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Monodisperse Iron Oxide Nanoparticles by Thermal Decomposition: Elucidating Particle Formation by Second-Resolved in Situ Small-Angle X-ray Scattering.

ABSTRACT: The synthesis of iron oxide nanoparticles (NPs) by thermal decomposition of iron precursors using oleic acid as surfactant has evolved to a state-of-the-art method to produce monodisperse, spherical NPs. The principles behind such monodisperse syntheses are well-known: the key is a separation between burst nucleation and growth phase, whereas the size of the population is set by the precursor-to-surfactant ratio. Here we follow the thermal decomposition of iron pentacarbonyl in the presence of oleic acid via in situ X-ray scattering. This method allows reaction kinetics and precursor states to be followed with high time resolution and statistical significance. Our investigation demonstrates that the final particle size is directly related to a phase of inorganic cluster formation that takes place between precursor decomposition and particle nucleation. The size and concentration of clusters were shown to be dependent on precursor-to-surfactant ratio and heating rate, which in turn led to differences in the onset of nucleation and concentration of nuclei after the burst nucleation phase. This first direct observation of prenucleation formation of inorganic and micellar structures in iron oxide nanoparticle synthesis by thermal decomposition likely has implications for synthesis of other NPs by similar routes.

SUBMITTER: Lassenberger A

PROVIDER: S-EPMC5445716 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature

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Monodisperse Iron Oxide Nanoparticles by Thermal Decomposition: Elucidating Particle Formation by Second-Resolved in Situ Small-Angle X-ray Scattering.

Lassenberger A A Grünewald T A TA van Oostrum P D J PDJ Rennhofer H H Amenitsch H H Zirbs R R Lichtenegger H C HC Reimhult E E

Chemistry of materials : a publication of the American Chemical Society 20170502 10

The synthesis of iron oxide nanoparticles (NPs) by thermal decomposition of iron precursors using oleic acid as surfactant has evolved to a state-of-the-art method to produce monodisperse, spherical NPs. The principles behind such monodisperse syntheses are well-known: the key is a separation between burst nucleation and growth phase, whereas the size of the population is set by the precursor-to-surfactant ratio. Here we follow the thermal decomposition of iron pentacarbonyl in the presence of o ...[more]

PMID: 28572705

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Project description:Recently, we reported time-resolved synchrotron small-angle X-ray scattering (TR-SAXS) studies during aqueous emulsion polymerization using a bespoke stirrable reaction cell (J. Am. Chem. Soc. 2021, 143, 1474-1484). This proof-of-concept study utilized a semifluorinated specialty monomer (2,2,2-trifluoroethyl methacrylate) to ensure high X-ray contrast relative to water. Herein, we extend this approach to emulsion polymerization of methyl methacrylate (MMA) in the presence or absence of sodium dodecyl sulfate (SDS) at 70 °C. Solution conductivity measurements for this anionic surfactant indicated a critical micelle concentration (CMC) of 10.9 mM at this temperature. Thus, SDS was employed at either 1.0 or 20.0 mM, which corresponds to well below or well above its CMC. Postmortem analysis by 1H NMR spectroscopy indicated MMA conversions of 93-95% for these three formulations. We demonstrate that the X-ray contrast between water and PMMA is sufficiently large to produce high-quality scattering patterns during TR-SAXS experiments. Such patterns were fitted using a hard-sphere scattering model to monitor the evolution in particle diameter. This enabled (i) determination of the time point for the onset of nucleation and (ii) the evolution in particle size to be monitored during the MMA polymerization. The final particle diameters obtained from such TR-SAXS studies were consistent with postmortem DLS analyses, while TEM studies confirmed that near-monodisperse latex particles were formed. Micellar nucleation occurs within just 2 min when the SDS concentration is well above its CMC, resulting in a high particle number concentration and relatively small latex particles. In contrast, when SDS is either absent or present below its CMC, particle nuclei are formed by homogeneous nucleation over significantly longer time scales (14-15 min). In the latter case, adsorption of SDS onto nascent particles reduces their coagulation, giving rise to a larger number of smaller particles compared to the surfactant-free polymerization. However, the characteristic time required for the onset of nucleation is barely affected because this is mainly controlled by the kinetics of homogeneous polymerization of the relatively water-soluble MMA monomer within the aqueous phase. These results suggest that the aqueous emulsion polymerization of several other (meth)acrylic monomers, and perhaps also vinyl acetate, may be amenable to TR-SAXS studies.

Dataset Information

Monodisperse Iron Oxide Nanoparticles by Thermal Decomposition: Elucidating Particle Formation by Second-Resolved in Situ Small-Angle X-ray Scattering.

Publications

Monodisperse Iron Oxide Nanoparticles by Thermal Decomposition: Elucidating Particle Formation by Second-Resolved in Situ Small-Angle X-ray Scattering.

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