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Assembling metal oxide nanoparticles to clays: towards advanced materials for environmental applications Pilar Aranda 1 , Carolina Belver 1,2 , Yorexis Gonzlez Alfaro 1 , Margarita Darder 1 , Eduardo Ruiz Hitzky 1 1 Instituto de Ciencia de

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Assembling metal oxide nanoparticles to clays: towards advanced materials for environmental applications

Pilar Aranda1, Carolina Belver1,2, Yorexis González‐Alfaro1, Margarita Darder1, Eduardo Ruiz‐Hitzky1

1 Instituto de Ciencia de Materiales de Madrid, CSIC, Spain 2 Autonomous University of Madrid, Spain

3rd Japanese‐Spanish Bilateral Symposium (SJ‐NANO 2013)

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This is a term coined at the National Institute for Materials Science (NIMS)1 in Japan to define the preparation of materials by arranging at the nanoscale structural units using different experimental approaches, such as physical and/or chemical manipulation of atoms and molecules, field‐ induced manipulation and self‐assembly synthetic. These methodologies can be applied to prepare sophisticated materials from very complex precursors but it can be also applied to the preparation of functional materials based on world‐spread resources as it is the case of clay minerals: this is the case of heterostructures consisting in assembling clay minerals with other inorganic solids.

Nanoarchitectonics

  • 1. http://en.wikipedia.org/wiki/Nanoarchitectonics

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Nanoarchitectonics

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Clays

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‐ Soil Science & Agronomy

‐ Adsorbents & Catalysts ‐ Petroleum Industry ‐ Cosmetics ‐ Pharmaceuticals & Bio‐Medical ‐ Environment preservation ‐ Civil Engineering ‐ Food: Additives & Packaging ‐ Animal Nutrition ‐ Industrial Specialties ‐ Energy ‐ Advanced Materials

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Clay minerals: main fields of interest

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Advanced applications of clays

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The concept of ecomaterials was created to denominate the ecologically‐benign materials, being proposed to encourage the development of materials that are non‐ damaging to the global environment

  • K. Yagi and K. Halada in EUROPEAN WHITE BOOK Material Science and Engineering, Chap. 6.10

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Ecomaterials

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Clay‐nanoparticle (NP) systems can be used for environmental remediation (water treatment). Examples: ‐ Supported NPs for photo‐decomposition of pollutants (e.g., [Ti‐NPs]‐clays) ‐Magnetic clays for the adsorption and recovering of pollutants (e.g., [Fe3O4‐NPs]‐clays & organoclays) ‐ Hexacyanoferrate supported on magnetic clays for Cs+ removal ‐ Superparamagnetic catalysts based on iron‐oxide NPs supported on clays for advanced oxidation processes (e.g. Fenton reactions)

Functional nanostructured clays: clay‐NPs

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Layered and fibrous clay minerals

‐ cation‐exchange ‐ swelling properties ‐ cation‐exchange ‐ nanopores ‐ surface Si‐OH groups

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Layered silicates:

  • montmorillonites
  • vermiculite

TiO2/ & SiO2‐TiO2/clay nanoarchitectures

  • E. Manova, P

. Aranda, M.A. Martin-Luengo, S. Letaief, E. Ruiz-Hitzky, Micropor. Mesopor. Mater. 131 (2010) 252–260 P . Aranda, R. Kun, M.A. Martín-Luengo, S. Letaïef, I. Dékány, E. Ruiz-Hitzky, Chem. Mater. 20 (2008) 84-89

Metal oxide NPs-clay nanoarchitectures

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Assembling of TiO2 and SiO2‐TiO2 NPs

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Assembling to sepiolite fibrous clay

generation of supported anatase NPs that can act as photocatalysts of high active surface area and easy recovering by filtration.

P . Aranda, R. Kun, M.A. Martín-Luengo, S. Letaïef, I. Dékány, E. Ruiz-Hitzky, Chem. Mater. 20 84-89 (2008)

  • E. Manova, P

. Aranda, M.A. Martin-Luengo, S. Letaief, E. Ruiz-Hitzky, Micropor. Mesopor. Mater. 131 (2010) 252–260

Assembling to layered clays

the heterostructures show specific surface areas more than 3 times larger than the pristine clay as it became delaminated due to the presence of titania or silica‐titania NPs (10‐15 nm diameter) between the silicate layeres

TiO2 TiO2 TiO2 TiO2 TiO2 TiO2 TiO2 TiO2 SiO2-TiO2 SiO2-TiO2 SiO2-TiO2 SiO2-TiO2 SiO2-TiO2 SiO2-TiO2 SiO2-TiO2 SiO2-TiO2
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20 40 60 80 100 20 40 60 80 100 120 irradiation time (min) TOC/TOC0 (%) KUN3-C2 KUN6-C2 KUN23 direct sepiolite KUN1-C2 S-TiO2 500oC/4h clay/TIPO/TMOS = 6/4/5, 10% TiO2-40% SiO2-50% clay clay/TIPO = 1/2, 36 % TiO2 clay/TIPO = 1/3, 46 % TiO2 direct photolysis CTAB-sepiolite clay/TIPO/TMOS = 2/6/1, 40% TiO2-10% SiO2-50% clay S-TiO2 500 oC/4h

Main interest in

photocatalysis: e.g., photocatalytic degradation of phenol using different TiO2- sepiolite heterostructures

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TiO2/ & SiO2‐TiO2/sepolite nanoarchitectures

Stabilization

  • f sepiolite and

anatase phase: S-doped TiO2/sepiolite

P . Aranda, R. Kun, M.A. Martín-Luengo, S. Letaïef, I. Dékány, E. Ruiz-Hitzky, Chem. Mater. 20, 84 (2008)

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Supported ferrofluids (“dry ferrofluids”)

Multifunctional porous & magnetic materials synthetized by treatment of silica, clays, zeolites, activated carbon.. with ferrofluids (eg., magnetite‐oleic acid NPs)

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  • 20000 -15000 -10000
  • 5000

5000 10000 15000 20000

  • 120
  • 100
  • 80
  • 60
  • 40
  • 20

20 40 60 80 100 120

M (emu / gNP) H (T)*10

4

NP10% NP35% NP20% NP50% NP

  • E. Ruiz-Hitzky, P

. Aranda, Y . González-Alfaro, Spain Pat. 201030333 (2010) & PCT ES2011/070145 (2011)

  • Y

. González-Alfaro, P . Aranda, F . M. Fernandes, B. Wicklein, M. Darder, E. Ruiz-Hitzky, Adv. Mater. 23 (2011) 5224–5228

Accesible at: http://www.icmm.csic.es/eng/sciact/Nanos tructured‐Hybrid‐Biohybrid‐and‐Porous‐ Materials‐Group.htm

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Adsorption of ionic & molecular pollutants (heavy metals, radionuclides,..) for their easy elimination from aqueous solutions

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Superparamagnetic Fe3O4‐sepiolite adsorbent

  • E. Ruiz-Hitzky, P

. Aranda, Y . González-Alfaro, Spain Pat. 201030333 (2010) & PCT ES2011/070145 (2011)

  • Y

. González-Alfaro, P . Aranda, F . M. Fernandes, B. Wicklein, M. Darder, E. Ruiz-Hitzky, Adv. Mater. 23 (2011) 5224–5228

Accesible at: http://www.icmm.csic.es/eng/sciact/Nanos tructured‐Hybrid‐Biohybrid‐and‐Porous‐ Materials‐Group.htm

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Several technologies based on Cs‐complexing ability of Prusian Blue (hexacyanoferrates of Fe, Cu or Ni (II)) are potentially of interest for removing and collecting radioactive cesium. One of them (JNC Corp) water‐soluble ferrocyanide, which works as an adsorbent, is added to cesium‐contaminated water so that it is bonded with cesium. Then, the resultant material is reacted by using iron chloride, which is a material for “magnetic substance” (sic). When an alkaline solution is added to it, a magnetic material containing cesium is generated. By using a magnet for magnetic separation, cesium can be removed and collected from the contaminated water.

http://techon.nikkeibp.co.jp/english/NEWS_EN/20111227/203092/

KFeIII[FeII(CN)6] ∙ yH2O (y = 1‐5)

“soluble” Prussian Blue (hexacyanoferrate, HCF)

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Specific adsorbent for radioactive Cs removal

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Amount of adsorbed Cs+ by sepiolite‐magnetite‐HCF based materials

Sample mmoles/g References SepNP50P‐Fe HCF 0.23 This work* SepNP50P‐Cu HCF 0.36 This work* Latex NPs/HCFs 0.02 – 0.04 Avramenko et al. J. Hazard. Mater. 2011, 186, 1343‐1350 Activated C/CuHCF 0.38 Li et al., Sep. Sci. Technol. 2009, 44, 4023‐4035 Magnetite/HCFs 0.12 Sasaki et al., Chem Lett. 2012, 41, 32‐34

CONCLUSION: The preliminary results at the laboratory level expect that the procedure here reported was satisfactorily applicable for the removal of radioactive Cs+ by magnet from water contaminated, even in the presence

  • f NaCl (e.g., 0.3 M).

* Cs removal capacity: 30‐50 g‐Cs/kg‐magnetic clay adsorbent

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Magnetic sorbent for radioactive Cs removal

  • E. Ruiz-Hitzky, P

. Aranda, M. Darder, Y . González-Alfaro, Spanish Patent P201330062 (2013)

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  • Clays are abundant and versatile eco‐materials that can be

assembled at the nanometric scale to metal oxide nanoparticles, leading to advanced functional materials relevant for applications in environmental remediation

  • Assembling of metal oxide NPs and clays can be reached using

ferrofluids in which are incorporated the NPs or via a colloidal route that use organoclays and sol‐gel methodologies

  • Environmental applications of the resulting NPs‐clay nano‐

architectures include their use as photocatalysts and superparamagnetic adsorbents (e.g. in elimination of radioactive cesium) & catalysts (e.g. in catalytic wet peroxide oxidation process of organic pollutants)

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Conclusions

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Financial support: CICYT (MAT2009‐09960 & MAT2012‐31759 projects) Ramón y Cajal Program (Dr. C. Belver contract)

Acknowledgements

Technical assistance:

  • Mr. Andrés Valera – FE‐SEM

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Thank you very much for your attention!!

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