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2010 MICINN-JST Workshop Barcelona, 10 March 2010
Innovating in nanocomposite materials
Eduardo Ruiz-Hitzky
Materials Science Institute of Madrid
National Research Council of Spain
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Materials Science Institute of Madrid
ICMM http://www.icmm.csic.es/
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Materials Science Institute of MadridMaterials Science Institute of Madrid
Spanish National Research CouncilSpanish National Research Council
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Materials Science Institute of MadridMaterials Science Institute of MadridDepartment of New Architectures in Materials Department of New Architectures in Materials
ChemistryChemistry
Research scientistsEduardo Ruiz HitzkyPilar Aranda Miguel CamblorAngeles Martín-LuengoAna M. de AndrésMargarita Darder
Sabbatical stageMakoto Ogawa
Posdoc contractsCarolina Belver
Posdoc collaboratorsAna I. Ruiz
Hybrid, Biohybrid and Porous Materials Group
PhD & Master studentsAlmudena GómezFrancisco FernandesBernd WickleinAna AlcântaraYorexis GonzálezAlex RojasEzzouhra ZatileFidel A. CastroSonia Valle
Technical supportTomás GarcíaAndrés Valera
2010 MICINN-JST Workshop Barcelona, 10 March 2010
the design and chemical synthesis of new functional porous and hybrid materials using different strategies based on:
i) structure-direction agents, ii) self-assembling, iii) sol-gel, iv) intercalation/delamination, v) reeze-drying structuration, vi) templated synthesis.
The tailoring of the porosity at the nanometre scale, the incorporation of specific functionalities, and the improvement of chemical and mechanical stability, constitute one of our main goals. Approaches based on the assembling of materials of biological origin and inorganic solids through supramolecularchemistry, bio-inspired and biomimetic concepts are also used to prepare bio-nanohybridmaterials.
to provide the nanostructured materials with predefined and desirable properties, for applications in: selective adsorption and catalysis, biomedicine and tissue engineering, environmental analysis and remediation, magnetic, optical and electrochemical devices, etc.
Aim of the Group
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Relevant scientific contributions
Organic-Inorganic Hybridmaterials based on organicderivatives of silicatesE.Ruiz-Hitzky & J.M. Rojo Nature, 287, 28 (1980)
Intercalation compoundsbased on intracrystallinecomplexation in 2D solidsE.Ruiz-Hitzky & B. Casal Nature 276, 596 (1978)
Functional nanocompositesbased on intercalation of conductingpolymers in 2D solids.E.Ruiz-Hitzky & P. Aranda Advanced Mater. 2, 545 (1990)
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Relevant scientific contributionsMicrowaves irradiation in the synthesis of materials. Example: organic synthesis using inorganic solids as supports (dry media conditions, i.e. without any solvent).E. Gutiérrez, A. Loupy, G. Bram, E. Ruiz-Hitzky Tetrahedron Lett., 30, 945- 948 (1989)
Sol-gel preparation of functionalhybrid materials. Example: self-templated synthesis of organosiliciccompounds.E. Ruiz-Hitzky, S. Letaïef, V. PrévotAdvanced Mater. 14, 439-443 (2002)
Bio-nanocomposites based onself-assembling of clay mineralsand biopolymers.M. Darder, M. Colilla, E. Ruiz-HitzkyChem. Mater. 15, 3774-3780 (2003)
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Research on nanostructured clay materials
Bionanocomposites, prepared from the assembly of
biopolymers and other entities of biological origin to
diverse types of inorganic solids.
Inorganic-inorganic nanocomposites, including the
assembling of nanoparticles (NPs) to inorganic solids
provided with high porosity and specific surface area.
Graphene-like based nanocomposites, generated
from precursors of natural origin (e.g. sugar). These
materials have unique characteristics: electrical
conductivity & elevated specific surface area.
2010 MICINN-JST Workshop Barcelona, 10 March 2010
- biopolymer-clay nanocomposites- clay-enzyme systems- clay-living cells- virus-clay nanocomposites
Bio-hybrid clay materials
Clay particle
enzyme
Clay particle
enzyme
Clay particle
enzyme
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Bio-polymers Inorganic Solids
AlginatePectinι-Carrageenan
ChitosanXanthan
MontmorilloniteSepioliteLaponiteLayered perovskites
Layered Double Hydroxides(LDH) e.g. [Zn2Al]poly
saccharides
proteins GelatinZein
Bio-nanocomposites in our Group
phospholipidsPhosphatidyl-
cholineMontmorilloniteSepiolite
MontmorilloniteSepiolite
E. RUIZ-HITZKY, K. ARIGA, Y. LVOV (Editors). Bio-inorganic Hybrid Nanomaterials: Strategies, Syntheses, Characterization and Applications, Wiley-VCH, Weinheim, 2007
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Sepiolite-chitosan
5 µm
M. Darder, P. Aranda, E. Ruiz-Hitzky, Adv. Mater. 19, 1309–1319 (2007)
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Development of an electronic tongue
Electrodes:• ion-selective electrode (ISE) for calcium • conductivity cell • pH half-cell electrode • homemade sensor based on a
biopolymer-clay nanocomposite
Application of this multisensorsystem for the efficient qualitative analysis of aqueous ionic complex liquids, such as nutrient solutions employed in soilless cultures.
Darder et al. Sensors & Actuators B, 135 530–536 (2009)
Pioneering use of Case-Based Reasoning(CBR) as pattern recognition tool (Artificial Intelligence)
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Bionano-compositesepiolite-chitosan
Bio-inspired cellular materials
M. Darder, P. Aranda, E. Ruiz-Hitzky “Bionanocomposites: a new concept of ecological, bioinspired and functional hybrid materials” Adv. Mater. 19, 1309-1319 (2007)
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Bio-inspired cellular materials
MATERIALS BASED ON COMPOSITE FOAMS MADE OF NATURAL COMPONENTS
FIRE RESISTANT, BIOCOMPATIBLE AND BIODEGRADABLE INSULATING composite foams have been developed by the assembling of a biopolymer matrix withparticles of silicates belonging to the groupof fibrous clays (sepiolite and palygorskite). These low-density materials are fireresistant, biocompatible andbiodegradable, showing mechanicalproperties suitable for diverse andwidespread applications: acoustical andthermal insulationOther applications: food packaging andsupport for solids with electrical, magneticor optical properties, and drugs andbiological species. Tissue engineering.
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Ultra-lightweight bionanocomposites from sepiolite assembled with polysaccharides and proteins
Bio-inspired cellular materials
E. Ruiz-Hitzky, P. Aranda, M. Darder, F.M. Moreira Martins, Fernandes, C.R. Santos Matos, Spanish Patent P. 200900104 (14/01/2009)
E. Ruiz-Hitzky, P. Aranda, M. Darder, A.C. Santos de Alcântara, Spanish PatentP. 200930326 (17/06/2009)
•Mechanically resistant•Flame retardantproperties•Electrical, thermal andsound insulatingproperties•Biocompatible•Aparent density <50 Kg.m-3
Density: 0.02 g/cm3
2010 MICINN-JST Workshop Barcelona, 10 March 2010
The xanthan-sepiolite bio-nanocomposites are able to assemble Influenza viral particles with a homogeneous distribution on the modified fibres.
E. Ruiz-Hitzky, M. Darder, P. Aranda, M. Á. Martín del Burgo, G. del Real , Advanced Materials, 21, 4167-4171, 2009
Virus-sepiolite bionanocomposites
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Virus-clay bionanocomposites
Bionanocomposites can act as supports of Influenza viruses, in which viruses still exhibit bioactivity.
These materials can be used as novel adjuvants useful as Influenza vaccines.
The presence of specific sialicacid receptors could be applied for selective detection of viruses.
This new approach can tentatively be applied to similar systems for immobilizing other viruses (HIV,..)
E. Ruiz-Hitzky, M. Darder, P. Aranda, M. Á. Martín del Burgo,G. del Real Adv. Mater. 21, 4167-4171, 2009
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Inorganic-inorganic Nanocomposites• Inorganic-inorganic Nanocomposites
TiO2 nanoparticles
sepiolite microfibers
TiO2 nanoparticles
sepiolite microfibers
organoarcilla
Si Si
OH
O
SiO
OH
OSi Si
OH
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SiO
OH
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Si Si
SiO
OH
OH
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OSi Si
SiO
OH
OH
O
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Si Si
OH
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SiO
OH
OSi Si
OH
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SiO
OH
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Si Si
SiO
OH
OH
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OSi Si
SiO
OH
OH
O
O
Si Si
OH
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SiO
OH
OSi Si
OH
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SiO
OH
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Si Si
SiO
OH
OH
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OSi Si
SiO
OH
OH
O
O
Si Si
OH
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SiO
OH
OSi Si
OH
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SiO
OH
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Si Si
SiO
OH
OH
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OSi Si
SiO
OH
OH
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Si Si
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SiO
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OSi Si
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SiO
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Si Si
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OH
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OSi Si
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OH
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Nanocompositesílice-organoarcilla
Si Si
OH
O
SiO
OH
OSi Si
OH
O
SiO
OH
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Si Si
SiO
OH
OH
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OSi Si
SiO
OH
OH
O
O
Si Si
OH
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SiO
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OSi Si
OH
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SiO
OH
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Nanocompositesílice-arcilla
Si(OCH3)4
organoclaysilica-organoclaynanocomposite
silica-claynanocomposite
2010 MICINN-JST Workshop Barcelona, 10 March 2010
the gel
transition
S. Letaïef & E. Ruiz-Hitzky, Chem. Comm., 2996-2997 (2003)
S. Letaïef, M.A. Martín-Luengo, P.Aranda, E. Ruiz-Hitzky, Adv. Funct. Mater. 16, 401-409 (2006)
Inorganic-inorganic Nanocomposites
organoarcilla
Si Si
OH
O
SiO
OH
OSi Si
OH
O
SiO
OH
O
Si Si
SiO
OH
OH
O
OSi Si
SiO
OH
OH
O
O
Si Si
OH
O
SiO
OH
OSi Si
OH
O
SiO
OH
O
Si Si
SiO
OH
OH
O
OSi Si
SiO
OH
OH
O
O
Si Si
OH
O
SiO
OH
OSi Si
OH
O
SiO
OH
O
Si Si
SiO
OH
OH
O
OSi Si
SiO
OH
OH
O
O
Si Si
OH
O
SiO
OH
OSi Si
OH
O
SiO
OH
O
Si Si
SiO
OH
OH
O
OSi Si
SiO
OH
OH
O
O
Si Si
OH
O
SiO
OH
OSi Si
OH
O
SiO
OH
O
Si Si
SiO
OH
OH
O
OSi Si
SiO
OH
OH
O
O
Nanocompositesílice-organoarcilla
Si(OCH3)4
organoclaysilica-organoclaynanocomposite
2010 MICINN-JST Workshop Barcelona, 10 March 2010
FE-SEMimage
Metal-oxide nanoparticles on sepiolite
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Applications of magnetic clay materials
200 300 400 500 600 700 800
abso
rban
cia
λ (nm)
azul limpio
transparente
ionic/molecular adsorption & elimination from aqueoussolutions
Controlled transport & targeted-drug delivery
Microwave antenna: NMR imaging & hyperthermia treatments
Magnetic fillers for polymers: microwave-shielding pannels
E. Ruiz-Hitzky, P. Aranda, Y. González, Spanish Patent, March 2010.
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Carbon-silicate nanocomposites
CNTs/clay systems
Graphene-like/silicates
Graphene-like/silica
graphene graphene oxide
carbon nanotube (CNT)
2010 MICINN-JST Workshop Barcelona, 10 March 2010
SepioliteHydrophilic Easy to functionalizeModest elastic modulus (55 GPa)High aspect ratioElectrical insulatorLow cost material
CNTHydrophobicDifficult to functionalizeHigh modulus (~1 TPa)High aspect ratioConductingHigh cost material
Assembling sepiolite and C-nanotubes
Complementarities? Synergic effect?Complementarities? Synergic effect?
E. Ruiz-Hitzky, F.M. Fernandes, Spanish Patent P200931135 (9/12/2009)
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Graphene-like/clay nanocomposites
2010 MICINN-JST Workshop Barcelona, 10 March 2010
A. Gómez-avilés, M. Darder, P. Aranda, E. Ruiz-Hitzky, Angew. Chem. 46, 923-925 (2007)
Caramel-sepiolite nanocomposites
Clay + suggar caramel graphene-like/clay nanocomposite
C12H22O11
H2SO496% H2O
Partial dehydration
Carbonaceousmaterials:
graphene/grapheneoxide
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Carbon-clay nanocomposites: applications
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Carbon-sepiolite behaves better
as electrode than the recovered
carbon
R. Fernández-Saavedra, M. Darder, A. Gómez-Avilés, P. Aranda, E. Ruiz-Hitzky, J. Nanosci. Nanotech. 8, 1741–1750 (2008)
nanocomposite carbon-sepiolite from caramel
templated carbon from caramel-sepiolite
-Graphene-like sepiolite presents enough electrical conductivity avoidongthe use of conventional “Super P” additives
Electrodes for Li-insertion (batteries)
Cheap & Ecological Advanced Materials
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Collaboration with Japanese Groups (3/3)
Waseda University (Tokyo) Prof. Makoto Ogawa
Currently: in sabbatical stage at the ICMM
Topic: Artificial Photosynthetic Approaches
Objectives• Conversion of solar energy into chemical energy • Incorporation of antenna molecules for light-harvesting to
demonstrate the versatility of biomimetic silicate-lipid membranes as support for artificial photosynthesis systems
• Satisfy the need for highly stable/stabilised photosensitizermolecules.
• Exchange between members of Spanish & Japanese teams
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Collaboration with Japanese Groups (2/3)
NIMS (Tsukuba) Prof. Katsuhiko Ariga
Topic: Nanostructured hybrid materials
E. Ruiz-Hitzky, K. Ariga, Y. Lvov (Editors). Bio-inorganic HybridNanomaterials: Strategies, Syntheses, Characterization andApplications, Wiley-VCH, Weinheim, 2007 (ISBN 978-3-527-31718-9)
E. Ruiz-Hitzky, M. Darder, P. Aranda, K. Ariga, “Advances in Biomimeticand Nanostructured Biohybrid Materials”, Adv. Mater. 22, 323-336 (2010)
2010 MICINN-JST Workshop Barcelona, 10 March 2010
Collaboration with Japanese Groups (1/3)
Toyota Research Lab. (Aichi) Dr. Yoshiaki Fukushima
Topic: Functional nanostructured porous & hybrid materialsCo-organization of the Japan-Spain Workshop on Organic-
Inorganic Hybrid Materials Based on Clays (Toyota Research Center, Aichi, Japan, 2005)
Co-organization of the Spanish-Japan-American Trilateral Meeting on Clays (Madrid & Sevilla, Spain, 2010)
Kansai Paint Ltd (Hiratsuka ) Dr. Kenji Miyagawa
Topic: Nanostructured hybrids based on the encapsulation of dyes into zeolites & clays
Research financed through CSIC-Kansai contract
A
B
zeolite-dye
sepiolite-dye
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B
zeolite-dye
sepiolite-dye
Before UV irradiation
After UV irradiation