Lawrence Berkeley National Laboratory
A Model for Nucleation When Nuclei Are Nonstoichiometric: Understanding the Precipitation of Iron Oxyhydroxide Nanoparticles
- Author(s): Legg, BA
- Zhu, M
- Zhang, H
- Waychunas, G
- Gilbert, B
- Banfield, JF
- et al.
Published Web Locationhttps://doi.org/10.1021/acs.cgd.6b00809
© 2016 American Chemical Society. Despite years of study, quantitative models for the nucleation and growth of metal oxyhydroxide nanoparticles from aqueous solution have remained elusive. The problem is complicated by surface adsorption, which causes the stoichiometry of the nucleus to differ from that of the bulk precipitate and causes the surface tension of the precipitate-water interface to depend upon solution chemistry. Here we present a variation of classical nucleation theory that can accommodate surface adsorption, and apply it to understand the nucleation of β-FeOOH (akaganeite) nanoparticles from aqueous FeCl3solutions. We use small-angle X-ray scattering (SAXS) to quantify nucleation rates over a range of concentrations (5-200 mM FeCl3) and temperatures (47-80 °C), then apply our model to estimate the critical nucleus size and surface tension at each condition. The surface tension varies from 0.07 J/m2in 200 mM solutions to 0.16 J/m2in 5 mM solutions. This behavior indicates that the nuclei contain an excess of Cl-and H+relative to the ideal FeOOH stoichiometry, and the coadsorption of Cl-and H+is critical for reducing surface tension into a range where classical nucleation pathways can operate. Furthermore, we find that the surface tension can be roughly estimated from aqueous solubility data alone, which may help to understand systems where surface tension data is unavailable.