title: The Molecular Mechanism of Iron(III) Oxide Nucleation.
abstract: A molecular understanding of the formation of solid phases from solution would be beneficial for various scientific fields. However, nucleation pathways are still not fully understood, whereby the case of iron (oxyhydr)oxides poses a prime example. We show that in the prenucleation regime, thermodynamically stable solute species up to a few nanometers in size are observed, which meet the definition of prenucleation clusters. Nucleation then is not governed by a critical size, but rather by the dynamics of the clusters that are forming at the distinct nucleation stages, based on the chemistry of the linkages within the clusters. This resolves a longstanding debate in the field of iron oxide nucleation, and the results may generally apply to oxides forming via hydrolysis and condensation. The (molecular) understanding of the chemical basis of phase separation is paramount for, e.g., tailoring size, shape and structure of novel nanocrystalline materials.
authors.affiliation: Department of Chemistry, Physical Chemistry, University of Konstanz , Universitätsstraße 10, D-78457 Konstanz, Germany.
authors.forename: Johanna
authors.initials: J
authors.lastname: Scheck
authors.affiliation: Department of Chemistry, Physical Chemistry, University of Konstanz , Universitätsstraße 10, D-78457 Konstanz, Germany.|Jülich Centre for Neutron Science, Outstation at the MLZ, Forschungszentrum Jülich, Lichtenbergstraße 1, D-85748 Garching, Germany.
authors.forename: Baohu
authors.initials: B
authors.lastname: Wu
authors.affiliation: Laboratory for Soft Matter Electron Microscopy, BIMF; University of Bayreuth , Universitätsstraße 30, D-95440 Bayreuth, Germany.
authors.forename: Markus
authors.initials: M
authors.lastname: Drechsler
authors.affiliation: Department of Chemistry, Physical Chemistry, University of Konstanz , Universitätsstraße 10, D-78457 Konstanz, Germany.
authors.forename: Rose
authors.initials: R
authors.lastname: Rosenberg
authors.affiliation: ISTerre, CNRS, F-38041 Grenoble, France.
authors.forename: Alexander E S
authors.initials: AE
authors.lastname: Van Driessche
authors.affiliation: Cohen Geochemistry, School of Earth and Environment, University of Leeds , LS2 9JT, Leeds, U.K.|German Research Centre for Geosciences, GFZ, 14473, Potsdam, Germany.
authors.forename: Tomasz M
authors.initials: TM
authors.lastname: Stawski
authors.affiliation: Department of Chemistry, Physical Chemistry, University of Konstanz , Universitätsstraße 10, D-78457 Konstanz, Germany.
authors.forename: Denis
authors.initials: D
authors.lastname: Gebauer