Wireless Light-Emitting Electrode Arrays for the Evaluation of Electrocatalytic Activity.

Water splitting has become a sustainable and clean alternative for hydrogen production. Commonly, the efficiency of such reactions is intimately related to the physico-chemical properties of the catalysts that constitute the electrolyzer. Thus, the development of simple and fast methods to evaluate the electrocatalytic efficiency of an electrolyzer is highly required. In this work, we present an unconventional method based on the combination of bipolar electrochemistry and light-emitting diodes, which allows the evaluation of the electrocatalytic performance of the two types of catalysts, composing an electrolyzer, namely for oxygen and hydrogen evolution reactions, respectively. The integrated light emission of the diode acts as an optical readout of the electrocatalytic information, which simultaneously depends on the composition of the anode and the cathode. The electrocatalytic activity of Au, Pt, and Ni electrodes, connected to the LED in multiple anode/cathode configurations, towards the water splitting reactions has been evaluated. The efficiency of the electrolyzer can be represented in terms of the onset electric field (ϵonset) for light emission, obtaining variations that are in agreement with data reported with conventional electrochemistry. This work introduces a straightforward method for evaluating electrocatalysts and underscores the importance of material characterization in developing efficient electrolyzers for hydrogen production.

Chemically-driven autonomous Janus electromagnets as magnetotactic swimmers.

An electromagnet is a particular device that takes advantage of electrical currents to produce concentrated magnetic fields. The most well-known example is a conventional solenoid, having the form of an elongated coil and creating a strong magnetic field through its center when it is connected to a current source. Spontaneous redox reactions located at opposite ends of an anisotropic Janus swimmer can effectively mimic a standard power source, due to their ability to wirelessly generate a local electric current. Herein, we propose the coupling of thermodynamically spontaneous redox reactions occurring at the extremities of a hybrid Mg/Pt Janus swimmer with a solenoidal geometry to generate significant magnetic fields. These chemically driven electromagnets, spontaneously transform the redox-induced electric current into a magnetic field with a strength in the range of µT, upon contact with an acidic medium. Such on-board magnetization allows them to perform compass-like rotational motion and magnetotactic displacement in the presence of external magnetic field gradients, without the need of using ferromagnetic materials for the swimmer design. The torque force experienced by the swimmer is proportional to the internal redox current, and by varying the composition of the solution, it is possible to fine-tune its angular velocity.

Highly Ordered Macroporous Poly-3,4- ortho-xylendioxythiophene Electrodes as a Sensitive Analytical Tool for Heavy Metal Quantification.

Highly ordered macroporous electrodes of the conducting polymer poly-3,4- ortho-xylendioxythiophene (PXDOT) are presented as a sensitive analytical tool for heavy metal ion quantification due to a controlled gain in electroactive area. They were designed by using colloidal crystal templates. A direct correlation between the final number of porous layers and the deposition charge ( Qd) employed for electropolymerization is observed. All the electrodes exhibit a surface-templated structure due to an interaction between the radical cation, formed during the electropolymerization, and the surface groups of the silica beads. The voltamperometric response of the macroporous PXDOT electrodes shows a rather fast electron transfer with Δ Ep values between 70 mV and 110 mV. Square wave anodic stripping voltammetric (SWASV) analysis of Cu2+ as a representative heavy metal ion shows a linear response in the subppm range. As a model application, the efficient quantification of Cu2+ in a commercial mezcal sample is validated by the standard addition method and the results correlate adequately with the values obtained by atomic absorption spectroscopy.

Modulation of Wetting Gradients by Tuning the Interplay between Surface Structuration and Anisotropic Molecular Layers with Bipolar Electrochemistry.

A new simple and versatile method for the preparation of surface-wetting gradients is proposed. It is based on the combination of electrode surface structuration introduced by a sacrificial template approach and the formation of a tunable molecular gradient by bipolar electrochemistry. The gradient involves the formation of a self-assembled monolayer on a gold surface by selecting an appropriate thiol molecule and subsequent reductive desorption by means of bipolar electrochemistry. Under these conditions, completion of the reductive desorption process evolves along the bipolar surface with a maximum strength localized at the cathodic edge and a decreasing driving force towards the middle of the surface. The remaining quantity of surface-immobilized thiol, therefore, varies as a function of the axial position, resulting in the formation of a molecular gradient. The surface of the bipolar electrode is characterized at each step of the modification by recording heterogeneous electron transfer. Also, the evolution of static contact angles measured with a water droplet deposited on the surface directly reveals the presence of the wetting gradient, which can be modulated by changing the properties of the thiol. This is exemplified with a long, hydrophobic alkane-thiol and a short, hydrophilic mercaptan.

Multilayer Langmuir-Blodgett films as diffractive external 3D photonic crystal in blue OLEDs.

Three-dimensional Langmuir-Blodgett films made of silica beads are theoretically and experimentally investigated in order to improve the relatively small efficiency of blue OLEDs. Using films made of 5 layers of beads, we fabricated OLEDs emitting at 476 nm, and measured a gain of around 40% on their external quantum efficiency. An optical model has been developed to accurately handle the fact that the organic emitting layer and the photonic extraction layer are separated by a distance greater than 1000 wavelength. The latter also permits to describe rapidly this three-dimensional optical OLED cavity, without redoing all the numerical simulations when the optical properties of the organic layers are changed (material index, thicknesses).

Combined macro-/mesoporous microelectrode arrays for low-noise extracellular recording of neural networks.

Microelectrode arrays (MEAs) are appealing tools to probe large neural ensembles and build neural prostheses. Microelectronics microfabrication technologies now allow building high-density MEAs containing several hundreds of microelectrodes. However, several major problems become limiting factors when the size of the microelectrodes decreases. In particular, regarding recording of neural activity, the intrinsic noise level of a microelectrode dramatically increases when the size becomes small (typically below 20-µm diameter). Here, we propose to overcome this limitation using a template-based, single-scale meso- or two-scale macro-/mesoporous modification of the microelectrodes, combining the advantages of an overall small geometric surface and an active surface increased by several orders of magnitude. For this purpose, standard platinum MEAs were covered with a highly porous platinum overlayer obtained by lyotropic liquid crystal templating possibly in combination with a microsphere templating approach. These porous coatings were mechanically more robust than Pt-black coating and avoid potential toxicity issues. They had a highly increased active surface, resulting in a noise level ∼3 times smaller than that of conventional flat electrodes. This approach can thus be used to build highly dense arrays of small-size microelectrodes for sensitive neural signal detection.

Nucleation of polystyrene latex particles in the presence of gamma-methacryloxypropyltrimethoxysilane: functionalized silica particles.

Silica/polystyrene nanocomposite particles with different morphologies were synthesized through emulsion polymerization of styrene in the presence of silica particles previously modified by gamma-methacryloxypropyltrimethoxysilane (MPS). Grafting of the silane molecule was performed by direct addition of MPS to the aqueous silica suspension in the presence of an anionic surfactant under basic conditions. The MPS grafting density on the silica surface was determined using the depletion method and plotted against the initial MPS concentration. The influence of the MPS grafting density, the silica particles size and concentration and the nature of the surfactant on the polymerization kinetics and the particles morphology was investigated. When the polymerization was performed in the presence of an anionic surfactant, transmission electron microscopy images showed the formation of polymer spheres around silica for MPS grafting densities lower than typically 1 micromole x m(-2) while the conversion versus time curves indicated a strong acceleration effect under such conditions. In contrast, polymerizations performed in the presence of a larger amount of MPS moieties or in the presence of a non ionic emulsifier resulted in the formation of "excentered" core-shell morphologies and lower polymerization rates. The paper identifies the parameters that allow to control particles morphology and polymerization kinetics and describes the mechanism of formation of the nanocomposite colloids.

Towards large amounts of Janus nanoparticles through a protection-deprotection route.

Janus silica nanoparticles, regioselectively functionalized by two different chemical groups, were synthesized through a multistep procedure based on the use of a polystyrene nodule as a protecting mask.

Three-dimensional colloidal crystals with a well-defined architecture.

Monodisperse silica spheres with diameters of 220-1100 nm were prepared by hydrolysis of tetraethyl orthosilicate (TEOS) in an alcoholic medium in the presence of water and ammonia. By grafting vinyl or amino groups onto silica surfaces using the coupling agents allyltrimethoxysilane and aminopropyltriethoxysilane, respectively, amphiphilic silica spheres were obtained and could be organized to form a stable Langmuir film at the air-water interface. The controlled transfer of this monolayer of particles onto a solid substrate gave us the ability to build three-dimensional regular crystals with a well-defined thickness and organization. These colloidal crystals diffract light in the UV, the visible, and the near-infrared (NIR) spectral regions, depending on the size of the silica spheres and according to Bragg's law. The depth of the photonic stop band can be tuned by varying the number of deposited layers of particles. By using successive depositions, we could prepare multilayered films with silica spheres of different sizes. The thickness of each slab in the binary crystals can be tuned at the layer level, while the crystalline order of each layer is well preserved.

Raman enhancement of azobenzene monolayers on substrates prepared by Langmuir-Blodgett deposition and electron-beam lithography techniques.

Nanostructured metallic platforms for Raman enhancement were fabricated using Langmuir-Blodgett and electron beam (e-beam) lithography techniques. The gold platforms were inscribed on thin glass slides with the purpose of using them in a transmission geometry experimental setup under a confocal microscope. The plasmon frequency of the gold nanostructures was determined in the visible-near-infrared range for various pattern sizes prepared by Langmuir-Blodgett transfer and e-beam lithography. The surface Raman enhancement factors were determined for a monolayer of azobenzene molecules adsorbed on gold through thiol bonding and compared for both LB transfer and e-beam samples for nanostructures of comparable geometries.

Langmuir-Blodgett films of micron-sized organic and inorganic colloids.

Multilayered films starting with silica or polymer particles in the micron-size range have been prepared using the Langmuir-Blodgett technique. The polymer particles made of highly cross-linked cores and hydrophilic shells were elaborated through a precipitation polymerization method that allows formation of particles with a low polydispersity. The influence of the surface function, the differences between organic and inorganic systems, and the characterization of these materials by means of reflectance infrared spectroscopy are also discussed.