Energetics of nanoparticle oxides interplay between surface energy and polymorphism？.docVIP

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Energetics of nanoparticle oxides interplay between surface energy and polymorphism？.doc

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Energetics of nanoparticle oxides interplay between surface energy and polymorphism？

Energeticsofnanoparticleoxides:interplaybetweensurface energyandpolymorphism{ AlexandraNavrotsky ThermochemistryFacilityandNEATORU,UniversityofCaliforniaatDavis,Davis,CA 95616,USA.E-mail:anavrotsky@ Received25thJuly2003,Accepted7thNovember2003 Article Review PublishedasanAdvanceArticleontheweb18thNovember2003 Manyoxidestendtoformdifferentstructures(polymorphs)forsmallparticles.Hightemperatureoxidemelt solutioncalorimetryhasbeenusedtomeasuretheenthalpyasafunctionofpolymorphismandsurfaceareafor oxidesofAl,Ti,andZr.Theresultscon?rmcrossoversinpolymorphstabilityatthenanoscale.Theenergies ofinternalandexternalsurfacesofzeoliticsilicaswithopenframeworkstructuresareanorderofmagnitude smallerthanthoseofoxidesofnormaldensity. Introduction energetically stable polymorph for speci?c surface areas exceeding y125 m2 g21. The thermodynamic stability of c-Al2O3 should be even greater than implied by this energy. Due to the presence of tetrahedral and octahedral sites in its Nanoscale phenomena are ubiquitous and important to geoscience. The realization is growing that many outcomes andratesofgeochemicalprocessesaregovernedbyphenomena at the nanometer scale, often in or at the surface of small particles.Surfaceinteractionsprobablyexertadisproportion- ate in?uence on the structure, chemistry, and movement of natural and anthropogenic nanomaterials in the Earth. In many cases, traditional distinctions between solutes, colloids and solids become vague. Nanoparticles, with sizes in the 1–100nmrange,lieintherealmbetweendissolvedmolecular clustersandcrystallinemacroscopicsolids.Theirpropertiesare differentfromthoseofeither. Finegrainedoxidesprecipitatedfromaqueoussolutionoften crystallize in structures different from those of coarsely crystallinematerials:c-aluminainsteadofcorundum,anatase andbrookiteinsteadofrutile,maghemiteinsteadofhematite, andahostofcomplexhydrousironoxyhydroxides.Ithasbeen suspected that differences in surface energy stabilize, as nanoparticles, polymorphs tha