Electrogeneration and Characterization of Poly(methylene blue) Thin Films on Stainless Steel 316 Electrodes-Effect of pH.

Methylene blue was electropolymerized on the surface of stainless steel 316. The addition of sodium oxalate and working at a pH near 11 allowed us to obtain steel electrodes coated with an electroactive polymer. This polymer shows electrochromic properties like those of the monomer, but also exhibits electroactivity at more positive potentials, which is associated with the active centers in the bridges between monomeric units. A digital video electrochemistry study allowed us to simultaneously quantify, on the one hand, the color changes on the entire surface of the stainless steel and on the other to separate the contribution of the active centers of the phenothiazine ring and of the inter-monomer bonds to the overall polymer response by means of assessing the mean color intensities. A reduction mechanism for the polymer, compatible with the pH variation of the observed electrochemical behavior, was proposed.

Design and Characterization of Effective Ag, Pt and AgPt Nanoparticles to H2O2 Electrosensing from Scrapped Printed Electrodes.

The use of disposable screen-printed electrodes (SPEs) has extraordinarily grown in the last years. In this paper, conductive inks from scrapped SPEs were removed by acid leaching, providing high value feedstocks suitable for the electrochemical deposition of Ag, Pt and Ag core-Pt shell-like bimetallic (AgPt) nanoparticles, onto screen-printed carbon electrodes (ML@SPCEs, M = Ag, Pt or AgPt, L = metal nanoparticles from leaching solutions). ML@SPCEs were characterized by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The results were compared to those obtained when metal nanoparticles were synthesised using standard solutions of metal salts (MS@SPCEs). Both ML@SPCEs and MS@SPCEs exhibited similar cyclic voltammetric patterns referred to the electrochemical stripping of silver or the adsorption/desorption of hydrogen/anions in the case of platinum, proving leaching solutions extremely effective for the electrodeposition of metallic nanoparticles. The use of both ML@SPCEs and MS@SPCEs proved effective in enhancing the sensitivity for the detection of H2O2 in phosphate buffer solutions (pH = 7). The AgPtL@SPCE was used as proof of concept for the validation of an amperometric sensor for the determination of H2O2 within laundry boosters and antiseptic samples. The electrochemical sensor gave good agreement with the results obtained by a spectrophotometric method with H2O2 recoveries between 100.6% and 106.4%.

Oscillatory Changes of the Heterogeneous Reactive Layer Detected with the Motional Resistance during the Galvanostatic Deposition of Copper in Sulfuric Solution.

Metallic copper was galvanostatically deposited on quartz|gold resonant electrodes by applying a constant current in a 0.5 M CuSO4/0.1 M H2SO4 aqueous solution. Galvanostatic copper deposition is one of the best methodologies to calibrate the electrochemical quartz crystal microbalances (EQCM), a gravimetric sensor to evaluate changes in mass during the electrochemical reactions through the Sauerbrey equation. The simultaneous measurement of mass, current density, and motional resistance by an EQCM with motional resistance monitoring allows us to characterize the processes occurring on the electrode surface and at the interfacial regions with unprecedented detail. During the galvanostatic copper deposition, Cu(H2O)4(OH)2 is accumulated close to the copper surface, generating a passive layer. This passive layer can act as Cu(2+) reservoir for the Cu(2+) → Cu process since the copper deposition is not affected. The analysis of motional resistance evolution in different experimental conditions reveals that the passive layer is formed by the reaction of oxidizing agents generated at the counter electrode with the metallic copper surface. The simplistic Cu(2+) → Cu process is completed with a more detailed mechanism, which includes the passive layer formation/dissolution and the transport of species from the counter electrode surface (Pt) to the working electrode surface. The results further support the calibration procedure of EQCM by the galvanostatic deposition of copper in sulfuric solutions. However, we suggest applying high current densities, separating the counter electrode and quartz|gold resonant electrode about 0.5 cm, and keeping oxygen in solution for the EQCM calibration. Moreover, the better interval time to calculate the Sauerbrey's constant from charge and resonant frequency data is between 150 and 300 s.

Motional Resistance Evaluation of the Quartz Crystal Microbalance to Study the Formation of a Passive Layer in the Interfacial Region of a Copper|Diluted Sulfuric Solution.

A hyphenated technique based on vis­NIR spectroscopy and electrochemical quartz crystal microbalance with motional resistance monitoring was employed to investigate the dissolution of copper in acid media. Changes in motional resistance, current, mass, and absorbance during copper dissolution allow the evolution of the interfacial region of copper|diluted sulfuric solution to be understood. In particular, motional resistance is presented in this work as a useful tool to observe the evolution of the passive layer at the interface. During the forced copper electrodissolution in sulfuric solution, SO4(2­) favors the formation of soluble [Cu(H2O)6]2+. On the contrary, OH­ involves the formation of Cu(H2O)4(OH)2, which precipitates on the electrode surface. The high viscosity and density of Cu(H2O)4(OH)2 formed on surface causes an increase in motional resistance independently of resonance frequency changes. During the copper corrosion in a more natural acidic environment, the results of electrochemical impedance spectra at open circuit potential indicate that corrosion is controlled by the diffusion of copper to the solution at short experimental times. However, copper diffusion is hindered by the formation of a passive layer on the electrode surface at long experimental times. During the copper corrosion, motional resistance shows an oscillatory response because of an oscillatory formation/dissolution of the passive later. Vis­NIR spectroscopy and electrochemical quartz crystal microbalance with motional resistance monitoring give new perspectives for reaching a deep understanding of metal corrosion processes and, in a future, other interfacial processes such as the catalysis or adsorption of (bio)molecules.

A Macroscopic Interpretation of the Correlation between Electrical Percolation and Mechanical Properties of Poly-(Ethylene Vinyl Acetate)/Zn Composites.

Elastic composites were prepared using a procedure involving hot plates and zinc powder that was directly dispersed into an EVA matrix. The correlation between the zinc content and the conductive properties of the material was studied via impedance spectroscopy, the thermal properties of the material were studied via differential calorimetry and the mechanical properties of the composites were studied via tensile strength curves, representing an important advancement in the characterization of this type of composite material. The composites' tensile strength and elongation at break decrease with the addition of filler since zinc particles act as stress-concentrating centres, while the composites' hardness and Young's modulus increase because of an increase in the stiffness of the material. The AC perturbation across the EVA/Zn composites was characterized using an RC parallel equivalent circuit that allowed us to easily measure their resistivity (ρp) and permittivity (εp). The dependence of these electrical magnitudes on the zinc content is correlated with their mechanical properties across the characteristic time constant τp = ρp·Îµp of this equivalent circuit. The dependence of the mechanical and electrical magnitudes on the zinc content is consistent with the formation of percolation clusters. The addition of graphite particles increases their potential performance. Three possible mechanisms for the electrical transport of the ac-perturbation across the EVA/Zn composites have been identified. Chemical corrosion in acid media causes the loss of zinc surface particles, but their bulk physical properties practically remain constant.

Overview and Recent Advances in Hyphenated Electrochemical Techniques for the Characterization of Electroactive Materials.

A hyphenated electrochemical technique consists of the combination of the coupling of an electrochemical technique with a non-electrochemical technique, such as spectroscopical and optical techniques, electrogravimetric techniques, and electromechanical techniques, among others. This review highlights the development of the use of this kind of technique to appreciate the useful information which can be extracted for the characterization of electroactive materials. The use of time derivatives and the acquisition of simultaneous signals from different techniques allow extra information from the crossed derivative functions in the dc-regime to be obtained. This strategy has also been effectively used in the ac-regime, reaching valuable information about the kinetics of the electrochemical processes taking place. Among others, molar masses of exchanged species or apparent molar absorptivities at different wavelengths have been estimated, increasing the knowledge of the mechanisms for different electrode processes.

A Comparative Study of Poly(Azure A) Film-Modified Disposable Electrodes for Electrocatalytic Oxidation of H2O2: Effect of Doping Anion.

In the present paper, poly(azure A) (PAA) films were electrosynthetized in the presence of different doping anions on disposable screen-printed carbon electrodes (SPCEs). The anions used included inorganic monoatomic (chloride and fluoride), inorganic polyatomic (nitrate and sulfate) and organic polyatomic (dodecyl sulfate, DS) species. The coated electrodes thus obtained were characterized by electrochemical techniques and SEM. They showed improved electrocatalytic activities towards hydrogen peroxide oxidation compared to that of a bare SPCE. In particular, the insertion of DS anions inside PAA films provided a special sensitivity to the electrocatalysis of H2O2, which endowed these electrodes with promising analytical features for H2O2 quantification. We obtained a wide linear response for H2O2 within a range of 5 µM to 3 mM and a limit of detection of 1.43 ± 0.10 µM (signal-to-noise ratio of 3). Furthermore, sensitivity was 72.4 ± 0.49 nA·µM-1∙cm-2 at a relatively low electrocatalytic oxidation overpotential of 0.5 V vs. Ag. The applicability of this boosted system was tested by the analysis of H2O2 in commercial samples of a hair lightener and an antiseptic and was corroborated by spectrophotometric methods.

Electromechanical phase transition in hexacyanometallate nanostructure (Prussian Blue).

This paper demonstrates the importance of the structural changeover in controlling the physical-chemical properties of hexacyanometalate-like materials (Prussian Blue). A meticulous in situ study of compositional variations using electroacoustic impedance techniques associated to electrogravimetric techniques in hexacyanoferrates containing K+ alkali metals reveals the existence of a nanostructural changeover coupled to a change of the magnetic properties of these electromagnetic materials. In the same way, the electroacoustic impedance techniques can be useful both in the understanding and in the in situ monitoring of the structural changeovers and the magnetic behavior of all kinds of materials.