Innovating in nanocomposite materials - Ministerio … · Innovating in nanocomposite materials ......

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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

Transcript of Innovating in nanocomposite materials - Ministerio … · Innovating in nanocomposite materials ......

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2010 MICINN-JST Workshop Barcelona, 10 March 2010

Materials Science Institute of Madrid

ICMM http://www.icmm.csic.es/

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2010 MICINN-JST Workshop Barcelona, 10 March 2010

Materials Science Institute of MadridMaterials Science Institute of Madrid

Spanish National Research CouncilSpanish National Research Council

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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

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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

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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)

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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)

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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.

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- 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

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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

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Sepiolite-chitosan

5 µm

M. Darder, P. Aranda, E. Ruiz-Hitzky, Adv. Mater. 19, 1309–1319 (2007)

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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)

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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)

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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.

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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

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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

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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

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Inorganic-inorganic Nanocomposites• Inorganic-inorganic Nanocomposites

TiO2 nanoparticles

sepiolite microfibers

TiO2 nanoparticles

sepiolite microfibers

organoarcilla

Si Si

OH

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SiO

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OSi Si

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Nanocompositesílice-organoarcilla

Si Si

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OSi Si

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SiO

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Nanocompositesílice-arcilla

Si(OCH3)4

organoclaysilica-organoclaynanocomposite

silica-claynanocomposite

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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

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SiO

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OSi Si

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Nanocompositesílice-organoarcilla

Si(OCH3)4

organoclaysilica-organoclaynanocomposite

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FE-SEMimage

Metal-oxide nanoparticles on sepiolite

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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.

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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)

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Graphene-like/clay nanocomposites

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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

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Carbon-clay nanocomposites: applications

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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

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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

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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)

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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

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zeolite-dye

sepiolite-dye

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zeolite-dye

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Before UV irradiation

After UV irradiation