residues:

ethylene tar (PY) and vacuum residue (VR), which were subjected to different heat treatment

(temperature: 440-460ºC, pressure 0-1 MPa, soak time 1.5-3 h). Pyrolysis conditions were selected

in order to have three mesophase pitches with mesophase content of 5, 56 and 93 % and different

microstructure. Three different series of activated carbons (AC) have been prepared by KOH

activation of the three mesophase pitches at 800ºC in N2 atmosphere, varying the KOH/precursor

ratio from 1:1 to 8:1. Methane adsorption isotherms were performed at 25 C to 4 MPa.

The results show a linear relation between the total volume of pores (Vt) or the volume of

micropores (VN2-DR) and the ratio of KOH used, independently of the kind of pitch used, to obtain

maximum values of Vt of 2.2 cm3/g and VN2-DR of 1.1 cm

3/g. The analysis of the results of textural

characterisation indicates that when comparing activated carbons obtained with the same KOH ratio,

those obtained with the petroleum pitch VR present a narrower porosity. Besides, it seems that the

ACs obtained from pitches of higher mesophase content develop a higher porosity, indicating the

influence of microstructure [3]. The highest amount of methane adsorbed a 25ºC and 3.5 bars (283

cm3/g) were obtained for sample VR460, activated with a ratio 4:1. However, the highest value of

methane expressed on a volumetric basis was obtained for a PY440 sample, activated with the same

KOH ratio, for which a value of 137 v/v was obtained. It is clear that the bulk density of the carbon

is relatively low and it must be increased.

Acknowledgements: This work has been financed by Ministerio de Ciencia e Innovación,

Proyectos Internacionales PLE2009-0052. M.C thanks Generalitat Valenciana for her grant of

research personal formation Santiago Grisolía.

References M. Krola, G. Gryglewicz b, J. Machnikowski. Fuel Processing Technology. 2011. 92, 158.

M. C. Monteiro de Castro, M. Martínez Ecandell, F. Rodríguez Reinoso. Carbon. 2010, 48, 636.

G. Stavropoulos. Fuel Processing Technology. 2005, 86, 1165.

P15

63

MID-INFRARED PHOTODETECTORS BASED ON GAASSB-CAPPED INAS

QUANTUM DOTS

K. Yamamoto, J. M. Ulloa, A. Guzman, A. Hierro*

ISOM and Department of Electronic Engineering, Technical University of Madrid, Ciudad

Universitaria s/n, 28040 Madrid, Spain

*E-mail: [email protected]

Quantum dot infrared photodetectors (QDIPs) are very attractive for many applications such

as infrared imaging, remote sensing and gas sensing, thanks to its promising features such as high

temperature operation, normal incidence response and low dark current [1]. However, the key issue

is to obtain a high-quality active region which requires an optimization of the nanostructure. By

using GaAsSb capping layer, InAs QDs have improved their optical emission in the range between

1.15 and 1.3 m (at Sb composition of 14 %), due to a reduction of a compressive strain in QD and

an increment of a QD height [2]. In this work, we have demonstrated strong and narrow intraband

photoresponses at ~ 5 m from GaAsSb-capped InAs/GaAs QDIPs under normal light-incidence.

The n-i-n QDIPs were grown on n+ Si-doped (001) GaAs substrates using solid-source

molecular beam epitaxy. The active region contained 20 periods of 16 monolayer (ML)-GaAsSb

capped InAs QDs (2.5 MLs) and separated by 50 nm-thick GaAs barrier layers. The Sb composition

in the GaAsSb capping layer was varied from 0 to 17 %. The typical dot density is 4.0 x 1010

cm-2

.

A -doping layer with a carrier concentration of 1.6 x 1016

cm-2

and a thickness of 2.5 nm was

located 2 nm below each QD layer. The whole active region was sandwiched between top and

bottom n-GaAs contact layers doped with Si to n = 2 x 1018

cm-3

. The QDIPs were processed into

mesa of 200 m in diameter, and a ring-shaped metallization using AuGe/Au was deposited on the

top of mesas and alloyed for ohmic contacts. An InSn bottom contact was chosen as the ground for

all of the measurements. Photoresponse at 12 K and direct absorption at room temperature were

measured by Fourier Transform Infrared spectroscopy (FTIR) using a normal light-incidence.

Photoresponse spectra of the QDIPs with GaAsSb-capping layers show a clear peak at ~5

m and with its spectral width of / ~ 0.3. The integrated intensity and the full width at half

maximum (FWHM) of the GaAs0.83Sb0.17-capped QDIP are 10 times higher and 30 % lower than

reference samples of GaAs-capped QDIP, respectively. The lower FWHM reflects the high-quality

QDs and their high homogeneity [2]. The stronger intensity with respect to the GaAs-capped sample

is attributed to a reduction of the electron-recapture probability due to a delocalization of the holes

from the QD-region that results from the valence band alignment between the QDs, the GaAsSb

capping layer, and the GaAs barrier.

References [1]. E.-T. Kim A. Madhukar, Z. Ye, J. C. Campbell, Appl. Phys. Lett. 2004, 84, 3277.

[2]. J. M. Ulloa, R. Gargallo-Caballero, M. Bozkurt, M. del Moral, A. Guzman, P.M. Koneraad, A. Hierro, Phys. Rev. B

2010, 81, 165305.

P16

64

ELECTROCHEMICAL IMPEDANCE CHARACTERIZATION OF

PbS QUANTUM DOT-SENSITIZED SOLAR CELL

Sojiro Hachiya,1 Qing Shen,

1,2 and Taro Toyoda

1

1Department of Engineering Science, Faculty of Informatics and Engineering,

The University of Electro-Communications, Tokyo, Japan 2PRESTO, Japan Science and Technology Agency, Saitama, Japan


Quantum dot (QD)-sensitized solar cells (QDSSCs) have attracted much attention because

the use of semiconductor QDs have some advantages in solar cell applications [1]. PbS QDs have a

possibility to obtain high conversion efficiency for solar cell applications, because they can absorb

visible and infrared light and have shown the potential to generate multiple excitons by one photon

absorption of UV or visible light [2]. However, using PbS QDs for solar cell application causes

problem of photostability. In previous study, ZnS coating for the PbS QDs has shown extreme

contributes to improve the photovoltaic properties of PbS QDSSCs. The role of ZnS layer does not

only prevent QDs from photocorrosion but also hinder back electron transfer from TiO2 to

electrolyte. To investigate the details of ZnS coating effects on the enhancement in the photovoltaic

performances of PbS QDSSCs, it is needed to study recombination resistance between TiO2 and

electrolyte surface.

In this work, we study the recombination resistance in PbS QDSSCs with ZnS coating using

electrochemical impedance characterization [3]. PbS QDs were adsorbed onto nanostructured TiO2

electrodes using successive ionic layer adsorption and reaction (SILAR) method for two cycles.

After adsorption of PbS QDs, the surfaces of the samples were coated with ZnS by SILAR method

for several cycles under various conditions (solvents and concentrations). Finally, sandwich

structure solar cells were prepared. The counter electrode was a Cu2S film on brass [4]. Mixture of

the 1M S and 1M Na2S solution (polysulfide redox system) was used as the regenerate redox couple.

We found that with increasing ZnS adsorption cycles, the value of recombination resistance

increased. This result indicate that ZnS layer also hinder the back electron transfer from TiO2 to

electrolyte.

References

[1]. A. J. Nozik, Physica E 2002, 14, 115.

[2]. A. J. Nozik, Chem. Phys. Lett. 2008, 457, 3 .

[3]. F. Fabregat-Santiago, J. Bisquert, G. Garcia-Belmonte, G. Boschloo, A. Hagfeldt, Sol.

Energy Mater. Sol. Cells 2005, 87, 117 [4]. G. Hodes, J. Manassen, and D. Cahen, J. Electrochem. Soc. 1980, 127, 544.

P17

65

N

N

R

2

O

O

O

O

O

O R

3

R

1

R

1

STUDIES OF SQUARAINES MOLECULES IN SOLUTION AND DEPOSITED

ONTO QUARTZ SUBSTRATE: FROM FEMTO TO MILLISECOND TIME-

SCALES

M. Marchena1, G. de Miguel

1, M. Ziółek

1, M, Zitnan

1, K. Abe

2, Y. Ogomi

2 , S. S.

Pandey2, S. Hayase

2 and A. Douhal*

1

1Departamento de Química Física, Sección de Químicas, Facultad de Ciencias del Medio

Ambiente, Universidad de Castilla-La Mancha, Av. Carlos III S/N, 45071 Spain 2Kyushu Institute of Technology, 2-4 Hibikino, Wakamatsu, Kitakyushu, Japan


The dynamics of five types of squaraines (SQs) molecules

1-3 in solution and deposited onto

quartz substrate have been studied from femto to millisecond time scales.

In solution, steady-state UV-vis absorption and emission spectra are narrow, with a Stokes

shift of about 300 cm-1

. Time-resolved picosecond experiments gave two lifetimes (for the seven

studied SQs) that have been assigned to two possible stereoisomers in the ground state in trans

configuration. Experiments with solvents of different polarity and viscosity were performed to probe

the twisting relaxation of the S1 state.

Nanosecond flash photolysis experiments showed the

transient signals of the cis photoisomer that is formed after

the twisting process of S1. The relaxation of this transient

signal follows the cis-trans back photoisomerization,

recovering the initial ground state of the SQs.

The femtosecond transient absorption results showed

a fast component which is to a large extent independent on

the used solvent and on the type of SQs. This component

presents as a rise at the maximum of the transient signal or as

a decay at the blue-side of the spectrum, producing a net

narrowing of the peak. We attribute this event to an

intramolecular vibrational-energy relaxation (IVR) process.

In pure SQs thin films, the formation of two species at the excited state, monomer and H- or

J-aggregates was proved. Non-exponential fit of the experimental time profiles together with the

power-dependence of the transient absorption signal makes us to propose a singlet-singlet

annihilation process to account for the rapid deactivation of the aggregate excited state.

Acknowledgements: This work was supported by the MICINN through the project MAT2008-

01609 and PLE-2009-0015. M. is grateful to JCCM for a postdoctoral contract.

References [1] S.S. Pandey, T. Inoue, N. Fujikawa, Y. Yamaguchi, S. Hayase, Thin Solid Films, 2010 519, 1066-1071.

[2] T. Inoue, S.S Pandey, N. Fujikawaa, Y. Yamaguchi, S. Hayase, J. Photochem. Photobiol. A, 2010, 213, 23-29.

[3] S. S. Pandey, T.Inoue, , N. Fujikawaa, Y. Yamaguchi, S. Hayase, J. Photochem. Photobiol. A, 2010, 214, 269-275.

550 575 600 625 650 675 700

-10

-5

0

5

10

0.7 s

1.8 s

4.8 s

11.5 s

A

/ a

.u.

Wavelength / nm

0 5 10 15 20 25 30

-1.0

-0.5

0.0

0.5

1.0

pr

= 630 nm

650 nm

630 nm

A

/ a

.u.

Time / s

pr

= 650 nm

N

N

F

F

F

O

O

O

O

N

N

F

F

F

O

O

O

O

SQ41

A B

P18

66

NANOSTRUCTURED ORGANIC SEMICONDUCTORS FOR SOLAR CELL

APPLICATIONS

M. Campoy-Quiles,1 Y. Ishii,

2 C. Müller,

1 M. I. Alonso,

1 M. Garriga,

1 A. R. Goñi,

1 H.

Murata2

1Institute of Materials Science of Barcelona (ICMAB-CSIC), Campus UAB, Bellaterra,

Spain, 08193 2School of Material Sciences, Japan Advanced Institute of Science and Technology (JAIST),

1-1 Ashahidai, Nomi, Ishikawa, Japan, 923-1292


Amongst the different emerging photovoltaic technologies, organic solar cells (OSCs) are

attracting increasing interest worldwide as they offer the prospect of very low-cost active layer

materials and substrates, low energy input and facile upscaling. Organic materials can be deposited

by solution-processing methods such as printing and coating, thereby boosting production

throughputs typically by a factor 10 to 100 compared to other thin-film technologies [1] at estimated

production costs as low as a few €´s/m2. Currently, the best OPV efficiencies are in the 7-8% range,

and further research is needed to bring OSCs to the 10-15% market uptake point.

The emergence of OSC has been facilitated by cell design concepts that are radically

different from the planar single heterojunction solar cells in production today. The basis of these

concepts is the existence of nanosized domains of the electron and donor materials resulting in a

bulk-distributed interface (aka bulk heterojunction) [2, 3]. The understanding and control of such

nanostructure, which governs the final performance of the OSC, is the topic of the current

collaboration between the Spanish and Japanese teams, following two strategies:

1) Use of controlled self assembly of the active materials by means of epitaxial

crystallization and/or amorphous scaffoldings [3]. This enables to simultaneously optimize many of

the requirements for highly efficient solar cell operation, including controlled nanostructure and

maximized device characteristics, relaxing the usual compromises forced upon conventional

binaries.

And 2) direct structuring of materials into nanofibers for a precise control of the

nanostructure of the active layer [4]. This approach is also expected to lead enhanced charge

transport and light harvesting via molecular orientation.

Acknowledgements: The authors thank the Spanish Ministry of Science and Innovation for

funding through the Japan-Spain collaboration program (project PLE2009-0086).

References [1] C. J. Brabec and J. R. Durrant, MRS Bulletin, 2008, 33, 670.

[2] M. Campoy-Quiles, T. Ferenczi, T. Agostinelli, P. G. Etchegoin, Y. Kim, T. D. Anthopoulos, P. N. Stavrinou, D. D.

C. Bradley and J. Nelson, Nature Materials, 2008, 7, 158. [3] M. Campoy-Quiles, Y. Kanai, A. El-Basaty, H. Sakai, H. Murata, Org. Electron. 2009, 10, 1120

[4] M. Campoy-Quiles, Y. Ishii, H. Sakai and H. Murata, Appl. Phys. Lett. 2008, 92, 213305.

P19

67

SYNTHESIS, STRUCTURAL AND ELECTRICAL CHARACTERIZATION OF

NEW Gd0.5Ba0.5B1-xB’xO3- (B, B’= Mn, Co, Fe) PEROVSKITE MATERIALS AS

COMPONENTS OF ELECTROCHEMICAL DEVICES FOR ENERGY

GENERATION

Daniel Muñoz Gil,1 Subakti,

1 Juan Peña Martínez,

1 Miguel Ángel Alario Franco,

1

Susana García Martín1

1Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad

Complutense, 28040-Madrid, Spain


Transition metal oxides of general formula Ln1-xAxBO3- (Ln=lanthanide A=Ca, Sr, Ba;

B=transition metal) with perovskite-related structures do have important electric and catalytic

properties. Some of them, like BaGdCo2O5+δ, have recently shown an excellent behaviour as

cathodes in fuel cells [1]. The composition of the compounds, the size of the cations and the

ordering or disordering between them play an important role in the modification of such properties.

In this sense, layered-type ordering of cations significantly improves the oxygen diffusion within the

anion sublattice in double perovskites of composition BaGdMn2O6-δ and BaGdCo2O6-δ [2].

We are studying the influence of the cation ordering in the crystal structure and electronic

properties of Gd0.5Ba0.5B1-xB‘xO3- (B, B‘= Mn, Co, Fe) and the behaviour of these materials as

cathodes in fuel cells and Li/Air batteries. Preparation of the compounds under different reducing or

oxidizing conditions have a significant effect on their crystal structure and microstructure. Our work

on these oxides by Selected Area Electron Diffraction and High Resolution Transmission Electron

Microscopy indicates that the ordered phases GdBaB2-xB‘xO6- show different superstructures of the

perovskite-type, associated to charge ordering effects and ordering of cations and/or vacancies.

Superstructure formation also affects the electronic properties of these materials. Area specific

resistance of BaGdMn2O6-δ on doped ceria electrolyte at different temperatures indicates that it is

acceptable as a cathode for IT-SOFC applications.

.

Acknowledgements: Authors thank the Spanish MICINN for funding Projects PIB2010JP-00181

and MAT2010-19837-C06 and CAM for Project MATERYENER-2, P2009/PPQ-1629.

References [1]. A. Tarancón, J. Peña-Martínez, D. Marrero-López, A. Morata, J.C. Ruiz-Morales, P. Núñez, Solid State Ionics

2008, 179, 2372.

[2]. A. A. Taskin et al. Progress in Solid State Chemistry 2007, 35, 481.

P20

68

SRTUCTURE AND ELECTRICAL PROPERTY OF VARIOUS METAL ION CO-

DOPED SCANDIA STABILIZED ZIRCONIA

N. Sonoyama1, M. Ikeda

1, Y. Ota

1, N. Imanishi

2, A. Hirano

2 Y. Takeda

2 and

O. Yamamoto2

1Materials Science and Engineering, Nagoya Institute of Technology , Gokiso-cyo, Showa-

ku, Nagoya 466-8555, Japan 2Department of Chemistry, Mie University, 1577 Kurimamachiyacho, Tsu, Mie, 514-8507,

Japan


Introduction

Scandia stabilized zirconia (ScSZ) receives a renaissance as a substitute of YSZ for the solid

electrolyte of low temperature operating SOFC. But, ScSZ with Sc2O3 concentration over 10%

shows rhombohedral to cubic phase transition around 650˚C [1, 2] and this impairs electrical

conductivity and the lifetime of SOFC device. In this paper, we have attempted at stabilizing cubic

phase of ScSZ by co-doping various valent ion with shorter ion radius than Zr4+

ion, and discussed

the correlation between electrical conductivity and the local structure.

Experimental

All the specimens used in this paper were synthesized by sol-gel method. Obtained gel was

dried at 110˚C over night and the dry precipitates were calcinated at 700˚C for 9h. The powder

obtained were pressed isostatically into a bar under a pressure of 120 MPa followed by sintering at

1600˚C for 8h. Detailed conditions for synthesis and measurement were mentioned elsewhere. [3]

Results and discussion In all Ga

3+ concentration region, no byproduct was

observed for the XRD patterns for (ZrO2)0.89(Sc2O3)0.11-x

(Ga2O3)x (0 ≤ x ≤ 0.07), synthesized in this study. In the

region 0.01≤ x ≤0.06, only the reflections attributable to the

cubic zirconia were obtained. This result demonstrates that

ScSZ can be stabilized to the cubic phase at room

temperature by Ga3+

co-doping.

The relationship between the electric conductivity

and temperature for (ZrO2)0.89(Sc2O3)0.11-x(Ga2O3)x (0 ≤ x ≤

0.07) is shown in Fig. 1. For the specimens with 0.01≤ x ≤

0.06, no conductivity jump was obtained. This result is

consistent with the XRD and TG-DTA data: the cubic phase

of (ZrO2)0.89(Sc2O3)0.11-x(Ga2O3)x (0.01 ≤ x ≤ 0.06) was

stabilized even at the room temperature and the stabilization

of cubic phase improved the electric conductivity at the lower

temperature region extensively. The results for other metal

co-doped system will be discussed in the presentation.

References

[1] T. Sakuma and H. Suto, J. Mater. Sci. 1986, 21, 4359.

[2] O. Yamamoto, et al., Solid State Ionics, 1995, 79, 137.

[3] Y. Ota, N. Sonoyama, et al., J. Electrochem. Soc. 2010, 157, B1707.

Fig. 1 Temperature dependence of the electrical

conductivity for (ZrO2)0.89(Sc2O3)0.11-x(Ga2O3)x

P21

69

ELECTROCHEMICALLY GROWN BI2TE3 THIN FILMS FOR

THERMOELECTRIC APPLICATIONS

Biswapriya Deb1, Y. Ishoda

1, O. Caballero-Calero

2, P. Díaz-Chao

2, M.S. Martín-

González2, Yoshikazu Shinohara

1

1 Eco Energy Group, National Institute for Materials Science (NIMS), 1-2-1 Sengen,

Tsukuba, Ibaraki 305-0047, JAPAN 2 Thermoelectrics group, IMM-Instituto de Microelectrónica de Madrid (CNM-CSIC), Isaac

Newton 8, PTM, E-28760 Tres Cantos, Madrid, Spain


Thermoelectricity has potential to meet the need of clean and low cost energy production.

Direct conversion of heat into electricity and vice versa could be ideal for power generation from the

waste heat and heat pumping. The application prospects of thermoelectric materials suffer mainly

from their low efficiency, which depends on their figure of merit (ZT). ZT is a dimensionless

quantity defined as α2σT/κ, where α, σ and κ stands for the Seebeck coefficient, electrical and

thermal conductivities respectively with T being the absolute temperature. Recent research predicts

that the efficiency of thermoelectric materials could be enhanced in nano scale (one or two

dimensional) due to the quantum confinement of electron charge carriers [1]. Bi2Te3 in bulk form

exhibits highest efficiency near room temperature [2], therefore thin films of Bi2Te3 nanoparticles

with performance optimization could lead to practical thermoelectric devices.

Bi2Te3 films were deposited onto a large area of n-Si substrate via electrochemical route,

following the fabrication procedure described in Martín-González et al [3]. The substrate was

evaporated with 5 nm of Ti and 150 nm of Au prior to the deposition. After deposition, the sample

was cut into four different pieces. Each piece underwent different heat treatment for 1 hour in a

controlled N2 atmosphere to opt mimize the carrier concentration. These films were then

characterized by SEM (morphological), XRD (structural) and XRF (elemental). Room temperature

Seebeck coefficient and electrical resistivity were measured using a custom built setup.

In this presentation we compared effect of different heat treatment on bismuth telluride

films. The obtained results are correlated with morphological, structural and elemental properties of

Bi2Te3 films.. A simple model is also presented here which could be used to resolve the substrate

effect on the overall transport properties.

References [1] D. M. Rowe, G. Ming, S. G. Willieams, G. K. Kuznetsov, Proceedings of the 17th International Conference on

Thermoelectrics 2000: 1499 – 1504. [2] B. Yim and F. Rosi, Solid-Sate Electron., 1972, 15: 1121

[3] M. Martín-González, J. Electrochem Society 2002, 149 (11): C546 – C554.

P22

70

POWER FACTOR OF Bi2Te3 FOAMS

Pablo Díaz-Chao, Begoña Abad, Olga Caballero-Calero, Marisol Martín-González

IMM-Instituto de Microelectrónica de Madrid (CNM CSIC), Isaac Newton 8, PTM,



Bismuth Telluride (Bi2Te3) is a well known material with one of the highest figure of merit

(ZT ~ 1) for thermoelectric applications at room temperature [1]. This high value of ZT is not

enough, however, to achieve high efficient devices. At this moment, the proposed strategies to

improve the thermoelectrical properties of the materials follow essentially two ways: the

improvement of transport properties (Seebeck coefficient (S) and electrical conductivity (σ)) by the

quantum confinement effects produced by the reduction of dimensionality, and the reduction of the

thermal conductivity by the introduction of phonon scattering sites.

In order to explore both ways, Bi2Te3 have been prepared by electrodeposition into

nanoporous Teflon® foams matrixes. The Bi2Te3 foams have been grown by applying different

potentials (-40mV – -60mV vs. Ag/AgCl) for different deposition times (4h – 40h). In this work, we

present the first results of the power factor (S2·σ) of the foams prepared. To this aim S and σ have

measured in a Linseis LSR-3 system at temperatures from 50ºC to 160ºC (figure 1). In order to

compare the obtained results, Bi2Te3 micron-thick films with bulk-like properties have been grown

by electrochemistry onto Au/Ti/Si substrate (figure 1). The structural (XRD) and morphological

(SEM) properties of both, the Bi2Te3 films and the Bi2Te3 foams, have been also studied.

50 100 1501E-9

1E-8

1E-7

1E-6

1E-5

1E-4

Si/Au/Bi2Te

3Film: 2h, -40mV

Teflon/Bi2Te

3: 4h,-40mV

Teflon/Bi2Te

3: 6h,-40mV

Teflon/Bi2Te

3: 7h,-60mV

Teflon/Bi2Te

3: 40h,-60mV

PF

(W

/m·K

2)

T (ºC) Fig. 1 Obtained results of the power factor of the Bi2Te3 foams

prepared by electrodeposition into Teflon® foam matrixes.

Acknowledgements: This work has been partially financed by a joint project with Japan:

NANOTHERMA (FCCI), ERC StG NanoTEC 240497. O.C.C. wants to acknowledge CSIC for

JAE-Doc.

References [1]. Christopher J. Vineis, Ali Shakouri, Arun Majumdar, Mercouri G. Kanatzidis. Advanced Materials. 22 (2010) 3970-

3980.

P23

71

Scheme 1. OSDAs used in this study.

RTH-TYPE ALUMINOSILICATE ZEOLITES SYNTHESIZED USING

PHOSPHOROUS CONTAINING STRUCTURE DIRECTING AGENTS

R. Simancas, J. A. Vidal-Moya, M. Hernández-Rodríguez, M. T. Navarro, A. Cantín,

D. Dari, N. Velamazán, J. L. Jordá, T. Blasco, F. Rey

Instituto de Tecnología Química (UPV-CSIC), Avda. de los Naranajos s/n. 46022-Valencia,

Spain


Zeolite RUB-13 possesses a RTH type structure consisting of a bidimensional eight member

ring channels system with an aperture of 4.1x3.8 Å.1,2

The synthesis and characterization of pure silica and aluminosilicate RUB-13 zeolites with

Si/Al framework molar ratio in the range 13 - ∞, which were obtained through a novel route using

phosphorous-containing organic moieties (shown in Scheme 1) instead of the classical quaternary

amine cations as organic structure directing agents (OSDA). The characterization of the as

synthesized and calcined RUB-13 zeolites was carried out by using a variety of techniques, and

more especially solid state NMR spectroscopy.

Gels of chemical composition 0.5 SDA+OH

- : (1-x) SiO2 : x Al2O3 : 7 H2O : 0.5 HF have

been prepared in fluoride or in alkaline media using the

phosphorous containing cations as SDA.

The XRD data of the as synthesized material are

characteristic of highly crystalline RUB-13 zeolite as

pure phase. The zeolite structure is maintained after

calcinating the samples at 1023 K during 5 h. The

positive charge of the phosphorous containing cations

entrapped into pure silica RUB-13 zeolite are compensated by fluoride anions or structural defects,

depending on the media employed for their syntheses. Al(III) cations substituting for Si atoms into

the zeolite framework introduces negative charges, which compensate the phosphorous containing

cations. 29

Si, 27

Al and 31

P MAS NMR spectra of RUB-13 zeolite with a Si/Al=18 as synthesized and

calcined forms were recorded. The 29

Si spectrum of the original sample shows two peaks at -113.7

ppm of Si(OSi)4 sites and at -106.9 ppm due to the contribution of Si(OSi)4 and of Si(OSi)4-n(OAl)n

sites. The 27

Al MAS NMR spectra indicate that all aluminum occupies framework sites in the

original samples, but calcination generates extraframework species (Aloct at -13 ppm, and distorted

Al sites and aluminophosphate at -32 ppm), so that only a small fraction remains at framework

positions. The 31

P MAS NMR spectrum of the original sample shows a peak that correspond to the

phosphonium species but upon calcinations a very broad band with several components in the range

(-10) ppm – (-40) ppm, which indicate the formation of phosphate-like species isolated and with

various degrees of condensation as well as aluminum phosphate.

Acknowledgements: The authors acknowledge Spanish Government (projects MAT2009-14528-

C02-01 and PLE2009-0054) for financial support. R.S., M.H.R. and N.V. thank to UPV, MICINN

and CSIC for Predoctoral fellowships, respectively.

References [1] Vortmann, S. et. al. Microporous Materials, 4 (1995), 111 - 121.

[2] Lee, G.S. J. Solid State Chem., 167 (2002) 289 – 298.

P24

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PREPARATION OF ACTIVATED CARBONS USING MESOPHASE PITCHES

CONTAINING TRANSITION METALS FOR ENERGY STORAGE

APPLICATIONS

Mateus Monteiro de Castro, Manuel Martínez Escandell, Miguel Molina Sabio, Francisco

Rodríguez Reinoso

Laboratorio de Materiales Avanzados (LMA). Departamento de Química Inorgánica,

Universidad de Alicante.03080 Alicante.

Activated carbons containing metal dispersed particles on the surface can find

applications in catalysis and adsorption processes in which gas-solid interactions are low [1, 2]. If

high surface area and microporosity are also required, the activation with KOH of carbon precursors

such as mesophase pitch or cokes is very adequate. Moreover, the technique of copyrolysis of

petroleum residues with dissolved organometallic compound produces mesophase pitches with a

large dispersion of the metal [3]. In this work mesophase pitches doped with first row

transition metals has been produced and the effect of the metal in the porous texture of the activated

carbons and their adsorption of hydrogen has been analysed.

Doped mesophase pitches have been prepared by co-pyrolysis of an ethylene tar with

different metals, Ti,V, Fe, Co, Ni and Cu, at 440ºC, pressure of 1 MPa, and 4 hours soak time, with

metal contents in the pirolysis mixture varying from 0 to 10 wt%. The mesophase pitches were

activated at 800ºC using a KOH:carbon ratio of 3:1 and a N2 flow of 100mL/min. The activated

carbons were washed with water in a Sohxlet.

The acetylacetonates decompose during pyrolysis at temperatures above 350° C, yielding

metal oxides, something confirmed by XRD. The analysis of mesophase pitches by SEM and TEM

indicate that they contain dispersed metal oxide nanoparticles, which aggregate forming clusters

of up to 2-3 microns. These oxides are reduced during the activation process, affecting to the porous

texture of the activated carbons. Generally, it has been observed that the presence of metals

produces a widening of porosity, which is notable in the case of Ni and Fe. For the latter, there is a

notable increase in BET surface area and mesopore volume, whereas microporosity almost remains

constant especially for samples containing less 3wt% Fe in the pyrolysis mixures. It also has to be

pointed out that there is a gradual decrease in micropore volume with increasing metal content. It

seems that the presence of metal catalyses the activation process. The adsorption of H2 at 25ºC to

100 bars has been studied. Results indicate that the amount of hydrogen adsorbed depends more on

the volume of microporosity than in the amount and quantity of metal used. Only when hydrogen

adsorption results are expressed per gram of carbon instead of gram of activated carbon

(carbon+metal) it seems that values of adsorbed hydrogen in doped activated carbon (Fe or Ni) are

slightly larger than for the undoped activated carbon.

Acknowledgements: This work has been financed by Ministerio de Ciencia e Innovación,

Proyects MAT2007-61734, Fondos FEDER, y PLE-2009-0052.

References [1] R. Strobel, J. Garche, P.T. Moseley, L. Jorissen, G.J. Wolf. J. Power Sources. 2006, 159, 781.

[2] K.M. Thomas, Catal. Today. 2007, 120, 389.

[3] M. Monteiro de Castro, M. Martínez-Escandell, M. Molina-Sabio, F. Rodríguez-Reinoso. Carbon. 2010, 48, 636.

P25

73

PHOTOVOLTAIC PROPERTIES AND ULTRAFAST CARRIER DYNAMICS OF

COMBINED CdS/CdSe QDs ADSORBED ON INVERSE OPAL TiO2 ELECTRODE

Yohei Onishi,1 Qing Shen,

1, 2 Kenji Katayama,

3 Taro Toyoda,

1

1 Department of Engineering Science, The University of Electro-Communications, Tokyo,

Japan 2 PRESTO, Japan Science and Technology Agency (JST), Saitama, Japan

3 Department of Applied Chemistry, Chuo University, Tokyo, Japan


Recently, semiconductor QD-sensitized solar cells (QDSSCs) have attracted much attention

as a candidate of low cost, environmentally friendly and high efficiency solar cells. The morphology

of TiO2 electrode and the choice of the sensitizers are very important factors deciding the

photovoltaic performance in QDSSCs. Up to now, we have demonstrated that inverse opal (IO)

TiO2 electrode is useful for QDSSCs [1]. On the other hands, the improvement in photocurrent was

reported for combined CdS/CdSe QDSSCs compared with CdSe QDSSCs [2-5]. However, detailed

mechanism for the improvement in photocurrent by combined CdS/CdSe QDs sensitization was

remained unexplained. In order to achieve a further improvement in photovoltaic performances of

QDSSCs, studies on the photoexcited carrier dynamics of the QDs, such as carrier transport, charge

injection and recombination, play an important role in connection with the photocurrent generation.

Recently, ultrafast carrier dynamics in QDSSCs have been investigated using a improved transient

grating (TG) method based on the change in the refractive index of the sample surface due to

photoexcited carrier [6,7].

In this study, we used combined CdS/CdSe QDs as sensitizer and adsorbed on IO TiO2

electrodes for the first time. Photovoltaic performances and ultrafast carrier dynamics for combined

CdS/CdSe QDSSCs and CdSe QDSSCs were investigated. The CdS deposition time was changed

from 0.5 h to 12 h, while the CdSe deposition time was fixed to be 6 h [2,3]. For the characterization

of carrier dynamics, the improved TG technique was applied. From photocurrent-voltage

characteristics, improvements in photocurrent and conversion efficiency (were confirmed in the

combined CdS/CdSe QDSSCs with CdS deposition time of 0.5 h (TiO2(IO)/CdS(0.5 h)/CdSe(6 h))

compared to the CdSe QDSSCs (TiO2(IO)/CdSe(6 h)). However, as the CdS deposition time

become longer than 1h, the photocurrent and conversion efficiency decreased. On the other hands,

the TG responses of all samples show a fast decay process and a slow decay process with lifetimes

of a few ps and a few tens to hundreds ps, respectively. The lifetimes of these two processes become

faster in the combined CdS/CdSe QDSSCs compared to the CdSe QDSSCs. This result implies that

recombination centers and interface states of electrons were decreased by the adsorption of the

combined CdS/CdSe QDs.

References [1] L, J. Diguna et al., Appl. Phys. Lett. 2007, 91, 023116. [2] O. Niitsoo et al., J. Photochem. Photobiol., A 2006, 181, 306.

[3] T. Toyoda et al., J. Appl. Phys. 2010, 108, 114304.

[4] Gonzalez-Pedro V et al., ACS Nano 2010, 4, 5783.

[5] Q. Zhang et al., Phys. Chem. Chem. Phys. 2011, 13, 4659.

[6] K. Katayama, M. Yamaguchi and T. Sawada, Appl. Phys. Lett. 2003, 82, 2775.

[7] Q.Shen et al., Appl. Phys. Lett. 2010, 97, 263113.

P26

74

Figure 1 Electronic absorption spectra of 10

M solution of unsymmetrical squaraine dyes

in Ethanol.

PHOTOVOLTAIC PERFOMANCE OF DYE SENSITIZED SOLAR CELLS BASED

ON UNSYMMETRICAL SQUARAINE DYES WITH EXTENDED

-CONJUGATION

Shyam S. Pandey,1 Yoshihiro Yamaguchi,

2 Shuzi Hayase

1

1Graduate School of Life Science and Systems Engineering, Kyushu Institute of Technology,

2-4, Hibikino, Wakamatsu, Kitakyushu, 808-0196, Japan. 2Nippon Steel Chemical Company Limited, 46-80, Nakabaru, Sakinohama, Tobata,

Kitakyushu, 804-8503, Japan


Dye sensitized solar cells (DSSCs) based on mimicking the natural photosynthesis are

gaining an increased attention as cheap alternative to silicon solar cells due to high photoconversion

efficiency (>10 %) similar to amorphous silicon [1]. Looking towards the most efficient sensitizers

used for DSSC fabrication indicate nearly 100 % photon harvesting in the visible region making an

urgent need for development novel sensitizers absorbing in NIR-IR wavelength region for

panchromatic sensitization and further enhancement in the efficiency of DSSCs. We have recently

reported that utilization of dye double layer architecture based DSSCs are capable for efficient

photon harvesting from both of the dyes leading to efficient photon harvesting in the wide

wavelength regions [2]. Our approach for high efficiency DSSCs is based on the utilization of NIR

dyes having sharp and intense absorption with potential organic or inorganic based visible dyes to

fabricate dye double layer DSSCs. In this context, squaraine dyes are one of the potential candidates

amongst NIR dyes intense and sharp light absorption with narrow full width at half maximum. They

basically bear a donor-acceptor-donor zwitterionic molecular framework having squaric acid core as

acceptor. The wavelength of such squaraine dyes can be tailored from visible to IR region based on

judicious molecular design using different donor moieties with extended -conjugation.

It has been reported that unsymmetrical

squaraine dyes are superior in performance as

compared to their symmetrical squaraine counterparts

due to unidirectional flow of electrons [3]. Electronic

absorption spectra along with the structure of

unsymmetrical squaraine dyes used to fabricate DSSCs

for the present investigation has been shown in the

figure 1. A perusal of this figure clearly indicates that

increasing the extent of -conjugation leads to

bathochromic shift of the absorption maximum. The

photovoltaic performance of DSSCs based on these

dyes will be discussed in terms structure-property

correlation.

References [1] M. A. Green, K. Emery, Y. Hishikawa and W.Warta, Prog. Photovoltaics, 2010, 18, 144.

[2] F. Inakazu, Y. Noma, Y. Ogomi and S. Hayase, Appl. Phys. Lett., 2009, 93, 093304.

[3] J. H. Yum, P. Walter, S. Huber, D. Rentsch, T. Geiger, F. Nuesch, F. D. Angelis,

M. Gratzel and M.K. Nazeeruddin, J. Am. Chem. Soc., 2007, 129, 10320.

P27

75

NANOMATERIALS FOR PESTICIDES DETECTION

Flavio Pino,1 Gemma Aragay,

1 Arben Merkoçi

1,2

1Nanobioelectronics & Biosensors Group, Institut Català de Nanotecnologia, CIN2 (ICN-

CSIC), Campus UAB, Barcelona, Spain 2ICREA, Barcelona, Catalonia, Spain


The use and abuse of pesticides and in particularly organophosphate pesticides (OPs) still is

a considerable alert problem for the national health system of different countries. Organophosphorus

derivatives are harmful compounds found in insecticides, pesticides and chemical-warfare agents.

They are widely utilized around the world.

Typical methods used for the detection and quantification of pesticides involve the use of

large instruments in laboratories (chromatography, high-performance liquid chromatography [1])

not allowing their application for in-situ measurements. The use of biosensors and their combination

with electrochemical [2] and optical techniques provides many advantages in terms of low cost and

friendly-use systems including their miniaturization for their further application in in-field

measurements [3]. However, it is still necessary the development of more accurate and sensitive

methods for trace amount of pesticide in biological samples for in-situ analysis. The use of

nanomaterials can give additional improvements to fit these requirements [4][5]. For example the

use of quantum dots (QDs) for biosensors readout signals can improve the detection limit and the

reproducibility of the system due to their good optical characteristics and high quantum yields of

photoluminescence (PL). Due to their tunable narrow-band emission and broad excitation spectra

QDs are also excellent donors for fluorescence resonance energy transfer (FRET)-based biosensors

suitable for in-situ analysis [6].

A general overview of the state of the art in the field of nanomaterials application for

pesticides sensing systems will be given. In addition a preliminary proposal for a novel

optical/electrochemical detection of chlorpyriphos, an OP pesticide, based on the use of quantum

dots will be described. Nanomaterials-based portable biosensors, both optical and electrochemical,

have high sensitivity for the detection of the analytes, which suggest that these technologies offer a

great promise for the rapid and in-situ detection and evaluation of OPs exposure.

Acknowledgment: We acknowledge the support given by MICINN (Madrid) for the project

PIB2010JP-00278.

References [1]. Z. Zou, Anal. Chem. 2006, 78, 5125

[2]. X. Llopis, Lab Chip, 2009, 9, 213.

[3]. Z. Zou, J.Anal. Chem. 2010, 82, 5125

[4]. A. de la Escosura-Muñiz, Trends in Anal. Chem. 2008, 27, 568.

[5]. A. Merkoçi, 2010, Ency. of Anal. Chem. [6]. H. Peng, J. Am. Chem. Soc. 2007, 129, 3048–3049

P28

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PROBING GEOMETRICAL COMPLEXITY IN CARBON NANOTUBULITE

USING SURFACE-ENHANCED RAMAN SCATTERING

Toshihiko Fujimori1 and Katsumi Kaneko

1

1Research Center for Exotic Nanocarbons (JST), Shinshu University, 4-17-1 Wakasato,

Nagano-city 380-8553 Japan


Geometrical complexity in carbon nanotubulites (e.g., carbon nanotubes, single-wall carbon

nanohorns) is based on non-hexagonal arrangements of carbon atoms in those honeycomb lattices. It

is thus desired to probe and control such carbon nanostructures for fabricating novel nanocarbon

materials. Since electric field of light is strongly enhanced at the vicinity of nanostructured metals

(e.g., gold or silver), ultrasensitive probing and photo-induced reactions can simultaneously proceed.

Surface-enhanced Raman scattering (SERS) is one experimental way to satisfy this point; we have

shown that SERS is a powerful technique to (1) probe a very small amount of pentagon-heptagon

arrangements (usually referred to a Thrower-Stone-Wales defect) in a single-wall carbon nanotube

(SWCNT) detection and (2) induce structural rearrangements of the Thrower-Stone-Wales defect

during exposure to the probe light [1].

In this study, we combined SERS and Raman spectral imaging techniques (spatial

resolution: 100 nm) to evaluate site-specific vibrational modes in SWCNTs and C60@SWCNTs. We

will show that the SERS spectral imaging provides much richer information related to local

vibrational states than in the regular Raman spectral imaging, likely indicating complex

nanostructures of the SWCNT stem from the non-hexagonal arrangements of carbon atoms. The

photo-induced coalescence reaction of C60 molecules encapsulated in the SWCNT was traced by

time-resolved SERS measurements at a certain site in the SERS spectral image. Detailed discussion

of the reaction route and possible intermediate geometries of coalesced C60 molecules will be

presented.

Acknowledgements: This work was supported by Japan Science and Technology Agency

Strategic Japanese-Spanish Cooperative Program: Nanotechnologies and New Materials for

Environmentak Challenges (PLE2009-0052) and Exotic Nanocarbons, Japan Regional Innovation

Strategy Program by the Excellence, JST.

References [1]. T. Fujimori et al., J. Am. Chem. Soc. 2010, 132, 6764.

P29

77

Fig. 1 Photocurrent density-

photovoltage characteristics of

CdSe QDSSCs without surface

modification (CdSe) and with

different surface modifications.

0.0 0.1 0.2 0.3 0.4 0.5 0.60

2

4

6

CdSe

CdSe/ZnS

CdSe/Zn2+

CdSe/S2-

Cu

rren

t d

en

sity

(m

A/c

m2)

Voltage (V)

EFFECTS OF SURFACE MODIFICATION ON PHOTOVOLTAIC PROPERTY

AND ULTRAFAST CARRIER DYNAMICS FOR QUANTUM DOT SENSITIZED

SOLAR CELLS

Qing Shen1,2

, Yasumasa Ayuzawa1, Kenji Katayama

3, Tsuguo Sawada

4

and Taro Toyoda1

1Department of Applied Physics and Chemistry,The University of Electro-Communications, 1-5-1

Chofugaoka, Chofu, Tokyo 182-8585, Japan 2PRESTO, Japan Science and Technology Agency, 4-8-1 Honcho Kawaguchi, Saitama 332-0012, Japan

3Department of Applied Chemistry, Faculty of Science and Technology, Chuo University, 1-13-27 Kasuga,

Bunkyo, Tokyo 112-8551, Japan 4Japan Science and Technology Agency, Kawaguchi Center Building, 4-1-8, Honcho, Kawaguchi-shi,

Saitama 332-0012 Japan

Email:[email protected]

In recent years, our group has been focusing on the preparation and

characterization of CdSe QDs prepared using the chemical bath deposition (CBD) method [1] and

applied to QD sensitized solar cells (QDSSCs) [2], in which the TiO2 nanoparticles electrode have

been used [3-5]. We have found that ZnS coating on the CdSe QDs can imporve the photovoltaic

properties significantly. In this study, we have modified CdSe QD surfaces with Zn2+

, S2-

and ZnS,

respectively. We have investigated the effects of these three kinds of surface modification on the

photovoltaic properties and ultrafast carrier dynamics for the CdSe QDSSCs. The ultrafast carrier

dynamics in the CdSe QDs was characterized using an improved transient grating (TG) method [4].

Fig. 1 shows

photocurrent density-voltage curves of CdSe

QDSSCs, in which the QD surfaces were not

modified and modified with Zn2+

, S2-

, and ZnS,

respectively. The photovoltaic conversion

efficiency, was improved significantly after

modifying the surface with Zn2+

or ZnS. However,

there is little effect of the modification with S2-

on

the photovoltaic properties. We also found that

there is a great decrease in the ultrafast electron

relaxation time of the CdSe QDs after surface

modification with Zn2+

or ZnS. However, the electron

relaxation time of the CdSe QDs is almost just a little after

the surface modifiction with S2-

.

References [1] S. Gorer and G. Hodes, J. Phys. Chem. 98, 5338 (1994).

[2] A. J. Nozik, Physica E 14, 115 (2002).

[3] Q. Shen, D. Arae, and T. Toyoda, J. Photochem. Photobiol. A: Chem. 164, 75 (2004).

[4] Q. Shen, K. Katayama, T. Sawada, M. Yamaguchi, and T. Toyoda, Jpn. J. Appl. Phys. 45, 5569 (2006).

[5] Q. Shen, J. Kobayashi, L. J. Diguna, and T. Toyoda, J. Appl. Phys. 103, 084304 (2008).

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PREPARATION AND CHARACTERIZATION OF POLYCYCLIC AROMATIC

HYDROCARBON-PILLARED SINGLE WALL CARBON NANOTUBE BUNDLES

Tsutomu Itoh1, Toshihiko Fujimori

1, Kazunori Fujisawa

1, Kyoichi Oshida

2,

Sang Young Hong3, Young Chul Choi

3, Kenji Takeuchi

1, Morinobu Endo

1,

Katsumi Kaneko1

1Shinshu University, 4-17-1 Wakasato, Nagano-shi, 380-8553, Japan

2Nagano National College of Technology, 716 Tokuma, Nagano-shi, 380-8550, Japan

3R&D Center, Hanwha Nanotech, 423-1, Cheongcheon-dong, Bupyeong-gu,

Incheon 403-030, Republic of Korea


We need to control both of the nanoporosity and electronic property of single wall carbon

nanotube (SWCNT) bundles for sustainable science and technology. Polycyclic aromatic

hydrocarbons (PAHs) adsorption on SWCNTs has been studied by Gotovac-Atlagić et al. and

Wesołowski et al [1-3]. They reported that electronic properties of SWCNT dramatically change due

to charge transfer interactions between PAHs and SWCNT. In this study, we inserted PAHs in the

SWCNT bundles to prepare the PAH-pillared SWCNT bundle for donating the selective molecular

adsorptivity and better electronic properties by the adsorption from solution. Examination of PAHs

treated SWCNT showed the presence of charge transfer interaction, which should originate from

intercalation and/or embedding of PAH molecules in the bundle or the internal tubespace,

respectively.

Acknowledgements: This work was supported by JST Strategic Japanese-Spanish Cooperative

Program: Nanotechnologies and New Materials for Environmental Challenges (PLE2009-0052).

This work was partly supported by JSPS KAKENHI: Grant-in-Aid for Scientific Research (A) (No.

21241026) and for Young Scientists (B) (No. 23710109). T. Itoh, T. Fujimori, K. Takeuchi, M.

Endo, and K. Kaneko were supported by Exotic Nanocarbons, Japan Regional Innovation Strategy

Program by the Excellence, JST.

References [1]. S. Gotovac, H. Honda, Y. Hattori, K. Takahashi, H. Kanoh, K. Kaneko. Nano lett. 2007, 7,583. [2]. S. Gotovac-Atlagić, T. Hosokai, T. Ohba, Y. Ochiai, H. Kanoh, N. Ueno, K. Kaneko. Phys. Rev. B 2010, 82,

075136.

[3]. R. P. Wesołowski, S. Furmaniak, A. P. Terzyk, P. A. Gauden. Adsorption 2011, 17, 1.

P31

79

PHOTOVOLTAIC CHARACTERIZATION OF FLOWER-LIKE

ZnO ELECTRODES ADSORBED WITH CdSe QDs

Shuzo Yamada,1 Eiji Hosono,

2 Haoshen Zhou,

2 Qing Shen,

1,3 Taro Toyoda

1

1 Department of Engineering Science, The University of Electro-Communications,

Tokyo, Japan 2 National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Japan

3 PRESTO, Japan Science and Technology Agency (JST), Saitama, Japan


In recent years, ZnO has attracted much attention as a porous oxide electrode of sensitized solar

cells (SSCs), because ZnO electrodes have some advantages such as a higher electric conductivity

compared with TiO2 and easier control of its morphology. Up to now, some approaches to improve

the photovoltaic properties of SSCs have been proposed by using different morphologies of ZnO

electrodes, like nanoparticle, nanotube, nanorod and nanowire. On the other hand, in future

applications, the SSCs are expected to be practically used with lower fabrication costs compared

with Si solar cells. Low temperature of synthesis of porous ZnO films provides a possibility to make

the SSCs cost down. In this study, we applied novel porous ZnO electrodes exhibiting flower-like

morphology to CdSe quantum dot (QD) SSCs (QDSSCs), which can be prepared at low

temperatures for SSCs. Flower-like ZnO electrodes allow better penetration of electrolyte and larger

ZnO-QD contact area. We investigated the optimum heating temperature in the preparation of ZnO

electrodes for better photovoltaic performances of CdSe QDs SSCs. Incident photon to current

conversion efficiency (IPCE) spectroscopy and photovoltaic properties were measured.

The porous ZnO were directly assembled on fluorine doped tin oxide (FTO) substrates by a

chemical bath deposition (CBD) method [1]. First, Zn(CH3COO)2・2H2O was dissolved in

methanol. The substrates were immersed in the above solution and were kept at 56 ℃ for 40 hours.

Finally, the samples were heated at 150 – 500 ℃ for 10 min in air. Then CdSe QDs were adsorbed

by immersing the electrodes in chemical solution containing 80 mM CdSO4, 80 mM Na2SeSO3 and

120 mM N(CH2COONa)3 at 10 ℃ [2]. Finally, the surfaces of the electrodes were modified by ZnS

coating [3]. The measurement was taken with 1 M S and 1M Na2S solution for electrolyte and a

Cu2S films as counter electrodes.

In the IPCE spectra of the CdSe QDSSCs, photosensitization by CdSe QDs could be clearly

confirmed in the visible region. The maximum IPCE value of 35 % was obtained for the QDSSCs

with the ZnO electrode heated at 150 ℃ and the IPCE value decreased with the increase of heating

temperature of ZnO electrode. Thus we found that there was an optimum heating temperature of the

ZnO fabrication for the IPCE and photovoltaic conversion efficiency η of the QDSSCs. The

maximum η of 0.9 % was obtained for CdSe QD sensitized flower-like ZnO solar cells.

References [1]. E.Hosono, S.Fujihara, T.Kimura, and H.Imai, J.Colloid interf. Sci. 2004, 272, 391.

[2]. S. Gorer and G. hodes, J. Phys. Chem. 1994, 98, 5338.

[3]. S.M. Yang et al., J. Mater. Chem. 2002, 12, 1459.

P32

80

METHANE ADSORPTIVITIES OF ACTIVATED CARBON MONOLITH

T. Kubo1, T. Ohba

1,

H. Kanoh

1, F. Rodrìguez-Reinoso

2,

M. Martínez Escandell2, J.M. Ramos-Fernández

2, and K. Kaneko

3

1Graduate School of Science, Chiba University, 1-33, Yayoi, Inage, Chiba 263-8522, Japan

2Laboratory of Advanced Materials University of Alicante AP. 99, E-03080 Alicante, Spain

3Research Center for Exotic NanoCarbons, Shinshu University, 4-17-1 Wakasato, Nagano, 380-

8553, Japan


Adsorption storage of natural gas can be contributed to clean energy society, if we can develop an efficient adsorbent for methane. Activated carbon (AC) is one of the promising adsorbents. Demand for a high performance AC is increasing year by year owing to the powerful adsorptivity for various substances. Above all, Activated Carbon Monolith (ACM) has a high application potential due to satisfactory porosity and high packing-density. Accordingly, ACM can be one of the most hopeful applicants for methane storage, because it can have a great adsorption capacity and high thermal conductivity for the efficient release of the heat of adsorption

[1,2]. Then,

we need to understand the relationship of methane adsorptivity and porosity of ACMs. ACMs were prepared for KOH activation and consolidation without binder. We used four

samples; pitch-based (ethylene tar) PY-89 and pitch based (vacuum residue) RV-93 in monolith and powder forms.

Methane adsorptivity and electrical conductivity of ACMs were measured. Porosities of ACMs were determined by N2 adsorption at 77 K. All samples have the surface area of about 2500 m

2 g

-1 and pore volume of 1.0 ml g

-1, being highly microporous. All samples show an excellent

methane adsorptivity at 303 K (Fig. 1); the methane adsorptivity of the monolith sample is almost similar to that of the powder sample. The monolith has no serious pore blocking for methane adsorption. This is also supported by the adsorption rate measurement. Furthermore, all samples release large heat of adsorption of more than condensation enthalpy of methane (Fig.2). Thus, all samples have strong adsorption potential. Electrical conductivity of the ACM is 30～50 S m

-1. The

electrical conductivity of the monolith sample is larger than that of powder because of high packing density. The high electronic conductivity brings about a high thermal conductivity which guarantees rapid dissipation of the large adsorption heat. Also the high electrical conductivity can lead to an energy saving desorption process.

References: [1] A.Silvestre-Albero, J.M.Ramos-Fernández, M Martínez-Escandell, A. Sepú lveda-Escribano, J. Silvestre-Albero,

and F. Rodríguez-Reinoso, Carbon, 2010, 48, 548. [2] V. Ruiz, C. Blanco, R. Santamaría, J.M. Ramos-Fernández, M. Martínez-Escandell, A. Sepú lveda-Escribano, and

F. Rodríguez-Reinoso et al., Carbon, 2009, 47, 195.

Fig .2 Isosteric heat of methane adsorption (qst) of ACMs

○：PY-89 (Powder) ●：PY-89 (Monolith)

△：RV-93 (Powder) ▲：RV-93 (Monolith)

Dashed Line: Condensation enthalpy of methane (8.2 kJ mol-1

)

Fig .1 Methane adsorption isotherms of ACMs at 303 K

○：PY-89 (Powder) ●：PY-89 (Monolith)

△：RV-93 (Powder) ▲：RV-93 (Monolith)

P33

81

CLUSTER-INDUCED ADSORPTION OF SUPERCRITICAL CH4 IN

CARBON NANOPORES

Tomonori Ohba,1 Katsumi Kaneko,

2 and Hirofumi Kanoh

1

1 Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522, Japan 2 Research Center for Exotic Nanocarbons, Shinshu University, 4-17-1 Wakasato, Nagano

380-8553, Japan


CH4 storage is one of important challenge to utilize clean energy resources. There are many

researches on adsorption of CH4 on nanoporous carbons at ambient temperature1-3

. However, we do

not understand sufficiently the essential mechanism of the supercritical CH4 adsorption in

nanopores. We apply in situ small angle X-ray scattering (SAXS) to assembled structure analysis of

supercritical CH4 in carbon nanopores; structure of supercritical CH4 adsorbed on single wall carbon

nanohorn (SWCNH) was evaluated from associated analysis of SAXS with grand canonical Monte

Carlo (GCMC) simulation.

SWCNH was oxidized in O2 atmosphere at 673 K for 1 h, named as ox-SWCNH. SAXS

measurements were performed using CuKa X-ray and a position sensitive proportional counter in

the scattering angular range of q = 0.2-5.0 . The SAXS profiles of SWCNH adsorbing CH4 were

obtained as a function of CH4 pressure. Density fluctuations were evaluated from Ornstein-Zernike

analysis of the SAXS profile near s = 0. GCMC simulations were conducted using a single center

Lennard-Jones potential for the intermolecular interaction of CH4 molecules and Steele 10-4-3

potential for the interaction between CH4 and a nanopore. The methodology of established GCMC

simulation was applied to the calculation of high pressure CH4 adsorption at 303 K

SWCNH doesn‘t have a molecular adsorption path into the internal nanopores, but ox-

SWCNH. Hence, SWCNH has only interstitial nanopores between SWCNH particles, while ox-

SWCNH has the interstitial and internal nanopores of SWCNH particles. The adsorption density of

CH4 in the interstitial nanopores is higher than that in the internal nanopores, because the interstitial

nanopores have stronger adsorption field. However, the adsorbed density in the internal nanopores

catches up with that in the interstitial nanopores above 4 MPa. The in situ SAXS measurements

show that CH4 molecules are dispersion and clustering in the interstitial and internal nanopores,

respectively. Specially, CH4 molecular assembly changes from dimeric cluster to trimeric cluster

about at 4 MPa. These results indicate that the intermolecular interaction of CH4 in the internal

nanopores is strongly enhanced by cluster formation and then, high density adsorption can be

achieved.

References [1]. Schlapbach, L and Züttel, A., Nature, 414, 353-358 (2001).

[2]. Bekyarova, E., Murata, K., Yudasaka, M., Kasuya, D., Iijima, S., Tanaka, H., Kanoh, H., and Kaneko, K., J. Phys.

Chem. B, 107, 4681-4684 (2003).

[3]. Murata, K., Hirahara, K., Yudasaka, M., Iijima, S., Kasuya, D., and Kaneko, K., J. Phys. Chem. B, 106, 12668-12669 (2002).

P34

82

STRUCTURES AND METHANE ADSORPTION PROPERTIES OF NANOPOROUS

CARBON MATERIALS

Hirotoshi Sakamoto,1 Tsutomu Itoh,

1 Katsumi Kaneko,

1

Ana María Silvestre-Albero,2 Joaquín Silvestre-Albero,

2 Francisco Rodríguez-Reinoso

2

1Research Center for Exotic Nanocarbons, Shinshu University,

Wakasato 4-17-1, Nagano, Japan 2 Laboratorio de Materiales Avanzados

Departamento de Química Inorgánica-Instituto Universitario de Materiales

Universidad de Alicante, Apartado 99, 03080 Alicante, Spain


Introduction

Methane storage is expected as one of the promising solutions for the current energy issues

because methane is green as energy source for its higher energy density and lower emission of CO2

per unit amount of heat than other hydrocarbons. Some excellent synthetic porous materials for

methane storage have been developed for decades such as carbon nanotubes, zeolites, metal-organic

frameworks, and so on.

Natural-resource based porous carbon materials should be re-evaluated for the recent

development of preparation method for them with excellent sorption properties, and then, this kind

of materials would be ―greener‖ in many aspects.

Results and discussion

A porous carbon material, LMA-23 has been developed towards the above-mentioned

purpose, prepared from peach stones with granular shape up to a few millimetres.

From TEM observations of LMA-23, randomly folded graphene sheets are stacked to form

micro and mesopore structure. In order to investigate its porous property, nitrogen adsorption

isotherm on LMA-23 was measured at 77 K, showing type I profile with microporosity providing

BET surface area of 1120 m2g

-1 and pore size distribution peaking at 0.56 nm by the HK method.

The isotherm exhibits a hysteresis loop in the relative pressure region over 0.42, which is supposed

to be due to its slit type mesoporosity.

Methane storage properties of LMA-23 were investigated by its sorption isotherms. At 77 K

(vapour pressure, P0 of methane is 1.16 kPa), the adsorption isotherm is similar to that of nitrogen

at 77 K with a smaller hysteresis loop, indicating methane molecules are accommodated in the pore

as the condensed form. The sorption amounts at higher temperature up to 100 kPa were measured to

be 31.3 ml(STP)g-1

at 273 K, and 20.1 ml(STP)g-1

at 298 K. Further characterization and

investigation are to be presented.

P35

83

SYNTHESIS OF ACTIVATED CARBONS WITH A HIGHLY DEVELOPED

MESOPOROSITY

J. Silvestre-Albero,1 A. Silvestre-Albero,

1 F. Rodríguez-Reinoso,

1 K. Kaneko

2, M.

Thommes3

1Laboratorio de Materiales Avanzados, Departamento de Química Inorgánica, Ap.99, E-

03080 Alicante, Spain 2Exotic Nanocarbon Research Center, Shinshu University, 4-17-1 Wakasato, 380-8553

Nagano, Japan 3Quantachrome Instruments, Boyton Beach, USA


The development of new nanoporous solids with extended pore diameter, i.e. pore size in the

mesoporous region, has extended its applications to research fields involving the adsorption of large

molecules (e.g., purification of bio-fluids and drug delivery) or stabilization of methane hydrates

[1,2]. Actually, mesoporous activated carbons are prepared by hard and soft-template technology,

e.g. nanocasting technology using mesoporous silica as a template. Apart from cost issues, these

techniques exhibit important drawbacks related with the scale-up (production cost and technological

issues) [3].

Synthesis of porous carbon materials starting from natural products (olive stones, apricot

stones, etc.) and using conventional activation procedures, i.e. physical activation with CO2 and

H2O or chemical activation with KOH or H3PO4, is actually the most economic and easy approach

for large-scale production [4]. Unfortunately, activated carbons prepared in this way exhibit a well-

developed porosity but mainly in the microporous range.

Here we propose the combination of chemical activation with ZnCl2 followed by physical

activation with CO2 and catalyzed by CaCl2 as an excellent approach for the preparation of activated

carbons with a highly developed cavitation-linked mesoporosity starting from natural products.

Experimental results show that the incorporation of CaCl2 as a catalyst in the physical

activation step using CO2 allows the preparation of carbon materials with a highly developed micro

and mesoporosity. N-nonane pre-adsorption experiments show that the microporosity is completely

blocked by the hydrocarbon whereas the mesoporous region, i.e. the hysteresis loop, is mainly

unaffected. The comparison of the gas adsorption measurements using different adsorbates (nitrogen

vs. argon) at cryogenic temperatures suggests the presence of cavitation effects in the mesoporous

structure, i.e. the mesoporous cavities must be connected with external surface through narrower

micro/mesoporous necks.

Acknowledgements: Authors acknowledge financial support from MEC (project PLE2009-0052)

and Generalitat Valenciana (PROMETEO/2009/002).

References [1]. M. Vallet-Regí, Chem. A Eur. J. 2006, 12, 5934.

[2]. T. Ohkubo, J. Miyawaki, K. Kaneko, R. Ryoo, N.A. Seaton, J. Phys. Chem. B 2002, 106, 6523.

[3]. R. Ryoo, S. Hoo Joo, S. Jun, J. Phys. Chem. B 1999, 103, 7743. [4]. H. Marsh, F. Rodríguez-Reinoso, Activated Carbon, Elsevier, London, 2006.

P36

84

PRODUCTION OF H2 FROM CH4 DECOMPOSITION OVER CATALYSTS

SUPPORTED ON SINGLE WALL CARBON NANOHORN

Shuwen Wang,1 Tomonori Ohba

1, Hirofumi Kanoh

1, Francisco Rodriguez-Reinoso

3,

Morinobu Endo2, Katsumi Kaneko

1,2

1Graduate School of Science, Chiba University, 1-33 Inage-ku, Yayoi-cho, Chiba,

263-8522, Japan 2Research Center for Exotic Nanocarbons (JST), Shinshu University, 4-17-1 Wakasato,

Nagano, 380-8553, Japan 3University of Alicante, Apartado 99, E-0308 Alicante, Spain


The catalytic decomposition of CH4 into H2 and carbon nanotubes shows a promising

alternative to the traditional methods of H2 production. Single wall carbon nanohorn (SWCNH) are

expected to provide an excellent catalyst support for CH4 decomposition reactions due to its unique

nanostructures[1]. This work reports the production of H2 during catalytic decomposition of

methane over metal catalysts supported on SWCNH. A number of the catalyst parameters, such as

the species of transitional metal used (e.g. Co, Fe, Cu, Ni), metal loading amount, composition of

their alloy, and the pretreatment method (H2 reduction or not) were investigated. Results indicate

that Ni-based catalysts appear to be superior to Fe, Co, and Cu towards H2 production, and the CH4

decomposition threshold temperature of the Ni catalysts supported on SWCNH is about 100K lower

than that supported on alumina. The optimized conditions are established for the production of CO2-

free H2.

Acknowledgements: This work was supported by JST Strategic Japanese-Spanish Cooperative

Program: Nanotechnologies and New Materials for Environmental Challenges (PLE2009-0052). M.

Endo and K. Kaneko were supported by Exotic Nanocarbons, Japan Regional Innovation Strategy

Program by the Excellence, JST.

References [1]Y. Aoki, K. Urita, D. Noguchi, T. Itoh, H. Kanoh, T. Ohba, M. Yudasaka, S. Iijima, K. Kaneko. Chem. Phys. Lett.

2009, 482, 269.

P37

85

PHOTOECITED HOLE DYNAMICS IN SEMICONDUCTOR QDs-SENSITIZED

SOLAR CELL MEASURED BY HETERODYNE TRANSIENT GRATING

METHOD

Hiroaki Hata,1,2

Kenji Katayama,1 Qing Shen,

2,3 Taro Toyoda

2

1 Department of Applied Chemistry, Chuo University, Tokyo, Japan

2 Department of Engineering Science, The University of Electro-Communications, Tokyo,

Japan 3 PRESTO, Japan Science and Technology Agency (JST), Saitama, Japan


The quantum dot-sensitized solar cells, a similar system to a dye-sensitized solar cell, have

attracted attention because it is expected that they have higher maximum efficiency. Various

improvements for the sensitizer and the structure of electrode have been intensively made. However,

little attention has been paid for the performance of electrolytes, although the electrolyte is a key

factor for the device performance. When the photoexcited holes are generated by the light

absorption of the sensitizer, they are transferred to electrolyte molecules, and they flow the current.

Recently, we have developed an improved method of the transient grating technique, the heterodyne

transient grating (HD-TG) method [1], which features a simple optical setup and highly sensitive

detection and can be applied for the carrier dynamics measurement. Here, we applied the NF-HD-

TG method to study the carrier dynamics in CdSe quantum dot-sensitized solar cell.

The photoelectrode was prepared by chemically adsorbing CdSe quantum dots on the

nanostructured TiO2 film and the surface was finished by the ZnS coating. A mixture of KCl and

Na2S were used as electrolyte solutions. The photoelectrode was measured in the electrolyte solution

or water using the HD-TG method. We could find a TG response only when the electrolyte solution

was used on the order of tens of milliseconds. It is supposed that holes transferred to the electrolyte

molecules were observed. This is the first demonstration of the lifetime measurement of the holes

transferred to the electrolyte molecules. The lifetime was 37 ms in this case, and it was observed

that the lifetime and the signal intensity, proportional to the carrier density, depends on the

electrolyte molecules and the electrode potentials. It is expected that this method could be utilized

for finding a new electrolyte for solar cell.

Reference [1]. Qing Shen et al., Appl. Phys. Lett. 97, 263113 (2010)

P38

86

PREPARATION OF LiMn2O4 CATHODE THIN FILMS BY

A MIST CVD PROCESS

Akihiro Yamaguchi,1

Kiyoharu Tadanaga,1 Atsushi Sakuda,

1

Akitoshi Hayashi,1 Masahiro Tatsumisago,

1 Mario Aparicio,

2 Alicia Duran

2

1 Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture

University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan

2 Institute de Ceramica y Vidrio, Consejo Superior de Investigaciones Cientificas, Madrid,

Spain 28049


In recent years, there is an increasing demand for all-solid-state thin-film batteries because of the

development of power sources for micro-electronic devices. Thin film batteries have been fabricated by

physical vapor deposition (PVD) process such as sputtering process. On the other hand, so-called the ―mist

CVD process‖ has been developed as a solution based process for thin films [1]. In the mist CVD process,

starting aqueous solution in source materials is atomized to form the mist particles by ultrasonic wave. The mists are transferred by a carrier gas to the reaction area to the deposition of thin films on the heated

substrate. This process possesses advantages of safety, cost-effective, light load to the environment,

multiplicity of applying to a lot of materials. Thus, the process is very attractive for the development of thin film batteries.

LiMn2O4 with spinel-type structure is one of the most attractive candidates to substitute commercial

LiCoO2 positive electrode, because of low-cost, high voltage, and non-toxicity. In the present study, LiMn2O4 thin films were prepared by the mist CVD process using aqueous

solution of lithium acetate and manganese acetate.

XRD patterns indicated that the thin films

obtained with substrate temperature of 200 oC exhibit

some weak LiMn2O4 diffraction peaks. After sintering

at 700 oC, the crystallinity was increased. FE-SEM

observation showed that the sintered film obtained with the deposition of about 30 min had dense

structure and no clacks with a thickness of about 750

nm. The electrochemical properties of LiMn2O4 thin film on Au / SiO2 substrate were evaluated in the three

electrode beaker cells using Li as the counter and

reference electrodes, and 1 M LiPF6 / (EC-DEC) as a

liquid electrolyte. Figure 1 shows cyclic voltammogram (CV) of a cell in the voltage range of

3.4 - 4.4 V. The CV exhibits typical anodic and

cathodic peaks at 3.95 and 4.15 V (vs. Li+/Li). In the

charge-discharge curves of a cell using LiMn2O4 thin

film sintered at 700 oC, the plateaus at 4.15 V and near

3.95 V (vs. Li+/Li) were observed. The initial

discharge capacity was about 80 mAh g-1

, and the cell showed good cycling performance during 10 cycles.

References [1] H. Nishinaka, T. Kawaharamura, S. Fujita, Jpn. J. Appl. Phys. 46 (2007) 6811-6813

Figure 1 Cyclic voltammograms of the cell

Li / 1M LiPF6 (EC-DEC) / LiMn2O4 sintered at 700 oC.

3.0 3.5 4.5 4.0 -0.1

-0.05

0

0.1

0.05

Potential (V)

25 oC,

3 mV s-1

Cu

rren

t (m

A)

P39

87

PHOTOCATALYTIC CHALLENGE TO CONVERT CO2 INTO METHANOL

Naveed Ahmed, Motoharu Morikawa, and Yasuo Izumi

Department of Chemistry, Graduate School of Science, Chiba University, Japan 263-8522


Carbon dioxide is one of the major greenhouse gases. It would be advantageous to capture CO2 from

emission source or the atmosphere and convert it to fuels using sustainable energy such as sunlight. An

efficient catalyst for the conversion is unknown partly because the thermodynamic limitation.

CO2(g) + 2H2O(g) CH3OH(g) + 1.5O2(g), G˚r = +689 kJ mol

–1

One of environmental challenges in catalysis is to obtain hydrogen from water splitting and to reduce CO2 using the hydrogen:

CO2(g) + 3H2(g) CH3OH(g) + H2O(g), G˚r = +2.9 kJ mol

–1.

Layered double hydroxides (LDHs) were chosen for this purpose due to the sorption capacity of CO2

in the layered space (1.4 mmol gsorbent–1

) and tunable semiconductor properties (band gap ≥ 3.0 eV) for photocatalysis as a result of the choice of metal cations.

LDH compounds formulated as [Zn3–xCuxMIII

(OH)8]+

2X2–

·mH2O (MIII

= Ga, Al; X = CO3, Cu(OH)4;

0 ≤ x ≤ 1.5) were synthesized from metal nitrates and Na2CO3 or (NH4)2CuCl4·2H2O at the pH 8 [1,2]. The

syntheses of LDHs consisting of [Cu(OH)4]2–

were performed under an argon atmosphere. Photocatalytic tests were performed in a quartz reactor in 2.3 kPa of CO2 and 21.7 kPa of H2 illuminated with UV-visible

light from 500-W xenon arc lamp.

The photocatalytic results are summarized in Table 1. Methanol formation was enabled using LDHs, especially containing Cu sites in clear

contrast to reported catalysts to produce

only CO [1]. The interlayer [Cu(OH)4]2–

sites were 5.3–5.9 times more effective than Cu sites in cationic layers [2]. In-situ

XAFS analysis revealed mechanism as in

Scheme 1. The feasibility of polymer electrolyte fuel cell to decompose water and

CO2 reduction using LDH by the produced

hydrogen was also demonstrated.

Table 1. Rates of photocatalytic conversion of CO2 and H2 over LDH photocatalysts.

Formation rate (nmol h–1 gcat–1) Selectivity to

CH3OH (mol%) CH3OH CO

[Zn3Al(OH)8]+

2(CO3)2–·mH2O 39 620 5.9

[Zn1.5Cu1.5Al(OH)8]+

2(CO3)2–·mH2O 130 370 26

[Zn3Ga(OH)8]+

2(CO3)2–·mH2O 51 80 39

[Zn1.5Cu1.5Ga(OH)8]+

2(CO3)2–·mH2O 170 79 68

[Zn3Ga(OH)8]+

2[Cu(OH)4]2–

·mH2O 300 130 71

[Zn1.5Cu1.5Ga(OH)8]+

2[Cu(OH)4]2–·mH2O 490 70 88

References [1] N. Ahmed, Y. Shibata, T. Taniguchi, Y. Izumi, J. Catal. 2011, 279, 123.

[2] N. Ahmed, M. Morikawa, Y. Izumi, Catal. Today, under review.

Scheme 1. SEM image and proposed reaction mechanism to

convert CO2 into methanol using LDH photocatalyst.

P40

88

SINGLE MOLECULE EMISSION BEHAVIOR OF A HEMICYANINE ANALOGUE

COVALENTLY ENCAPSULATED WITHIN CORE-SHELL SILICA

NANOPARTICLES

Boiko Cohen,1 Cristina Martin,

1 Srikant Iyer,

2 Ulrich Wiesner

2, Abderrazzak Douhal

1

1Departamento de Quımica Fisica, Facultad de Ciencias Ambientales y Bioquímica and

INAMOL, Universidad de Castilla-La Mancha, Carlos III S/N 45071 Toledo, Spain 2 Department of Materials Science and Engineering, Department of Chemistry and

Chemical Biology, Cornell University, Ithaca, New York 14853

E-mail: [email protected]; corresonding author: [email protected]

Fluorescent silica nanoparticles are good candidates for robust emitters with potential

applications in nanophotonics and medicine.[1] Recently, we used single molecule spectroscopy to

map the distribution of individual chromophores interacting with silica-based nanomaterials.[2]

Here, we present our results from ensemble average and single molecule spectroscopy studies on the

fluorescence enhancement mechanism of DY-630-maleimide covalently incorporated into two

different sized core-shell silica nanoparticles (NP). Single molecule experiments (Figure 1A) show

increased photobleaching stability and a 10-fold increase in the lifetimes upon encapsulation, in

agreement with the ensemble average experiments. Two subpopulations of molecules are identified

and assigned to molecules embedded within and on the surface of the core, respectively. Single

molecule fluorescence lifetime and polarization trajectories (Figure 1) provide evidence that under

certain conditions intermolecular interactions between several encapsulated molecules, such as

energy hopping and singlet – singlet annihilation, can occur within single NPs.

2.5

2.0

1.5

1.0

0.5

0.0

Inte

ns

ity

/ c

nts

3020100

Time / s

2.05 ns

6

4

2

0

Inte

ns

ity

[c

nts

/ms

]

35302520151050

Time [s]

1.00.80.60.4

P

perp

par

12

8

4

0

Co

rre

lati

on

Am

plitu

de

0.80.60.40.2

Lag Time [s]

20

0

Int.

[c

nts

]

12840Time [s]

Figure 1. A) Representative photobleach trace of single DY-630-maleimide nanoparticle complex; B) III and I -

polarized fluorescence traces (bottom pannel) along with the calculated polarization trajectory (top pannel)

corresponding to emission from multiple DY-630-MI chromophores and energy hopping; C) Typical intensity trace (top

pannel) and interphoton arrival-time distribution (bottom pannel) for the 15 nm-NP.

Acknowledgments: This work was supported by MICINN through projects UNCM05-23-025,

MAT2008-01609, and Consolider-Ingenio 2010 (MULTICAT, CDS2009-00050). B.C. thanks the

MICINN for the Ramon y Cajal contract. C.M. thanks MEC for the PhD fellowship.

References [1] A. Burns et al., Chem. Soc. Rev. 2006, 35,1028-1042.

[2] B. Cohen et al., J. Am. Chem. Soc. 2010, 132, 5507-5514; B. Cohen et al., Phys. Chem. Chem. Phys. 2011, 13, 1819-

1826.

A B C

P41

89

THE CAGED ANTI-CANCER DRUG TOPOTECAN ACTING AS AN EXCITED-STATE

ENERGY TRANSFER DONOR TO A RHODAMINE-CYCLODEXTRIN NANOCARRIER

Maria Rosaria di Nunzio1, YiLun Wang

1, Milo Malanga

2, László Jicsinszky

2, and

Abderrazzak Douhal1*

1Departamento de Química Física, Sección de Químicas, Facultad del Medio Ambiente and INAMOL,

Universidad de Castilla-La Mancha, Avda. Carlos III, S.N. 45071 Toledo, Spain.

E-mail: [email protected] 2CYCLOLAB Cyclodextrin Research & Development Laboratory Ltd., Budapest, P.O.Box 435, H-1525

Hungary


Supramolecular host-guest complexes between small molecules and cyclodextrins (CDs) are of great

technological importance in drug delivery.1 A valuable information for a deeply insight understanding on the fluidity of

biological membranes, the conformation of proteins, the kind of interactions between drugs and proteins, and the time

scale of the involved processes has been given by the fluorescence excitation energy transfer (FET) process.2-3 In this

work, we report on steady-state and time-resolved picosecond experiments using the anti-cancer drug topotecan (TPT)

in solution as well as within a rhodamin-B-subsituted β-cyclodextrin (6-monodeoxy-6-mono[(5/6)-rhodamin-B-

ylureido]-β-cyclodextrin, Rh-βCD). An energy transfer process from the initially excited-state donor (TPT in this case)

to the acceptor: Rh-βCD is clearly evidenced from the results.

Fig. 1 – (A) Emission spectra (λexc = 371 nm) of Rh-βCD in water upon addition of different concentrations of TPT (0-28.12

μM). Emission for Rh-βCD by energy transfer is clear evidenced when the contribution of a solution of Rh-βCD in water of the same concentration is subtracted from the whole spectrum, see the inset; (B) Emission spectra (λexc = 371 nm) of TPT in water after

subsequent additions of Rh-βCD with water (0-12.5 μM).

The typical red emission (λmax = 583 nm) of the rhodamin-B, excited in a region where it weakly absorbs (λexc =

371 nm), increases upon addition of TPT (Fig. 1A). The resonance interaction between both chromophores of the

complex TPT:Rh-βCD is further supported by the existence of an isoemissive point at ~ 570 nm (Figure 1B), which

points toward a correlation between these emissions. The fluorescence dynamics (ps – ns regime) of TPT in water was

investigated, in presence of not substituted CD, and interacting with the Rh-βCD structures. We believe that these results

contribute in a relevant way to the fields of drug delivery and nanosensors.

Acknowledgements: This work was supported by the JCCM and MICINN through projects PCI08-5868 and

MAT2008-01609, respectively. M.R.d.N., Y.L.W, an M.M. thank CYCLON Network (MRTN-CT-2008-Project

237962) for the Marie Curie fellowship.

References [1] Douhal, A. Editor, ―Cyclodextrin Materials Photochemistry, Photophysics and Photobiology‖, Vol. 1, 2006,

Elsevier, ISBN-13: 978-0-444-52780-6.

[2] Zhong, D. P.; Pal, S. K.; Wang, C.; Zewail, A. H. Proc. Natl. Acad. Sci. U.S.A. 2001, 98, 11873–11878.

[3] Peters, T., Jr. Biochemistry Genetics and Medical Applications; Academic Press: San Diego, 1996; pp 76–132

400 500 600 7000.0

4.0x10-7

8.0x10-7

1.2x10-6

B

[Rh-CD] / M

12.5

0

Em

iss

ion

in

ten

sit

y /

a.

u.

Wavelength / nm

400 500 600 700

0.0

1.0x10-7

2.0x10-7

3.0x10-7

2-1

2

[TPT]/[Rh-CD]

0

3.10

Difference

Em

iss

ion

in

ten

sit

y /

a.

u.

Wavelength / nm

1

400 500 600 7000.0

2.0x10-7

4.0x10-7

Em

iss

ion

in

ten

sit

y /

a.

u.

Wavelength / nm

[TPT] / M

28.12

0

A

P42

90

PROTON AND ELECTRON TRANSFER REACTION DYNAMICS WITHIN

MESOPOROUS SILICATE HOSTS

M. Gil1, C. Martin

1, J. A. Organero

1, M. T. Navarro

2, A. Corma

2 and A. Douhal

1

1Departamento de Química Física, Facultad de Ciencias Ambientales y Bioquímica y

INAMOL, Universidad de Castilla-La Mancha, Av. Carlos III s/n. 45071 Toledo, Spain. 2Instituto de Tecnología Química, UPV-CSIC, Av. de los Naranjos s/n, 46022, Valencia,

Spain.


Encapsulation of 7-hydroxyquinoline (7HQ) within mesoporous silicates of MCM-41 type

stabilizes ground state populations of anionic and zwitterionic forms of the dye even in aprotic

solvent through the formation of H-bonds with the nanohost [1]. Photobehavior of the trapped dye

may be altered through chemical modifications of the silicate framework. Introduction of titania

(TiO2) domains into the channels of MCM-41 is an efficient way to enhance a catalytical activity of

the material.

In this contribution, we report on the fs-dynamics of 7HQ within TiO2-doped silicate

materials and compare the findings to those using purely siliceous supports. The dynamics within

pure MCM-41 involve proton-transfer and relaxation processes at the femto- to picosecond time

scale [1]. However, the incorporation of TiO2 gives to the system a new deactivation channel, an

electron injection to the titania. This leads to a significant shortening of the observed emission decay

times (Figure). These results give new insight into the electron and proton transfer processes in the

confined media.

Fs-emission decays of 7HQ interacting with mesoporous hosts in DCM suspension.

Acknowledgments: This work was supported by the MICINN through projects Consolider

Ingenio 2010 (CSD2009-0050, MULTICAT) and MAT2008-01609.

References [1] M. Gil, C. Martin, J. A. Organero, M. T. Navarro, A. Corma, A. Douhal, J. Phys. Chem. C 2010, 114, 6311.

0 2 4 6 8 10 12

0.0

0.2

0.4

0.6

0.8

1.0

No

rma

lize

d in

ten

sity / a

.u.

Time / ps

Mesoporous TiO2

MCM-41, 3% TiO2 doping

MCM-41

P43

91

N

N C

C O

O

e -

h

0 2 4 6 8 10 200 400 6000.0

0.2

0.4

0.6

0.8

1.0

Al2O

3

ZrO2

ZnO

TiO2

Em

iss

ion

in

ten

sit

y

Time / ps

PHOTOSTUDIES OF AN ORGANIC DYE CELLS INTERACTING WITH

DIFFERENT SEMICONDUCTORS FOR UNDERSTAND THE BEHAVIOUR OF

DSSC

Cristina Martín, Marcin Ziółek, Boiko Cohen, Maria Marchena and Abderrazzak

Douhal*

Departamento de Química Física, Facultad de Ciencias Ambientales y Bioquimica and

Inamol, Universidad de Castilla-La Mancha, Carlos III, S.N., 45071 Toledo, Spain.


Recently, we have reported on the ultrafast events of TPC1 in different environments, and

interacting with titania nanoparticles, nanotubes and nanorods [1-3]. Here we report on studies of

primary events involved in the interaction of TPC1 with ZnO, ZrO2 and Al2O3 nanoparticles in a

liquid suspension, as well as TPC1 encapsulated in Al- and Ti-doped MCM-41 mesoporous sieves

(Figure 1). The emission transients of the relaxed S1 state of TPC1 show a non-exponential decay

with the averaged half-lifetimes of 4 ps, 11 ps and 150 ps for ZnO, ZrO2 and Al2O3, respectively.

For Al2O3, the dynamics depends on the dye‘s concentration indicating the presence of fluorescence

self-quenching, while for ZnO and ZrO2 the lifetime is determined by the electron injection to the

conduction band and trap states of the semiconductors. Furthermore, to get better understanding of

the limiting processes on the efficiency of the complete solar cell, we constructed dye sensitized

solar cells consisting of the studied

semiconductors and TPC1. The performance

of the cells was characterized by the J-V

curves. The results show remarkable

differences (between the nanoparticles and the

semiconductor molecular sieves) due to

changes in the interfacial charge separation

dynamics, electron recombination and dye

regeneration by the electrolyte, but

surprisingly the electron injection remains

comparable.

We believe that the present study is

important for a better understanding of the

photobehaviour of organic dyes interacting

with semiconductors and new mesoporous

materials involved in solar cells and

photocatalysis to develop clean-energy tools.

Acknowledgments: This work was supported by the MICINN and EU through projects

MAT2008-01609, Consolider-Ingenio 2010 (CDS2009-00050) and NANOSOL (FP7/2007-2013-

Project 235286), respectively. We thank Prof. Licheng Sun and Dr. Xichuan Yang for giving us the

TPC1 dye, and C. M. thanks the MEC for the PhD fellowship.

References: [1] M. Ziółek, X. Yang, L. Sun, A. Douhal, 2010, PCCP, 12:8098-8107.

[2] M. Ziółek, I. Tacchini, M. T. Martínez, X. Yang, L. Sun and A. Douhal, 2011. PCCP 13: 4032-4044.

[3] M. Ziółek, C. Martín, M. Navarro, H. Garcia and A. Douhal, 2011. J. Phys. Chem. C DOI: 10.1021/jp201627t.

Figure 1: Representative fs-emission transient showing

electron injection dynamics in different materials.

P44

92

6 7 8 9 10 11 12 13 14 15-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30

An

iso

tro

py

Time / ns

TSPP

TSPP+QA--CD

TSPP+HSA

Figure 1. Time-resolved anisotropy

decays of the studied systems.

Figure 2. Fluorescence up-conversion

signals of the studied systems

FEMTO-MICROSECOND STUDIES OF A PORPHYRIN IN CHEMICAL AND

BIOLOGICAL NANOCAVITIES

Y. Wang1, B. Cohen

1, J. A. Organero

1, M. Malanga

2, L. Jicsinszky

2 and A. Douhal

1

1Departamento de Quimica Fisica, Facultad de Ciencias del Medio Ambiente, Universidad

de Castilla-La Mancha, Avenida. Carlos III, s/n, 45071 Toledo, Spain, 2Department of Synthesis, CYCLOLAB R&D Lab. Ltd., IX. Illatos ut 7, H-1097 Budapest,

Hungary


The fs-μs dynamics of porphyrins and their derivatives is studied extensively due to their

application in the field of photodynamic therapy.[1,2] Additionally, the potential use of

cyclodextrins as drug nano-carriers has prompted a vigorous research.[3] We report on the

interaction of 5,10,15,20-tetrakis(4-sulfonatophenyl)-porphyrin (TSPP) with quaternary ammonium

modified β-cyclodextrin (QA-β-CD) and human serum albumin

(HSA) protein in aqueous solutions. TSPP forms 1:1 and 1:2

complexes with QA-β-CD, while with the HSA protein only 1:1

complex has been found. The chemical and biological nano-

cavities have significant effect on the relaxation of the Qx state

(from 9.1 ns to 11.3 ns in QA-β-CD and 11.6 ns in HSA).

Furthermore, the rotational times (400 ps for the free TSPP, 1.6

ns in QA-β-CD and 19 ns in HSA protein), obtained from

picosecond anisotropy

measurements, clearly

indicate the robustness

of the formed

complexes (Figure 1). The confined environment also

affects the ultrafast dynamics (from 190 fs in aqueous

solution to 150 fs in QA-β-CD and to 100 fs in HSA

protein) of the encapsulated molecule (Figure 2). We also

discuss the obtained results of ns-μs experiments.

Acknowledgments: This work was supported by the MICINN and EU through projects

MAT2008-01609, UNCM08-1E-068, UNCM08-1E-050 and CYCLON Network (MRTN-CT-2008-

Project 237962), respectively.

References

[1] J. S. Baskin, H. Yu and A. H. Zewail, J. Phys. Chem. A. 2002, 106, 9837.

[2] A. Synak, M. Ziolek, J. A. Organero and A. Douhal, J. Phys. Chem. B. 2010, 114, 16567. [3] K. Uekama, F. Hirayama and T. Irie, Chem. Rev.1998, 98, 2045.

0 5 10 15 20

0.0

0.2

0.4

0.6

0.8

1.0 TSPP

TSPP - QA--CD

TSPP - HSA

No

rma

lize

d I

nte

ns

ity

Time / ps

exc

=415nm

obs

=630nm

P46

93

OBSERVATION OF LARGE FLUORESCENCE QUENCHING OF NILE-RED

WITHIN MCM-41

Elisa Poyatos, Cristina Martín and Abderrazzak Douhal*

Departamento de Química Física, Facultad de Ciencias Ambientales y Bioquimica and

Inamol, Universidad de Castilla-La Mancha, Carlos III, S.N., 45071 Toledo, Spain.

*E-mail: [email protected]

Recently, we have reported on the spectroscopy and ultrafast dynamics events of several

dyes undergoing proton transfer and twisting motion within nanochannels and nanopores [1-4].

In this contribution, we will present our results on steady-state and ps-resolved emission

measurements of Nile Red (NR) interacting with regular and Al doped MCM-41. As references

we also studied NR in dichloromethane DCM solution and silica particles suspension.

The steady-state absorption/reflectance and emission spectra suggest a strong interaction

between the dye and the MCM-41 framework, and at least two different structures of NR

interacting with these nanochannels. These results agree with the multiexponential behavior of

the emission decay that highlights the quenching of the fluorescence. Besides that, we observed

a concentration dependence of the parent used solution to make the complexes, and the washing

effect of microstructures on the absorption and emission behavior.

The results are interpreted in terms of specific/site interactions and possible aggregates

format when interacting with the silica mesoporous material.

Figure 1. Emission decays of NR in (1) DCM, (2) MCM-41, and (3) Al doped MCM-41. Excitation wavelength: 635

nm, emission wavelength: 670 nm and (IRF) the instrumental response function (80 ps). The inset shows the molecular structure and MCM-41.

This study may help for better understanding of the behaviour of NR when used in cells

or comparable restricting systems.

Acknowledgments: This work was supported by the MICINN through projects MAT2008-

01609 and Consolider-Ingenio 2010 (CDS2009-00050). C.M. thanks the MEC for the PhD

fellowship.

References: [1] M. Gil, C. Martin, J. A. Organero, M. T. Navarro, A. Corma, A. Douhal, J. Phys. Chem. C 2010, 114, 6311.

[2] B. Cohen, Felix Sánchez, A. Douhal, J. Am. Chem. Soc, 2010, 132 (15), 5507.

[3] B. Cohen, C. Martín, N. Alarcos, J.A. Organero, A. Douhal et al. Phys. Chem. Chem. Phys, 2011, 13(5), 1819.

[4] M. Ziółek, C. Martín, M. Navarro, H. Garcia, A. Douhal, 2011. J. Phys. Chem. C DOI: 10.1021/jp201627t.

1.5 3.0 4.5 6.00.0

0.5

1.0

(1)

(2)

(3)

No

rma

lize

d C

ou

nts

time / ns

IRF

P47

94

PHOTOBIOHAVIOR OF (E)-2-((2-HYDROXYBENZYLIDENE)AMINO)-4-

NITROPHENOL) WITHIN MESOPOROUS MATERIALS

Noemí Alarcos1, Juan A. Organero

1, Félix Sanchez

2, Abderrazzak Douhal

1*

1

Departamento de Química Física, Facultad de Ciencias Ambientales y Bioquímica,

Universidad de Castilla-La Mancha, Toledo, Spain 45071. 2Departamento de Síntesis, Consejo Superior de Investigaciones Científicas (CSIC),

Sede C/ Juan de la Cierva, 3, Madrid, Spain E-28006.


Understanding the parameters that control the relaxation pathways of chromophores

encapsulated and interacting with silica based mesoporous materials is of fundamental

importance to various fields of nanoscience. Recently, we have reported on studies of different

dyes interacting with several silica based materials (zeolites and mesoporous materials) using

femtoecond to nanosecond time-resolved spectroscopies [1-3]. In this contribution, we focus on

the photodynamics of (E)-2-((2-hydroxybenzylidene)amino)-4-nitrophenol) (HBAN),

encapsulated and covalently bonded to silica based mesoporous materials (MCM-41 and Al

doped MCM-41). The complexes were investigated using steady state absorption and emission

spectroscopies as well as ps-time-correlated single-photon counting techniques. Upon caging

within MCM-41, we observed: i) a blue shift in the emission spectrum, ii) new components in

the emission decays and iii) an increasing in the lifetimes of the molecule. The behavior is due

to the interactions of the dye with the H-bonding sites (−Si−O−Si−, −OH) of the silicate

framework. For Al-MCM-41, the lifetimes of HBAN decreases. Furthermore, covalently

bonding HBAN to MCM-41 opens an additional decay channel for the tautomers through

proton-transfer reaction to the silica surface. We believe that these results are relevant to the

development of nanophotonic devices based on silica mesoporous nanomaterials and can help

for a better understanding of nanocatalysis.

Figure: emission decays (excited at 371 nm

and gated at 500 nm) of HBAN(1),

HBAN:MCM-41(2), HBAN covalently bonded

to MCM-41(4) and HBAN:Al-MCM-41(3) in

ACN suspension.

Acknowledgements: This work is supported by the MICINN through projects Consolider

Ingenio 2010 (CSD2009-0050, MULTICAT) and MAT2008-01609.

References [1]M. Ziolek, M. Gil, J. A. Organero, A. Douhal, J. Phys. Chem. C, 2010, 114, 9554

[2]B. Cohen, S. Wang, J. A. Organero, L. Franciscato, F. Sánchez, A. Douhal, J. Phys. Chem. C, 2010, 114, 6281.

[3] M. Gil, C. Martín, J. A. Organero, A. Douhal, J. Phys. Chem. C, 2010, 114, 6311.

1 2 3 4

0.01

0.1

1

IRF

(4)(3)

(2)

Co

un

ts

Time / ns

(1)

Author Index

Surname InstitutionName Contributions

Abad IMM - CSICBegoña P2, P11, P22

Alarcos Universidad de Castilla-La ManchaNoemí P46

Amador San Pablo CEU UniversityUlises OC19, P10

Aoyagi Ristumeikan Global Innovation Research (JST)Yoshinobu

Aparicio Instituto de Cerámica y Vidrio (CSIC)Mario OC7, OC8, P38

Aragay Institut Català de NanotecnologiaGemma P9, P27

Arakawa Japan Science and Technology Agency (JST) Atsushi

Atorrasagasti Ministerio de Ciencia e Innovacion (MICINN)Ignacio

Bauluz Ministerio de Ciencia e Innovacion (MICINN)Cristina

Bisquert Universitat Jaume I de CastellóJuan OC17, P7

Boronat Universidad Politecnica de Valencia - CSICMercedes L1

Briones IMM - CSICFernando P2

Buitrago Universidad de AlicanteRobinson P4

Caballero IMM - CSICOlga OC2, P11, P12, P21, P22

Campoy-Quiles Institute of Materials Science of BarcelonaMariano P18

Casco Universidad de AlicanteMirian Elizabeth P14

Castro Universidad de AlicanteMateus P24

Cohen Universidad de Castilla-La ManchaBoiko P40, P43, P44

De Miguel Universidad de Castilla-La ManchaGustavo OC15,P8, P17

Deb National Institute for Materials ScienceBiswapriya P21

Di Nunzio Universidad de Castilla-La ManchaMaria Rosaria P41

Diaz Universidad Politecnica de Valencia - CSICUrbano P5

Díaz IMM - CSICPablo P2, P11, P12, P21, P22

Douhal Universidad de Castilla-La ManchaAbderrazzak OC15, L2, P8, P17, P40, P41, P42, P43, P44, P45, P46

Durán Instituto de Cerámica y Vidrio (CSIC)Alicia OC7, OC8, P38

Endo Dept. of International Affairs (JST)Suzuka

Fujimori Shinshu UniversityToshihiko OC3, P28, P30

García Universidad Complutense de MadridSusana OC19, P19

García Universidad Politecnica de Valencia - CSICHermenegildo OC10

Garcia-Alvarado San Pablo CEU UniversityFlaviano OC19, P10

García-Linares Universidad Politecnica de MadridPablo

Gianotti Universidad Politecnica de Valencia - CSICEnrica P5

Gil Universidad de Castilla-La ManchaMichal P42

Gimenez Universitat Jaume I de CastellóSixto P7

González Ministerio de Ciencia e Innovacion (MICINN)Carolina

Hachiya University of Electro-CommunicationsSojiro P16

Haruta Tokyo Metropolitan UniversityMasatake OC9, OC10

Hata University of Electro-CommunicationsHiroaki P37

Hayase Kyushu Institute of TechnologyShuzi OC14, OC15, P8, P17, P26

Hernandez-Rodriguez Universidad Politecnica de Valencia - CSICManuel OC6, P3, P23

Imai Tokyo Institute of TechnologyHiroyuki OC5, P13

Imanishi Mie UniversityNobuyuki OC18, P20


Itoh Shinshu UniversityTsutomu OC3, P30, P34

Izumi Chiba UniversityYasuo P39

Kaizu University of TokyoToshiyuki OC12

Kaneko Shinshu UniversityKatsumi OC3,L7, P28, P30, P32, P33, P34, P35, P36

Kubo Chiba UniversityTakashi P32

López Universidad Politécnica de MadridManuel P6

Luque Universidad Politécnica de MadridAntonio OC13, L5

Marchena Universidad de Castilla-La ManchaMaria OC15,P8, P17, P43

Martí Universidad Politécnica de MadridAntonio

Martín IMM - CSICMaría Soledad OC1, OC2, P2, P11, P12, P21, P22

Martín Universidad Complutense de MadridNazario OC11

Martín Universidad de Castilla-La ManchaCristina P40, P42, P43, P44, P45

Merkoçi Institut Català de NanotecnologiaArben OC20, P9, P27

Mora Universitat Jaume I de CastellóIván L6

Moran Universidad Complutense de MadridEmilio

Mosa Instituto de Cerámica y Vidrio (CSIC)Jadra OC8

Nakanishi Dept. of International Affairs (JST)Akira

Ohba Chiba UniversityTomonori OC3, P32, P33, P36

Onishi University of Electro-CommunicationsYohei P25

Organero Universidad de Castilla-La ManchaJuan Angel P42, P44, P46

Pandey Kyushu Institute of TechnologyShyam S. OC14, OC15, P8, P17, P26

Pino Institut Català de NanotecnologiaFlavio P27

Poyatos Universidad de Castilla-La ManchaElisa P45

Prieto Ministerio de Ciencia e Innovacion (MICINN)Carlos

Rey Universidad Politecnica de Valencia - CSICFernando OC6, P3, P23

Rodríguez-Reinoso Universidad de AlicanteFrancisco OC4, P4, P14, P24, P32, P34, P35, P36

Sakamoto Shinshu UniversityHirotoshi P34

Sakuda Osaka Prefecture UniversityAtsushi P1, P38

Sepúlveda-Escribano Universidad de AlicanteAntonio OC4, P4

Serena Ministerio de Ciencia e Innovacion (MICINN)Pedro Amalio

Shen University of Electro-CommunicationsQing OC16, P16, P25, P29, P31, P37

Shinohara National Institute for Materials ScienceYoshikazu OC1, L3, P21

Silvestre Universidad de AlicanteJoaquín OC4, P34, P35

Simancas Universidad Politecnica de Valencia - CSICRaquel OC6, P23

Sonoyama Nagoya Institute of TechnologyNoriyuki P20

Tadanaga Osaka Prefecture UniversityKiyoharu OC7, P1, P38

Tatsumi Tokyo Institute of TechnologyTakashi OC5, L4, P13

Toyoda University of Electro-CommunicationsTaro OC16, P16, P25, P29, P31, P37

Wang Shinshu UniversityShuwen OC3, P36

Wang Universidad de Castilla-La ManchaYilun P41, P44

Yamada University of Electro-CommunicationsShuzo P31

Yamaguchi Nippon Steel Chemical Company, LimitedYoshihiro OC14, P26


Yamaguchi Osaka Prefecture UniversityAkihiro P38

Yamamoto Universidad Politecnica de MadridKenji P6, P15

Yanagida Osaka University (JST)Shozo L8

Yindeesuk University of Electro-CommunicationsWitoon

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