Experimental and molecular dynamics characterization of dense microemulsion systems: morphology, conductivity and SAXS.

Microemulsions are exciting systems that are promising as tuneable self-assembling templating reaction vessels at the nanoscale. Determination of the nano-structure of microemulsions is, however, not trivial, and there are fundamental questions regarding their design. We were able to reproduce experimental data for an important microemulsion system, sodium-AOT-n-heptane-water, using coarse-grained simulations involving relatively limited computational costs. The simulation allows visualization and deeper investigation of controversial phenomena such as bicontinuity and ion mobility. Simulations were performed using the Martini coarse-grained force field. AOT bonded parameters were fine-tuned by matching the geometry obtained from atomistic simulations. We investigated several compositions with a constant ratio of surfactant to oil while the water content was varied from 10 to 60% in weight. From mean square displacement calculation of all species, it was possible to quantify caging effects and ion mobility. Average diffusion coefficients were calculated for all charged species and trends in the diffusion coefficients were used to rationalize experimental conductivity data. Especially, the diffusion coefficient of charged species qualitatively matched the variation in conductivity as a function of water content. The scattering function was calculated for the hydrophilic species and up to 40% water content quantitatively matched the experimental data obtained from small angle X-ray scattering measurements. For higher water contents, discrepancies were observed and attributed to a nearby phase separation. In particular, bicontinuity of water and oil was computationally visualized by plotting the coordinates of hydrophilic beads. Equilibrated coarse-grained simulations were reversed to atomistic models in order both to compare ion mobility and to catch finer simulation details. Especially, it was possible to capture the intimate ion pair interaction between the sodium ion and the surfactant head group.

Electrically induced anisotropy in a colloidal dispersion of nanospheres as measured by electric birefringence.

Electrically induced birefringence experiments were performed on dispersions consisting of sulfate latex nanospheres of two different sizes and charges dispersed in an electrolyte solution, at various ionic strengths. The induced birefringence was found to have an important contribution increasing as a quadratic power law of the volume fraction of the spheres. This shows that interparticle interactions play a role in the observed birefringence. The data were analyzed, using a theory from Hafkenscheid and Vlieger [Physica 75 (1974) 57], in terms of the changes of the interparticle separations in the directions parallel and perpendicular to the applied electric field.

Environmentally Friendly Carbon-Preserving Recovery of Noble Metals From Supported Fuel Cell Catalysts.

The dissolution of noble-metal catalysts under mild and carbon-preserving conditions offers the possibility of in situ regeneration of the catalyst nanoparticles in fuel cells or other applications. Here, we report on the complete dissolution of the fuel cell catalyst, platinum nanoparticles, under very mild conditions at room temperature in 0.1 M HClO4 and 0.1 M HCl by electrochemical potential cycling between 0.5-1.1 V at a scan rate of 50 mV s(-1) . Dissolution rates as high as 22.5 µg cm(-2) per cycle were achieved, which ensured a relatively short dissolution timescale of 3-5 h for a Pt loading of 0.35 mg cm(-2) on carbon. The influence of chloride ions and oxygen in the electrolyte on the dissolution was investigated, and a dissolution mechanism is proposed on the basis of the experimental observations and available literature results. During the dissolution process, the corrosion of the carbon support was minimal, as observed by X-ray photoelectron spectroscopy (XPS).

The interpretation of dielectric spectroscopy measurements on silica and hematite sols.

Experimental data on the dielectric response of silica and hematite sols from the literature are interpreted using an analytical theory developed previously (Chassagne, C., Bedeaux, D., and Koper, G. J. M., J. Phys. Chem B105, 11,743 (2001), and Physica A, to be published). The theory is found to correctly predict both the relaxation frequency and the dielectric permittivity enhancement at low frequencies with only one free parameter. This parameter can be the zeta potential or the Stern layer conductance, in the case that the zeta potential is fixed to agree with the electrophoretic mobility measurements.

High yield, controlled synthesis of graphitic networks from dense micro emulsions.

We report on the production of Carbon Nano Networks (CNNs) from dense microemulsions in which catalyst nanoparticles have been synthesized. CNNs are 3D carbon networks, consisting of branches and junctions, and are mesoporous, graphitic, and conductive being suitable as electrode materials.

New method to determine the viscoelastic properties of admicelles around the stick-slip transition.

We report on a new method by which, for the first time, the viscoelastic properties of an adsorbed surfactant layer on a solid surface are measured. It is based on an analysis of the amplitude and the phase angle of the pressure fluctuations induced by a pulsating flow of a Newtonian surfactant solution through cylindrical pores. This method is subsequently used to determine the viscoelastic properties of an admicelle, formed when flushing surfactant solutions through nanopores, around the stick-slip transition. We find that the admicelle responds elastically for flow strengths below the transition and beyond the viscous. This is in agreement with the hypothesis formulated earlier (Cheikh, C.; Koper, G. J. M. Phys. Rev. Lett. 2003, 91, 156102).