Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 11, Issue 12, Pages 3541-3551Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200401050
Keywords
anatase; nanoparticle assembly; nanostructures; nonaqueous synthesis; surface chemistry
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Nanoparticle powders composed of surface-functionalized anatase crystals with diameters of about 3 nm self-organize into different structures upon redispersion in water. The assembly is directed by a small amount of a low-molecular-weight functional ligand (the assembler) adsorbed on the surface of the nanoparticles. The ligand functionality determines the anisotropy of the resulting structures. Multidentate ligands, such as trizma ((HOCH2)(3)CNH2) and serinol ((HOCH2)(2)CNH2), with a chargeable terminal group preferentially induce the formation of anisotropic nanostructures several hundreds of nanometers in total length, whereas all the other investigated ligands (ethanolamine H2N(CH2)(2)OH, glycine hydroxamate H2NCH2CONHOH, dopamine (OH)(2)C6H3(CH2)(2)NH3Cl, tris (HOCH2)(3)-CCH3) mainly lead to uncontrolled agglomeration. Experimental data suggests that the anisotropic assembly is a consequence of the water-promoted desorption of the organic ligands from the 10011 faces of the crystalline building blocks together with the dissociative adsorption of water on these crystal faces. Both processes induce the preferred attachment of the titania nanoparticles along the [001] direction. The use of polydentate and charged ligands to functionalize the surface of nanoparticles thus provides a versatile tool to control their arrangement on the nanoscale.
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