Electrochemical Properties of Silver Nanoparticles in Mesoporous Silica and Titania Films: Specific Behavior of Titania Composite.

Electrochemical behavior of silver nanoparticles in mesoporous oxides electrodes is investigated. Mesoporous SiO2 and TiO2 films deposited on FTO (fluorine-doped tin oxide) and containing Ag nanoparticles (NPs) are used as electrodes. The study of voltammetric curves (CVs) and the diffusion of Ag+ ions out of the films highlight the importance of the retention of Ag+ ions by the TiO2 films. By varying several factors such as the speed rate or the initial potential, we observe the existence of the two potentials' anodic peaks. These are explained by the nature of two silver NP populations created in two distinct areas in the film and with different size distributions, as shown by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. The size distributions of the two NP populations allow the position and shape of each of the oxidation peaks in the CVs to be adequately simulated.

Two-liquid wetting and phase electrowetting as a probe for surface chemistry of hydrophobic materials.

Two-liquid contact angle measurement and electrowetting under low frequency are two measurement methods extremely sensitive to surface polarity and charge density. The theory underlying these two methods are described and have been applied to hydrophobic coatings. By combining these two methods, we successfully demonstrated the variations of the surface properties of polymer-based hydrophobic coatings when exposed to different chemical environments (pH modification or molecular grafting) with real-time phase electrowetting measurements.

Photoelectrochemical Behavior of Silver Nanoparticles inside Mesoporous Titania: Plasmon-Induced Charge Separation Effect.

The self-assembly block copolymer method was used to synthesize mesoporous titania films and silver nanoparticles (NPs) were grown inside the films. Such silver NPs-titania films are known for their multicolor photochromic properties due to a photo-oxidation reaction of silver in the presence of titania under light excitation which is attributed to a plasmon induced charge separation. Here, the photoelectrochemical properties of these composite films have been investigated at different light wavelengths and chemical environment in order to characterize the light-induced redox reactivity modifications. Cyclic voltammetry study shows that the Ag+ electro-reduction peak potential varies depending on the light irradiation, which determines the state of the silver nanoparticles complexed or not by titania.

Electroactive Area from Porous Oxide Films Loaded with Silver Nanoparticles: Electrochemical and Electron Tomography Observations.

Electrochemical studies of nanomaterial-based electrodes have been widely developed for catalyst and energy-harvesting applications. The evolution of these electrodes over time and their efficiency have been extensively studied and analyzed in order to optimize their performance. However, the electrochemical responses of electrodes are rarely studied in terms of the position of the active species within these electrodes. In this paper, we highlight that the spatial location of silver nanoparticles (NPs) embedded inside semiconductive porous films, TiO2 or Fe2O3, is crucial for the electrochemical response. In fact, by using cycling voltammetry and electron tomography experiments, we show the existence of an "electroactive area", corresponding to a reduced thickness of the sample in close vicinity to a fluorine-doped tin oxide substrate where most of the electrochemical responses originate. Our results demonstrate that, for a film thickness of several hundred nanometers, only less than 30 nm close to the substrate responds electrochemically. However, cyclic voltammetry empties the electroactive area of silver NPs. Therefore, application of chronoamperometry coupled to irradiation allowed regeneration of this area thanks to an increased diffusion of silver species. In this paper, we also show the significant diffusion of silver species within the film during electrochemical experiments, a phenomenon even increased by irradiation. These results are therefore an important step that shows the importance of the localization of active species within a porous film and help in understanding and increasing the durability of nanomaterial-based electrodes.

Development of Biphasic Formulations for Use in Electrowetting-Based Liquid Lenses with a High Refractive Index Difference.

Commercial electrowetting-based liquid lenses are optical devices containing two immiscible liquids as an optical medium. The first phase is a droplet of a high refractive index oil phase placed in a ring-shaped chassis. The second phase is electrically conductive and has a similar density over a wide temperature range. Droplet curvature and refractive index difference of two liquids determine the optical strength of the lens. Liquid lenses take advantage of the electrowetting effect, which induces a change of the interface's curvature by applying a voltage, thereby providing a variable focal that is useful in autofocus applications. The first generation of lens modules were highly reliable, but the optical strength and application scope was limited by a low refractive index difference between the oil and conductive phase. Described herein is an effort to increase the refractive index difference between both phases, while maintaining other critical application characteristics of the liquids, including a low freezing point, viscosity, phase miscibility, and turbidity after thermal shock. An important challenge was the requirement that both phases have to have matching densities and hence had to be optimized simultaneously. Using high throughput experimentation in conjunction with statistical design of experiments (DOE), we have developed a series of empirical models to predict multiple physicochemical properties of both phases and derived ideal locations within the formulation space. This approach enabled the development of reliable liquid lenses with a previously unavailable refractive index difference of Δ nD of ≥0.290, which enabled true optical zooming capability.

Two liquids wetting and low hysteresis electrowetting on dielectric applications.

This study focuses on electrowetting using two immmiscible liquids on a dielectric coating. It is demonstrated that low contact angle of oil on the hydrophobic surfaces is a key parameter to obtain a low hysteresis system, below 2 degrees . On the basis of these results, three aspects of the wetting properties have been studied: the influence of the surface hydrophobic properties, the design of the liquids according to the hydrophobic surface, and a graphical method to solve the Bartell-Osterhof equation and predict the wetting properties of two liquids on a surface. These results define clear design rules to obtain a low hysteresis system, useful for many applications from liquid lenses to displays and laboratory-on-a-chip.