Modification of Cu(111) Surface with Alkylphosphonic Acids in Aqueous and Ethanol Solution. An Experimental and Theoretical Study

Alkylphosphonic acids are well known for their ability to form self-assembled monolayers on hydroxide surfaces. A crucial step to understanding fundamentally how these surfaces are created is the elucidation of the interaction process that leads to such interface creation. In this study, we employed electrochemical impedance spectroscopy (EIS), Monte Carlo and molecular dynamics to understand this process. The interaction with the Cu(111) surface of three different alkylphosphonic acids (hexyl-, octyl- and decylphosphonic acids) is evaluated in an aqueous acidic and in an ethanol solution by Monte Carlo and molecular dynamics simulations, while EIS measurements are used to put in evidence the impact of the layer made in ethanol on copper protection. Nyquist diagrams of copper samples modified with an alkylphosphonic monolayer showed a higher polarization resistance that mitigates the copper corrosion in an aqueous acid medium. The phase–frequency Bode plots had higher and broader phase maxima for a modified copper surface with phosphonic moieties, which confirmed the ability of this organic layer to prevent copper corrosion.

The Infiltration of Silver Nanoparticles into Porous Silicon for Improving the Performance of Photonic Devices

Hybrid nanostructures have a great potential to improve the overall properties of photonic devices. In the present study, silver nanoparticles (AgNPs) were infiltrated into nanostructured porous silicon (PSi) layers, aiming at enhancing the optoelectronic performance of Si-based devices. More specifically, Schottky diodes with three different configurations were fabricated, using Al/Si/Au as the basic structure. This structure was modified by adding PSi and PSi + AgNPs layers. Their characteristic electrical parameters were accurately determined by fitting the current–voltage curves to the non-ideal diode equation. Furthermore, electrochemical impedance spectroscopy was used to determine the electrical parameters of the diodes in a wide frequency range by fitting the Nyquist plots to the appropriate equivalent circuit model. The experimental results show a remarkable enhancement in electrical conduction after the incorporation of metallic nanoparticles. Moreover, the spectral photoresponse was examined for various devices. An approximately 10-fold increment in photoresponse was observed after the addition of Ag nanoparticles to the porous structures.

Fabrication and Characterization of a Marine Wet Solar Cell with Titanium Dioxide and Copper Oxides Electrodes

One of the effective ways of utilizing marine environments is to generate energy, power, and hydrogen via the effect of photocatalysts in the seawater. Since the ocean is vast, we are able to use its large area, but the power generation system must be of low cost and have high durability against both force and corrosion. In order to meet those requirements, this study focuses on the fabrication of a novel marine wet solar cell composed of a titanium dioxide photoanode and a copper oxide photocathode. These electrodes were deposited on type 329J4L stainless steel, which possesses relative durability in marine environments. This study focuses on the characterization of the photocatalytic properties of electrodes in seawater. Low-cost manufacturing processes of screen-printing and vacuum vapor deposition were applied to produce the titanium dioxide and copper oxides electrodes, respectively. We investigated the photopotential of the electrodes, along with the electrochemical properties and cell voltage properties of the cell. X-ray diffraction spectroscopy (XRD) of the copper oxides electrode was analyzed in association with the loss of photocatalytic effect in the copper oxides electrode. Although the conversion efficiency of the wet cell was less than 1%, it showed promising potential for use in marine environments with low-cost production. Electrochemical impedance spectroscopy (EIS) of the cell was also conducted, from which impedance values regarding the electrical properties of electrodes and their interfaces of charge-transfer processes were obtained. This study focuses on the early phase of the marine wet solar cell, which should be further studied for long-term stability and in actual marine environmental applications.

Improvement of La0.8Sr0.2MnO3−δ Cathode Material for Solid Oxide Fuel Cells by Addition of YFe0.5Co0.5O3

The high efficiency of solid oxide fuel cells with La0.8Sr0.2MnO3−δ (LSM) cathodes working in the range of 800–1000 °C, rapidly decreases below 800 °C. The goal of this study is to improve the properties of LSM cathodes working in the range of 500–800 °C by the addition of YFe0.5Co0.5O3 (YFC). Monophasic YFC is synthesized and sintered at 950 °C. Composite cathodes are prepared on Ce0.8Sm0.2O1.9 electrolyte disks using pastes containing YFC and LSM powders mixed in 0:1, 1:19, and 1:1 weight ratios denoted LSM, LSM1, and LSM1, respectively. X-ray diffraction patterns of tested composites reveal the presence of pure perovskite phases in samples sintered at 950 °C and the presence of Sr4Fe4O11, YMnO3, and La0.775Sr0.225MnO3.047 phases in samples sintered at 1100 °C. Electrochemical impedance spectroscopy reveals that polarization resistance increases from LSM1, by LSM, to LSM2. Differences in polarization resistance increase with decreasing operating temperatures because activation energy rises in the same order and equals to 1.33, 1.34, and 1.58 eV for LSM1, LSM, and LSM2, respectively. The lower polarization resistance of LSM1 electrodes is caused by the lower resistance associated with the charge transfer process.

Effects of tensile stress on electrochemical characteristics and structural morphology of P110SS steels in carbon dioxide-saturated solution

A high-temperature autoclave was used to grow CO2 corrosion-product films on P110SS steel specimens while the surface of the specimens was continuously subjected to tensile stress in a four-point bending jig; the autoclaving times were 6, 18, 36, and 72 h. A scanning electron microscope was used to observe the surface topography of the corrosion-product films formed on the P110SS steels. An X-ray diffraction was used to analyze the phase compositions of the corrosion products. The electrochemical performance of the films was investigated using electrochemical impedance spectroscopy and potentiodynamic polarization curves. The results showed that tensile stress could hinder the formation of corrosion-product films; the integrity and compactness of the films worsened, but the phase compositions of the films did not change. The applied tensile stress resulted in a smaller grain size of the corrosion-product films, and the grain boundaries increased. In addition, owing to the induced tensile stress, the charge transfer resistances decreased, and the corrosion current densities increased for the P110SS steels with corrosion-product films in a 3.5 wt.% NaCl solution saturated with CO2.

Electrochemical Detection Platform Based on RGO Functionalized with Diazonium Salt for DNA Hybridization

In this paper, we propose an improved electrochemical platform based on graphene for the detection of DNA hybridization. Commercial screen-printed carbon electrodes (SPCEs) were used for this purpose due to their ease of functionalization and miniaturization opportunities. SPCEs were modified with reduced graphene oxide (RGO), offering a suitable surface for further functionalization. Therefore, aryl-carboxyl groups were integrated onto RGO-modified electrodes by electrochemical reduction of the corresponding diazonium salt to provide enough reaction sites for the covalent immobilization of amino-modified DNA probes. Our final goal was to determine the optimum conditions needed to fabricate a simple, label-free RGO-based electrochemical platform to detect the hybridization between two complementary single-stranded DNA molecules. Each modification step in the fabrication process was monitored by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) using [Fe(CN)6]3−/4− as a redox reporter. Although, the diazonium electrografted layer displayed the expected blocking effect of the charge transfer, the next steps in the modification procedure resulted in enhanced electron transfer properties of the electrode interface. We suggest that the improvement in the charge transfer after the DNA hybridization process could be exploited as a prospective sensing feature. The morphological and structural characterization of the modified electrodes performed by scanning electron microscopy (SEM) and Raman spectroscopy, respectively, were used to validate different modification steps in the platform fabrication process.

Electrochemical Sensing of Idarubicin—DNA Interaction Using Electropolymerized Azure B and Methylene Blue Mediation

A highly sensitive electrochemical DNA sensor for detection of the chemotherapeutic drug idarubicin mediated by Methylene blue (MB) has been developed. DNA from fish sperm has been immobilized at the electropolymerized layers of Azure B. The incorporation of MB into the DNA layers substantially increased the sensor sensitivity. The concentration range for idarubicin determination by cyclic voltammetry was from 1 fM to 0.1 nM, with a limit of detection (LOD) of 0.3 fM. Electrochemical impedance spectroscopy (EIS) in the presence of a redox probe ([Fe(CN)6]3−/4−) allowed for the widening of a linear range of idarubicin detection from 1 fM to 100 nM, retaining LOD 0.3 fM. The DNA sensor has been tested in various real and artificial biological fluids with good recovery ranging between 90–110%. The sensor has been successfully used for impedimetric idarubicin detection in medical preparation Zavedos®. The developed DNA biosensor could be useful for the control of the level of idarubicin during cancer therapy as well as for pharmacokinetics studies.

Mathematical Modelling of Glyphosate Molecularly Imprinted Polymer-Based Microsensor with Multiple Phenomena

The massive and careless use of glyphosate (GLY) in agricultural production raises many questions regarding environmental pollution and health risks, it is then important to develop simple methods to detect it. Electrochemical impedance spectroscopy (EIS) is an effective analytical tool for characterizing properties at the electrode/electrolyte interface. It is useful as an analytical procedure, but it can also help in the interpretation of the involved fundamental electrochemical and electronic processes. In this study, the impedance data obtained experimentally for a microsensor based on molecularly imprinted chitosan graft on 4-aminophenylacetic acid for the detection of glyphosate was analyzed using an exact mathematical model based on physical theories. The procedure for modeling experimental responses is well explained. The analysis of the observed impedance response leads to estimations of the microscopic parameters linked to the faradic and capacitive current. The interaction of glyphosate molecules with the imprinted sites of the CS-MIPs film is observed in the high frequency range. The relative variation of the charge transfer resistance is proportional to the log of the concentration of glyphosate. The capacitance decreases as the concentration of glyphosate increases, which is explained by the discharging of the charged imprinted sites when the glyphosate molecule interacts with the imprinted sites through electrostatic interactions. The phenomenon of adsorption of the ions in the CMA film is observed in the low frequency range, this phenomenon being balanced by the electrostatic interaction of glyphosate with the imprinted sites in the CS-MIPs film.

Performance Improvement of Gold Electrode towards Methanol Electrooxidation in Akaline Medium: Enhanced Current Density Achieved with Poly(aniline-co-2-hydroxyaniline) Coating at Low Overpotential

Electronically conducting poly (aniline-co-2-hydroxyaniline) (PACHA), a copolymer of aniline and 2-hydroxyaniline (2HA), was electrochemically coated on gold substrate for methanol electrooxidation in alkaline media. The electrochemical behavior of PACHA coated gold electrode towards methanol electrooxidation was investigated via cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) for application in an alkaline fuel cell. Methanol electrooxidation was observed at two different electrode potentials depending on the concentration of the base. At the PACHA coated gold electrode, the methanol oxidation peak was observed at lower overpotential (at 0.19 V) in a solution of high base concentration (1.8 M NaOH), which was 30 mV lower than the peak for the uncoated gold electrode. In addition, the Faradic current Imax obtained on the PACHA coated electrode (20 mA) was two times higher as compared to the Faradic current Imax of the un-modified gold electrode (10 mA). In solution of lower base concentration (0.06 M NaOH), the electrooxidation of methanol became sluggish on both electrodes, as indicated by peak shifting towards positive potential and with reduced faradaic current (at 0.74 V on PACHA coated electrode; Imax 10 mA). The electrooxidation of methanol at both lower and higher electrode potentials was analyzed mechanistically and discussed in light of the literature. EIS results were interpreted using Nyquist and Bode plots. The charge transfer resistance was decreased and pseudo-capacitive behavior changed to conductive behavior when external applied potential was increased from 0.1 V to 0.4 V.