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Synthesis of Ag–Au nanoparticles of different sizes, compositions, element configurations (alloy- and core–shell-like) and electrocatalytic activities by using precursor-loaded PS–P2VP reverse micelles as nanoreactors. 

AOT reverse micelles are a common and convenient model system for studying the effects of nanoconfinement on aqueous solutions. The reverse micelle shape is important to understanding how the constituent components come together to form the coherent whole and the unique properties observed there. The shape of reverse micelles impacts the amount of interface present and the distance of the solute from the interface and is therefore vital to understanding interfacial properties and the behavior of solutes in the polar core. In this work, we use previously introduced measures of shape, the coordinate-pair eccentricity (CPE) and convexity, and apply them to a series of simulations of AOT reverse micelles. We simulate the most commonly used force field for AOT reverse micelles, the CHARMM force field, but we also adapt the OPLS force field for use with AOT, the first work to do so, in addition to using both 3- and 4-site water models. Altogether, these simulations are designed to examine the impact of the force field on the shape of the reverse micelles in detail. We also study the time autocorrelation of shape, the water rotational anisotropy decay, and how the CPE changes between the water pool and AOT tail groups. We find that although the force field changes the shape noticeably, AOT reverse micelles are always amorphous particles. The shape of the micelles changes on the order of 10 ns. The water rotational dynamics observed match the experiment and demonstrate slower dynamics relative to bulk water, suggesting a two-population model that fits a core/shell hypothesis. Taken together, our results indicate that it is likely not possible to create a perfect force field that can reproduce every aspect of the AOT reverse micelle accurately. However, the magnitude of the differences between simulations appears relatively small, suggesting that any reasonably derived force field should provide an acceptable model for most work on AOT reverse micelles. 

The core−shell assembly motif is ubiquitous in chemistry. While the most obvious examples are core/shell-type nanoparticles, many other examples exist. The shape of the core/shell constructs is poorly understood, making it impossible to separate chemical effects from geometric effects. Here, we create a model for the core/shell construct and develop proof for how the eccentricity is expected to change as a function of the shell. We find that the addition of a constant thickness shell always creates a relatively more spherical shape for all shapes covered by our model unless the shape is already spherical or has some underlying radial symmetry. We apply this work to simulated AOT reverse micelles and demonstrate that it is remarkably successful at explaining the observed shapes of the chemical systems. We identify the three specific cases where the model breaks down and how this impacts eccentricity. 

The vapor-liquid equilibrium (VLE) of methane + water mixtures has been studied with nuclear magnetic resonance (NMR) spectroscopy. This work had two primary goals. The first goal was to develop methods that broaden the utility of NMR spectroscopy for VLE measurements. In this regard, we report a method by which the liquid-phase and vapor-phase compositions are measured in separate experiments by adjusting the height of the liquid phase in the sample tube. We also report a method for hastening phase equilibration by adding glass beads to the sample and repeatedly inverting the sample tube. The second goal of this work was to collect VLE data on a challenging mixture with real-world importance. Mixtures of methane + water are a useful test case because of their challenging characteristics, including the widely differing vapor pressures of the two components. One use for accurate VLE data on methane + water mixtures is to better predict the formation of harmful liquid phases in natural gas pipelines. Herein we utilize 1H NMR spectroscopy to measure the VLE of methane + water mixtures at temperatures of 299.73, 307.98, and 323.25 K, and pressures ranging from 0.69 MPa to 13.89 MPa. Experiments were carried out with a 600 MHz spectrometer. Mixtures were prepared and equilibrated in a high pressure zirconia sample tube with an integrated needle valve. NMR-based VLE measurements on the liquid phase are in good agreement with available literature data and with Henry’s Law predictions at low pressures. However, the commonly used GERG-2008 model for natural gas systems deviates dramatically from the experimental data for the liquid phase. NMR-based VLE measurements on the vapor-phase resulted in measured water concentrations that are systematically lower than available literature data and models. This systematic offset is likely caused by peak overlap in the NMR spectra. 

Confining water to nanosized spaces creates a unique environment that can change water's structural and dynamic properties. When ions are present in these nanoscopic spaces, the limited number of water molecules and short screening length can dramatically affect how ions are distributed compared to the homogeneous distribution assumed in bulk aqueous solution. Here, we demonstrate that the chemical shift observed in ¹⁹F NMR spectroscopy of fluoride anion, F⁻, probes the location of sodium ions, Na⁺, confined in reverse micelles prepared from AOT (sodium dioctylsulfosuccinate) surfactants. Our measurements show that the nanoconfined environment of reverse micelles can lead to extremely high apparent ion concentrations and ionic strength, beyond the limit in bulk aqueous solutions. Most notably, the ¹⁹F NMR chemical shift trends we observe for F⁻ in the reverse micelles indicate that the AOT sodium counterions remain at or near the interior interface between surfactant and water, thus providing the first experimental support for this hypothesis 

Aerosol-OT reverse micelles represent a chemical construct where surfactant molecules self-assemble to stabilize water nanodroplets 1-10 nm in diameter. Although commonly assumed to adopt a spherical shape, all-atom molecular dynamics simulations and some experimental studies predict a non-spherical shape. If these aggregates are not spher- ical, then what shape do they take? Because the tools needed to evaluate the shape of something that lacks regular structure, order, or symmetry are not well developed, we present a set of three intuitive metrics  coordinate-pair eccentricity, convexity, and the curvature distribution  that estimate the shape of an amorphous object and we demonstrate their use on a simulated Aerosol-OT reverse micelle. These metrics are all well-established methods and principles in mathematics, and each provides unique information about the shape. Together, these metrics provide intuitive descriptions of amorphous shapes, facilitate ways to quantify those shapes, and follow their changes over time.