title: Precursor-directed assembly of complex oxide nanobeads: the role of strongly coordinated inorganic anions.
abstract: The use of an inorganic perrhenate ligand in the structure of early-transition-metal alkoxide precursors permits to achieve uniform self-assembly of the primary nanoparticles produced by their hydrolysis. The latter has been carried out in a hydrocarbon reaction medium by the addition of water with vigorous stirring, either in the pure form or in solutions in parent alcohols. The self-assembly is guided by the surface charge enhanced by the presence of strongly coordinated anions as determined by zeta potential measurements. The aggregation process has been followed in real time by nanoparticle tracking analysis (NanoSight technique). The reaction products are spherical aggregates with a size that can be efficiently controlled through the polarity of the reaction medium. The produced nanobeads have been characterized by TEM, SEM-EDS, DLS, nitrogen adsorption, and FTIR. The coordination of metal centers has been investigated using EXAFS spectroscopy. The aggregates remain amorphous on thermal treatment of up to 700 °C (24 h treatment) but crystallize when treated at 1000 °C. This latter process is associated with the total loss of rhenium content and offers early-transition-metal oxides as products.
authors.affiliation: Department of Chemistry, BioCenter SLU, Box 7015, 75007 Uppsala, Sweden.
authors.forename: Olesya A
authors.initials: OA
authors.lastname: Nikonova
authors.forename: Jean-Marie
authors.initials: JM
authors.lastname: Nedelec
authors.forename: Vadim G
authors.initials: VG
authors.lastname: Kessler
authors.forename: Gulaim A
authors.initials: GA
authors.lastname: Seisenbaeva
mesh_terms: D000438:Alcohols / Q000737:chemistry; D006838:Hydrocarbons / Q000737:chemistry; D054118:Nanospheres / Q000737:chemistry*; D010087:Oxides / Q000737:chemistry*; D012211:Rhenium / Q000737:chemistry*
chemical_list: D000438:Alcohols; D006838:Hydrocarbons; D010087:Oxides; C015428:perrhenate; D012211:Rhenium