Analysis of network formation and long-term stability in silica nanoparticle stabilized emulsions.

Emulsions are widely used in industrial applications, including in food sciences, cosmetics, and enhanced oil recovery. For these industries, an in depth understanding of the stability and rheological properties of emulsions under both static and dynamic conditions is vital to their successful application. Presented here is a thorough assessment of a model nanoparticle (NP) stabilized dodecane-in-water emulsion as a route to improved understanding of the relationship between NP properties, microstructure and droplet-droplet interactions on the stability and rheological properties of emulsions. Emulsions are obtained here with low NP loadings without the need for added electrolyte through the use of an optimized silica NP (SNP) surface modification procedure. The prepared emulsions were characterized via optical microscopy, cryo-scanning electron microscopy (cryo-SEM), zeta potential analysis and laser scanning confocal microscopy (LSCM), enabling quantification of the emulsion droplet size, SNP interfacial coverage/morphology and surface charge. The correlation of these properties with the rheology of the emulsions is investigated through small amplitude oscillatory shear experiments which provide significant insight into the origins of the emulsions' rheological behavior and their stability. In addition, long-term stability, droplet-droplet network formation and microstructural evolution are found to be readily detectable shortly after preparation through measured progression of the emulsion's rheological properties.

Stabilization of Oil-in-Water Emulsions with Noninterfacially Adsorbed Particles.

Classical (surfactant stabilized) and Pickering (particle stabilized) type emulsions have been widely studied to elucidate the mechanisms by which emulsion stabilization is achieved. In Pickering emulsions, a key defining factor is that the stabilizing particles reside at the liquid-liquid interface providing a mechanical barrier to droplet coalescence. This interfacial adsorption is achieved through the use of nanoparticles that are partially wet by both liquid phases, often through covalent surface modification of or surfactant adsorption to the nanoparticle surfaces. Herein, we demonstrate particle-induced stabilization of an oil-in-water emulsion with fully water wet nanoparticles (no interfacial adsorption) via synergistic interaction with low concentrations of surfactants. Laser scanning confocal microscopy analysis allows for unique and vital insights into the properties of these emulsions via both three-dimensional imaging and real-time monitoring of particle dynamics at the oil-water interface. Investigation of these "non-Pickering" particle stabilized emulsions suggests that the nonadsorbed particles impart stability to the emulsion primarily via entropic forces imparted by the accumulation of silica nanoparticles in the coherent phase between dispersed oil droplets.

Self-assembly of nanoparticles onto the surfaces of polystyrene spheres with a tunable composition and loading.

Functional colloidal materials were prepared by design through the self-assembly of nanoparticles (NPs) on the surfaces of polystyrene (PS) spheres with control over NP surface coverage, NP-to-NP spacing, and NP composition. The ability to control and fine tune the coating was extended to the first demonstration of the co-assembly of NPs of dissimilar composition onto the same PS sphere, forming a multi-component coating. A broad range of NP decorated PS (PS@NPs) spheres were prepared with uniform coatings attributed to electrostatic and hydrogen bonding interactions between stabilizing groups on the NPs and the functionalized surfaces of the PS spheres. This versatile two-step method provides more fine control than methods previously demonstrated in the literature. These decorated PS spheres are of interest for a number of applications, such as catalytic reactions where the PS spheres provide a support for the dispersion, stabilization, and recovery of NP catalysts. The catalytic properties of these PS@NPs spheres were assessed by studying the catalytic degradation of azo dyes, an environmental contaminant detrimental to eye health. The PS@NPs spheres were used in multiple, sequential catalytic reactions while largely retaining the NP coating.

Template assisted preparation of high surface area macroporous supports with uniform and tunable nanocrystal loadings.

The incorporation of catalytic nanocrystals into macroporous support materials has been very attractive due to their increased catalyst mass activity. This increase in catalytic efficiency is attributed in part to the increased surface area to volume ratio of the catalysts and the use of complementary support materials that can enhance their catalytic activity and stability. A uniform and tunable coating of nanocrystals on porous matrices can be difficult to achieve with some techniques such as electrodeposition. More sophisticated techniques for preparing uniform nanocrystal coatings include atomic layer deposition, but it can be difficult to reproduce these processes at commercial scales required for preparing catalyst materials. In this study, catalytic nanocrystals supported on three dimensional (3D) porous structures were prepared. The demonstrated technique utilized scalable approaches for achieving a uniform surface coverage of catalysts through the use of polymeric sacrificial templates. This template assisted technique was demonstrated with a good control over the surface coverage of catalysts, support material composition, and porosities of the support material. A series of regular porous supports were each prepared with a uniform coating of nanocrystals, such as NaYF4 nanocrystals supported by a porous 3D lattice of Ti1-xSixO2, Pt nanocrystals on a 3D porous support of TiO2, Pd nanocrystals on Ni nanobowls, and Pt nanocrystals on 3D assemblies of Au/TiO2 nanobowls. The template assisted preparation of high surface area macroporous supports could be further utilized for optimizing the use of catalytic materials in chemical, electrochemical, and photochemical reactions through increasing their catalytic efficiency and stability.

Role of interparticle interactions on microstructural and rheological properties of cellulose nanocrystal stabilized emulsions.

HYPOTHESIS: Microstructural and rheological properties of particle-stabilized emulsions are highly influenced by the nanoparticle properties such as size and surface charge. Surface charge of colloidal particles not only influences the interfacial adsorption but also the interparticle network formed by the non-adsorbed particles in the continuous phase. EXPERIMENTS: We have studied oil-in-water emulsions stabilized by cellulose nanocrystals (CNCs) with two different degrees of surface charge. Surface charge was varied by means of acidic or basic desulfation. Confocal microscopy coupled with rheology as well as cryogenic scanning electron microscopy were employed to establish a precise link between the microstructure and rheological behavior of the emulsions. FINDINGS: CNCs desulfated with hydrochloric acid (a-CNCs) were highly aggregated in water and shown to adsorb faster to the oil-water interface, yielding emulsions with smaller droplet sizes and a thicker CNC interfacial layer. CNCs desulfated using sodium hydroxide (b-CNCs) stabilized larger emulsion droplets and had a higher amount of non-adsorbed CNCs in the water phase. Rheological measurements showed that emulsions stabilized by a-CNCs formed a stronger network than for b-CNC stabilized emulsions due to increased van der Waals and H-bonding interactions that were not impeded by electrostatic repulsion.

Microwave assisted formation of monoreactive perfluoroalkylsilane-based self-assembled monolayers.

We demonstrate the use of microwave radiation as a tool to accelerate the formation of perfluoroalkylsilane based self-assembled monolayers (SAMs) on silicon oxide surfaces. Surface coverage of these SAMs of monoreactive perfluoroalkylsilanes increased in proportion to the duration over which the solutions were heated by microwave radiation.

Electrochemically active nickel foams as support materials for nanoscopic platinum electrocatalysts.

Platinum is deposited on open-cell nickel foam in low loading amounts via chemical reduction of Pt cations (specifically, Pt(2+) or Pt(4+)) originating from aqueous Pt salt solutions. The resulting Pt-modified nickel foams (Pt/Ni foams) are characterized using complementary electrochemical and materials analysis techniques. These include electron microscopy to examine the morphology of the deposited material, cyclic voltammetry to evaluate the electrochemical surface area of the deposited Pt, and inductively coupled plasma optical emission spectrometry to determine the mass of deposited Pt on the Ni foam substrate. The effect of potential cycling in alkaline media on the electrochemical behavior of the material and the stability of Pt deposit is studied. In the second part of this paper, the Pt/Ni foams are applied as electrode materials for hydrogen evolution, hydrogen reduction, oxygen reduction, and oxygen evolution reactions in an aqueous alkaline electrolyte. The electrocatalytic activity of the electrodes toward these processes is evaluated using linear sweep voltammetry curves and Tafel plots. The results of these studies demonstrate that nickel foams are acceptable support materials for nanoscopic Pt electrocatalysts and that the resulting Pt/Ni foams are excellent electrocatalysts for the hydrogen evolution reaction. An unmodified Ni foam is shown to be a highly active electrode for the oxygen evolution reaction.

Colloidal core-shell materials with 'spiky' surfaces assembled from gold nanorods.

A series of core-shell materials with 'spiky' surfaces are prepared through the self-assembly of gold nanorods onto polystyrene microspheres. Loading of the nanorods is finely tuned and the assemblies exhibit surface plasmon resonance properties. The 'spiky' surface topography of the assembled structures could serve as a versatile substrate for surface-enhanced Raman spectroscopy based sensing applications.