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

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.

Simple method for the synthesis of inverse patchy colloids.

Inverse patchy colloids (IPC's) have recently been introduced as a conceptually simple model to study the phase-behavior of heterogeneously charged units. This class of patchy particles is referred to as inverse to highlight that the patches repel each other in contrast to the attractive interactions of conventional patches. IPCs demonstrate a complex interplay between attractions and repulsions that depend on their patch size and charge, their relative orientations as well as on charge of the substrate below; the resulting wide array of different types of aggregates that can be formed motivates their fabrication and use as model system. We present a novel method that does not rely on clean-room facilities and that is easily scalable to modify the surface of colloidal particles to create two polar regions with the opposite charge with respect to that of the equatorial region. The patch size is characterized by electron microscopy and fluorescently labeled to facilitate using confocal microscopy to study their phase behavior. We show that the pH can be used to tune the charges of the IPCs thus offering a tool to steer the self assembly.