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5. Reactividad <strong>de</strong> sólidos porosos basados<br />

en arcillas inducida por microondas:<br />

aplicaciones medioambientales<br />

Palabras clave: arcillas pilareadas, sepiolita, activación<br />

con microondas<br />

Se han <strong>de</strong>sarrollo materiales porosos basados en<br />

esmectitas naturales ricas en hierro que se modifican<br />

por inserción <strong>de</strong> pilares <strong>de</strong> alúmina o mixtos <strong>de</strong> alúmina/óxidos<br />

<strong>de</strong> hierro. Su eficacia para <strong>de</strong>gradar contaminantes<br />

fenólicos se ha ensayado en reacciones <strong>de</strong><br />

hidroxilación en presencia <strong>de</strong> agua oxigenada. La transformación<br />

<strong>de</strong>l fenol en catecol e hidroquinona, catalizada<br />

por estos materiales que incluyen hierro, resulta<br />

ser especialmente favorecida mediante activación con<br />

microondas comparada con la activación térmica convencional.<br />

Por otro lado, materiales porosos basados en<br />

sepiolita modificada por tratamientos básicos y por<br />

<strong>de</strong>pósito <strong>de</strong> óxidos <strong>de</strong> metales <strong>de</strong> transición como el<br />

Ni(II) se han aplicado en reacciones soportadas en fase<br />

seca (ausencia <strong>de</strong> disolventes) y asistidos por microondas.<br />

La aplicación a la <strong>de</strong>gradación controlada <strong>de</strong> un<br />

pesticida clorado como el lindano, es especialmente útil<br />

en el caso <strong>de</strong> la sepiolita tratada con NaOH.<br />

5. Reactivity of modified mineral-based<br />

porous solids induced by microwave irradiation:<br />

environmental applications<br />

Keywords: pillared clays, sepiolite, microwave irradiation<br />

Porous materials based on aluminium- or aluminiumiron<br />

pillared naturally occurring Fe-rich smectites have<br />

been <strong>de</strong>veloped. Their efficiency to <strong>de</strong>compose phenolic<br />

contaminants has been checked in reactions of<br />

hydroxylation with hydrogen peroxi<strong>de</strong>. The catalytic<br />

transformation of phenol to catechol and hydroquinone<br />

on these Fe-containing materials is specially favored<br />

un<strong>de</strong>r microwave irradiation, compared to conventional<br />

heating. In this line of work we can also inclu<strong>de</strong>, sepiolite<br />

based porous materials prepared by base treatment<br />

and <strong>de</strong>posit of transition metal oxi<strong>de</strong>s and used in supported<br />

reactions un<strong>de</strong>r dry media conditions with<br />

microwave irradiation. The application towards <strong>de</strong>composition<br />

of a chlorinated pestici<strong>de</strong> (lindane) has been<br />

studied in <strong>de</strong>pth.<br />

1. Salvador, Raquel; Casal, Blanca; Yates, Malcolm; Martín-Luengo, Mª Angeles; Ruiz-Hitzky, Eduardo; Appl. Clay Sci. 22, 103-113, 2002<br />

2 . Letaief, Sadok; Casal, B.; Kbir-Ariguib, N.; Trasbelsi-Ayadi, M.; Ruiz-Hitzky, Eduardo; Clay Miner. 37, 517-529, 2002<br />

3. S. Letaïef, B. Casal, P. Aranda, A. Martín-Luengo, E. Ruiz-Hitzky, Appl. Clay Sci. (in press).<br />

Proyectos:<br />

<strong>Materiales</strong> porosos <strong>de</strong>rivados <strong>de</strong> sepiolita y otras arcillas: tratamientos con microondas. Código: MAT2000-1451, Período:<br />

28/12/2000 - 27/12/2003, Fuente <strong>de</strong> financiación: CICyT, Importe total (euros): 63.707, Investigador Principal: Aranda, P.,<br />

Investigadores: Ruiz-Hitzky, E.; Casal, B.; Galván, J.C.; Martín-Luengo, M.A., Becarios y Doctorandos: Sadok L.; Salvador, R.<br />

6. Sílices y silicatos <strong>de</strong> porosidad<br />

controlada<br />

Palabras clave: sílice, silicatos, sólidos mesoporosos<br />

Se ha proseguido con el estudio <strong>de</strong> nuevas mesofases<br />

organo-inorgánicas <strong>de</strong>rivadas <strong>de</strong> sílice preparadas en<br />

nuestro grupo mediante procedimientos <strong>de</strong> autoensamblaje<br />

<strong>de</strong> alcoxisilanos con ca<strong>de</strong>nas <strong>de</strong> tensioactivos<br />

catiónicos que actúan como auto-plantillas (“selftemplating”).<br />

Tanto las fases hexagonales como laminares<br />

presentan capacidad <strong>de</strong> inclusión <strong>de</strong> especies<br />

neutras (polioxietilenos) o aniónicas (do<strong>de</strong>cilsulfato y<br />

otros tensioactivos). Estos sistemas son <strong>de</strong> gran interés<br />

como mo<strong>de</strong>los <strong>de</strong> membrana, vesículas y liposomas<br />

mostrando capacidad <strong>de</strong> incorporación <strong>de</strong> especies<br />

bioactivas. Por otro lado, se prosigue la preparación <strong>de</strong><br />

materiales en lámina <strong>de</strong>lgada a partir <strong>de</strong> sílices porosas<br />

<strong>de</strong> tipo MCM41 por EBE (Electron Beam Evaporation).<br />

Los sistemas porosos resultantes analizados por SEM y<br />

AFM confirman la baja rugosidad <strong>de</strong> los films y la existencia<br />

<strong>de</strong> matrices (arrays) <strong>de</strong> poros or<strong>de</strong>nados orientados<br />

paralelamente a la superficie <strong>de</strong>l substrato. Los<br />

indices <strong>de</strong> refractividad son <strong>de</strong>l or<strong>de</strong>n <strong>de</strong> 1, 40-1, 45,<br />

inferiores a los <strong>de</strong>l SiO 2<br />

másico.<br />

6. Silica and silicates of controlled<br />

porosity<br />

Keywords: silica, silicates, mesoporous solids<br />

As a continuation of the work already started, the study<br />

of organo-inorganic mesophases <strong>de</strong>rived from silica<br />

through procedures of self-assembly of cationic surfactants,<br />

acting as self-templating agents, has been followed.<br />

These species in their hexagonal or lamellar phases<br />

show ability to enclose neutral (polyethylene oxi<strong>de</strong>)<br />

or anionic species (do<strong>de</strong>cylsulphate and other surfactants).<br />

The systems prepared in this manner have great<br />

interest as membrane mo<strong>de</strong>ls, vesicles and liposomes,<br />

showing ability to incorporate bioactive species, as<br />

well. Moreover, the preparation of thin films by electron<br />

beam evaporation (EBM) on MCM-41 type porous silicas<br />

is being further <strong>de</strong>veloped. The resulting porous<br />

systems have been analyzed by SEM and AFM and in<br />

this way their low rugosity and the existence of arrays<br />

of pores parallel to the substrate surface has been confirmed.<br />

The refractive in<strong>de</strong>xes found for these solids<br />

are 1, 40-1, 45 lower than those corresponding to the<br />

bulk SiO 2 .<br />

1. Hernán<strong>de</strong>z-Velez, M.; Sánchez-Garrido, O.; Bueno-Barbeyto, R.M.; Shmytko, I.M.; García-Poza, M.M.; Vázquez-Burgos, L.; Martínez-<br />

Duart, J.M.; Ruiz-Hitzky E., Thin Films Solids, 402 (2002) 111-116<br />

2. Ruiz-Hitzky E., Letaïef S., Prévot V., Adv. Mater. 14, 439-443, 2002<br />

3. Ruiz-Hitzky E., Aranda P. J. Mater. Chem. 12 (2002) xi-xv<br />

Proyectos: MAT2000-0096-P4-02<br />

101

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