A Study of the Long-Term Electrochemical Stability of Thin-Film Titanium-Platinum Microelectrodes and Their Comparison to Classic, Wire-Based Platinum Microelectrodes in Selected Inorganic Electrolytes.

This paper discusses the electrochemical properties of thin-film, planar, titanium-platinum (Ti-Pt) microelectrodes fabricated using glass or silicon substrates and compares their performance to the classic platinum (Pt) microelectrodes embedded in glass. To analyze the possible differences coming both from the size of the tested electrodes as well as from the substrate, short- and long-term electrochemical tests were performed on selected water electrolytes (KCl, HCl, KOH). To study the electrochemical response of the electrodes, the cyclic voltammetry (CV) measurements were carried out at different scanning rates (from 5 to 200 mV/s). Long-term tests were also conducted, including one thousand cycles with a 100 mV/s scan rate to investigate the stability of the tested electrodes. Before and after electrochemical measurements, the film morphology was analyzed using a scanning electron microscope (SEM). The good quality of the thin-film Pt electrodes and the high repeatability in electrochemical response have been shown. There are minor differences in standard deviation values taken from electrochemical measurements, comparing thin-film and wire-based electrodes. Damages or any changes on the electrodes' surfaces were revealed by SEM observations after long-term electrochemical tests.

Single-compartment hydrogen peroxide fuel cells with poly(3,4-ethylenedioxythiophene) cathodes.

Single-compartment hydrogen peroxide fuel cells have recently emerged as a promising energy conversion platform since H2O2 is a high energy-density liquid that functions as both fuel and oxidizer. Finding suitable electrocatalysts is challenging since most metallic electrodes also catalyze the disproportionation reaction of H2O2 into H2O and O2, representing a significant loss mechanism in peroxide fuel cells. Herein we demonstrate that the conducting polymer poly(3,4-ethylenedioxythiophene), PEDOT, is a versatile electrocatalyst for peroxide fuel cells without generating losses due to disproportionation. We find that PEDOT is a cathodic catalyst for reduction of peroxide to water, performing at a level on par with the best reported inorganic catalysts. Using PEDOT as the cathode and nickel as the anode material, open circuit potentials in the range of 0.5-0.6 V are possible, with power densities of 0.20-0.30 mW cm-2. We provide evidence to understand mechanistically how PEDOT functions as a catalyst for hydrogen peroxide reduction to water. The result of our efforts is a scalable hydrogen peroxide fuel cell cathode, which serves to demonstrate also the capabilities of organic semiconducting materials as electrocatalysts.

Single nucleotide polymorphism detection using gold nanoprobes and bio-microfluidic platform with embedded microlenses.

The use of microfluidics platforms combined with the optimal optical properties of gold nanoparticles has found plenty of application in molecular biosensing. This paper describes a bio-microfluidic platform coupled to a non-cross-linking colorimetric gold nanoprobe assay to detect a single nucleotide polymorphism associated with increased risk of obesity fat-mass and obesity-associated (FTO) rs9939609 (Carlos et al., 2014). The system enabled significant discrimination between positive and negative assays using a target DNA concentration of 5 ng/µL below the limit of detection of the conventionally used microplate reader (i.e., 15 ng/µL) with 10 times lower solution volume (i.e., 3 µL). A set of optimization of our previously reported bio-microfluidic platform (Bernacka-Wojcik et al., 2013) resulted in a 160% improvement of colorimetric analysis results. Incorporation of planar microlenses increased 6 times signal-to-loss ratio reaching the output optical fiber improving by 34% the colorimetric analysis of gold nanoparticles, while the implementation of an optoelectronic acquisition system yielded increased accuracy and reduced noise. The microfluidic chip was also integrated with a miniature fiber spectrometer to analyze the assays' colorimetric changes and also the LEDs transmission spectra when illuminating through various solutions. Furthermore, by coupling an optical microscope to a digital camera with a long exposure time (30 s), we could visualise the different scatter intensities of gold nanoparticles within channels following salt addition. These intensities correlate well to the expected difference in aggregation between FTO positive (none to small aggregates) and negative samples (large aggregates).

Tailoring nanoscale properties of tungsten oxide for inkjet printed electrochromic devices.

This paper focuses on the engineering procedures governing the synthesis of tungsten oxide nanocrystals and the formulation of printable dispersions for electrochromic applications. By that means, we aim to stress the relevancy of a proper design strategy that results in improved physicochemical properties of nanoparticle loaded inks. In the present study inkjet printable nanostructured tungsten oxide particles were successfully synthesized via hydrothermal processes using pure or acidified aqueous sol-gel precursors. Based on the proposed scheme, the structure and morphology of the nanoparticles were tailored to ensure the desired printability and electrochromic performance. The developed nanomaterials with specified structures effectively improved the electrochemical response of printed films, resulting in 2.5 times higher optical modulation and 2 times faster coloration time when compared with pure amorphous films.

Statistical mixture design and multivariate analysis of inkjet printed a-WO3/TiO2/WOX electrochromic films.

An efficient mathematical strategy in the field of solution processed electrochromic (EC) films is outlined as a combination of an experimental work, modeling, and information extraction from massive computational data via statistical software. Design of Experiment (DOE) was used for statistical multivariate analysis and prediction of mixtures through a multiple regression model, as well as the optimization of a five-component sol-gel precursor subjected to complex constraints. This approach significantly reduces the number of experiments to be realized, from 162 in the full factorial (L=3) and 72 in the extreme vertices (D=2) approach down to only 30 runs, while still maintaining a high accuracy of the analysis. By carrying out a finite number of experiments, the empirical modeling in this study shows reasonably good prediction ability in terms of the overall EC performance. An optimized ink formulation was employed in a prototype of a passive EC matrix fabricated in order to test and trial this optically active material system together with a solid-state electrolyte for the prospective application in EC displays. Coupling of DOE with chromogenic material formulation shows the potential to maximize the capabilities of these systems and ensures increased productivity in many potential solution-processed electrochemical applications.

Inkjet printed and "doctor blade" TiO2 photodetectors for DNA biosensors.

A dye sensitized TiO(2) photodetector has been integrated with a DNA detection method based on non-cross-linking hybridization of DNA-functionalized gold nanoparticles, resulting in a disposable colorimetric biosensor. We present a new approach for the fabrication of dye sensitized TiO(2) photodetectors by an inkjet printing technique-a non-contact digital, additive, no mask and no vacuum patterning method, ideal for cost efficient mass production. The developed biosensor was compared against a dye sensitized photodetector fabricated by the traditional "doctor blade" method. Detection of gold nanoparticle aggregation was possible for concentrations as low as 1.0 nM for the "doctor blade" system, and 1.5 nM for the inkjet printed photodetector. The demonstrated sensitivity limits of developed biosensors are comparable to those of spectrophotometric techniques (1.0 nM). Our results show that a difference higher than 17% by traditional photodetector and 6% by inkjet printed in the photoresponses for the complementary and non-complementary gold nanoprobe assays could be attained for a specific DNA sequence from Mycobacterium tuberculosis, the etiologic agent of human tuberculosis. The decrease of costs associated with molecular diagnostic provided by a platform such as the one presented here may prove of paramount importance in developing countries.