Effect of mechanical coating with Ni and Ni-5% Al on the structure and electrochemical properties of the Mg-50% Ni alloy

The Mg-Ni metastable alloys (with amorphous or nanocrystalline structures) are promising candidates for anode application in nickel-metal hydride rechargeable batteries due to its large hydrogen absorbing capacity, low weight, availability, and relative low price. In spite of these interesting features, improvement on the cycle life performance must be achieved to allow its application in commercial products. In the present paper, the effect of mechanical coating of a Mg-50 at.% Ni alloy with Ni and Ni-5 at.% Al on the structure, powder morphology, and electrochemical properties is investigated. The coating additives, Mg-Ni alloy and resulting nanocomposites (i.e., Mg-Ni alloy + additive) were investigated by means of X-ray diffraction and scanning electron microscopy. The Mg-Ni alloy and nanocomposites were submitted to galvanostatic cycles of charge and discharge to evaluate their electrode performances. The mechanical coating with Ni and Ni-5% Al increased the maximum discharge capacity of the Mg-Ni alloy from of 221 to 257 and 273 mA h g(-1), respectively. Improvement on the cycle life performance was also achieved by mechanical coating.

Application of the Potentiometric Stripping Analysis with Constant Current for the Determination of Lithium Ions Using a Spinel-Type Manganese (IV) Oxide-Modified Carbon Paste Electrode

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electrochemical characterization of the paste carbon modified electrode with KSr2Ni0.75Nb4.25O15-delta solid in catalytic oxidation of the dipyrone

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Development of an electrochemical sensor for potassium ions based on KSr(2)Nb(5)O(15) modified electrode

In the work described by this paper, we studied the development of a selective potassium ion sensor constituted of a carbon paste electrode modified (CPEM) with a novel KSr(2)Nb(2)O(15). The material KSr(2)Nb(2)O(15) is an oxide with the tetragonal tungsten bronze structure (TTB) type are in forefront both in the area of research as well as in industrial applications. The sensor response to potassium ions was linear in the concentration range 1.26 x 10(-5) at 1.62 x 10(-3) mol L(-1) (E (mV) = 32.7 + 51.1 log [K(+)]). The sensor based KSr(2)Nb(2)O(15), of the TTB-type presented very good potentiometric response, with a slope of 51.1 mV/dec (at 25 degrees C) and detection limit for the potassium ions of 7.27 x 10(-5) mol.L(-1)

Electrochemical evaluation of the a carbon-paste electrode modified with spinel manganese(IV) oxide under flow conditions for amperometric determination of lithium

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structure and ferro/piezoelectric properties of SrBi(4)Ti(4)O(15) films deposited on TiO(2) buffer layer

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electrochemistry of organometallic compounds. Part III. Oxidations of methyl derivatives of organocobalt(III) complexes with delocalized electronic structure in dimethylformamide

The influence of the equatorial ligand on the electrochemical oxidation of the compounds [H3CCo(chel)B], where chel is bis (dimethylglyoximato), (DH)2; bis(salicylaldehyde)ethylenediimine, salen; bis(salicylaldehyde) o-phenylenediimine, salophen; bis(salicylaldehyde)cyclohexylenediimine, salcn; bis(acetylacetone) ethylenediimine, bae; and where B is pyridine when chel is (DH2), and dimethylformamide (DMF) when chel represents a Schiff base (salen, salcn, salophen and bae), was studied by means of cyclic voltammetry in DMF, 0.2 M in tetraethylammonium perchlorate, between 25 and -25°C, with a platinum disk working electrode. Absorption spectra in the visible and near ultraviolet regions for these compounds in DMF at 25°C were obtained. The complexes exhibit a reversible one-electron oxidation, at -20°C with scan rates >0.5 V s-; chemical reactions following electron transfer are not detected under these conditions. At slower potential or higher temperatures, the oxidized product decomposes chemically in a solvent-assisted (or nucleophile-assisted) reaction, yielding products which are electroactive in the applied potential range. The behavior of the [H3CCo (DH2)py] derivative is better described as a quasi-reversible charge transfer followed by an irreversible chemical reaction. Experimental evidence suggests that in the case of the [H3CCo(bae)] derivative at -20°C, the reactive -species is pentacoordinated and weakly adsorbed at the electrode surface. The value of E 1 2 and the energies of the first two absorption bands in the visible spectra reveal the ability of the studied complexes to donate and to delocalize electronic charge. © 1982.

Photoelectrochemical properties of FTO/m-BiVO4 electrode in different electrolytes solutions under visible light irradiation

Photoelectrochemical properties of FTO/BiVO4 electrode were investigated in different electrolytic solutions, potassium chloride (KCl) and sodium sulphate (Na2SO4), and under visible light irradiation condition. In order to accomplish that, an FTO/BiVO4 electrode was built by combining the solution combustion synthesis technique with the dip-coating deposition process. The morphology and structure of the BiVO4 electrode were investigated through X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. Photoelectrochemical properties were analyzed through chronoamperometry measurements. Results have shown that the FTO/BiVO4 electrode presents higher electroactivity in the electrolyte Na2SO4, leading to better current stabilization, response time, and photoinduced current density, when compared to KCl electrolyte. Besides, this electrode shows excellent performance for methylene blue degradation under visible light irradiation condition. In Na2SO4, the electrode has shown higher degradation rate, 51 %, in contrast to 44 % in KCl, plus higher rate constant, 174 × 10-4 min-1 compared to 150 × 10-4 min-1 in KCl. Results presented in this communication leads to the indication of BiVO4 thin films as alternate materials to use in heterogeneous photoelectrocatalysis, more specifically in decontamination of surface water. © 2013 Springer-Verlag Berlin Heidelberg.

Investigation of the structural, optical and dielectric properties of highly (100)-oriented (Pb0.60Ca0.20Sr0.20)TiO3 thin films on LaNiO3 bottom electrode

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Determination of uronic acids in sugarcane bagasse by anion-exchange chromatography using an electrode modified with copper nanoparticles

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Oxygen reduction reaction catalyzed by epsilon-MnO2: Influence of the crystalline structure on the reaction mechanism

The oxygen reduction reaction (ORR) was studied in KOH electrolyte on carbon supported epsilon-manganese dioxide (epsilon-MnO2/C). The epsilon-MnO2/C catalyst was prepared via thermal decomposition of manganese nitrate and carbon powder (Vulcan XC-72) mixtures. X-ray powder diffraction (XRD) measurements were performed in order to determine the crystalline structure of the resulting composite, while energy dispersive X-ray analysis (EDX) was used to evaluate the chemical composition of the synthesized material. The electrochemical studies were conducted using cyclic voltammetry (CV) and quasi-steady state polarization measurements carried out with an ultra thin layer rotating ring/disk electrode (RRDE) configuration. The electrocatalytic results obtained for 20% (w/w) Pt/C (E-TEK Inc., USA) and alpha-MnO2/C for the ORR, considered as one of the most active manganese oxide based catalyst for the ORR in alkaline media, were included for comparison. The RRDE results revealed that the ORR on the MnO2 catalysts proceeds preferentially through the complete 4e(-) reduction pathway via a 2 plus 2e(-) reduction process involving hydrogen peroxide as an intermediate. A benchmark close to the performance of 20% (w/w) Pt/C (E-TEK Inc., USA) was observed for the epsilon-MnO2/C material in the kinetic control region, superior to the performance of alpha-MnO2/C, but a higher amount of HO2- was obtained when epsilon-MnO2/C was used as catalyst. The higher production of hydrogen peroxide on epsilon-MnO2/C was related to the presence of structural defects, typical of this oxide, while the better catalytic performance in the kinetic control region compared to alpha-MnO2/C was related with the higher electrochemical activity for the proton insertion kinetics, which is a structure sensitive process. (C) 2012 Elsevier Ltd. All rights reserved.

Performance evaluation and characterization of symmetric capacitors with carbon black, and asymmetric capacitors using a carbon foam supported nickel electrode

This thesis evaluates a novel asymmetric capacitor incorporating a carbon foam supported nickel hydroxide positive electrode and a carbon black negative electrode. A series of symmetric capacitors were prepared to characterize the carbon black (CB) negative electrode. The influence of the binder, PTFE, content on the cell properties was evaluated. X-ray diffraction characterization of the nickel electrode during cycling is also presented. The 3 wt% and 5 wt% PTFE/CB symmetric cells were examined using cyclic voltammetry (CV) and constant current charge/discharge measurements. As compared with symmetric cells containing more PTFE, the 3 wt% cell has the highest average specific capacitance, energy density and power density over 300 cycles, 121.8 F/g, 6.44 Wh/kg, and 604.1 W/kg, respectively. Over the 3 to 10 wt% PTFE/CB range, the 3 wt% sample exhibited the lowest effective resistance and the highest BET surface area. Three asymmetric cells (3 wt% PTFE/CB negative electrode and a nickel positive) were fabricated; cycle life was examined at 3 current densities. The highest average energy and power densities over 1000 cycles were 20 Wh/kg (21 mA/cm2) and 715 W/kg (31 mA/cm2), respectively. The longest cycle life was 11,505 cycles (at 8 mA/cm2), with an average efficiency of 79% and an average energy density of 14 Wh/kg. The XRD results demonstrate that the cathodically deposited nickel electrode is a typical α-Ni(OH)2 with the R3m structure (ABBCCA stacking); the charged electrodes are 3γ-NiOOH with the same stacking as the α-type; the discharged electrodes (including as-formed electrode) are aged to β’-Ni(OH)2 (a disordered β) with the P3m structure (ABAB stacking). A 3γ remnant was observed.

Local degradation of structural, mechanical, electrical and chemical properties of membrane electrode assembly in polymer electrolyte fuel cell

Polymer electrolyte fuel cell (PEMFC) is promising source of clean power in many applications ranging from portable electronics to automotive and land-based power generation. However, widespread commercialization of PEMFC is primarily challenged by degradation. The mechanisms of fuel cell degradation are not well understood. Even though the numbers of installed units around the world continue to increase and dominate the pre-markets, the present lifetime requirements for fuel cells cannot be guarantee, creating the need for a more comprehensive knowledge of material’s ageing mechanism. The objective of this project is to conduct experiments on membrane electrode assembly (MEA) components of PEMFC to study structural, mechanical, electrical and chemical changes during ageing and understanding failure/degradation mechanism. The first part of this project was devoted to surface roughness analysis on catalyst layer (CL) and gas diffusion layer (GDL) using surface mapping microscopy. This study was motivated by the need to have a quantitative understanding of the GDL and CL surface morphology at the submicron level to predict interfacial contact resistance. Nanoindentation studies using atomic force microscope (AFM) were introduced to investigate the effect of degradation on mechanical properties of CL. The elastic modulus was decreased by 45 % in end of life (EOL) CL as compare to beginning of life (BOL) CL. In another set of experiment, conductive AFM (cAFM) was used to probe the local electric current in CL. The conductivity drops by 62 % in EOL CL. The future task will include characterization of MEA degradation using Raman and Fourier transform infrared (FTIR) spectroscopy. Raman spectroscopy will help to detect degree of structural disorder in CL during degradation. FTIR will help to study the effect of CO in CL. XRD will be used to determine Pt particle size and its crystallinity. In-situ conductive AFM studies using electrochemical cell on CL to correlate its structure with oxygen reduction reaction (ORR) reactivity

In Situ SHINERS at Electrochemical Single-Crystal Electrode/Electrolyte Interfaces: Tuning Preparation Strategies and Selected Applications

We have studied Au(55 nm)@SiO2 nanoparticles (NPs) on two low-index phases of gold and platinum single crystal electrodes in ClO4– and SO42– ion-containing electrolytes by both electrochemical methods and in-situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS). We showed the blocking of the electrode with surfactants originating from the synthesis of as-prepared SHINERS NPs. We introduce an efficient procedure to overcome this problem, which provides a fundamental platform for the application of SHINERS in surface electrochemistry and beyond. Our method is based on a hydrogen evolution treatment of the SHINERS-NP-modified single-crystal surfaces. The reliability of our preparation strategy is demonstrated in electrochemical SHINERS experiments on the potential-controlled adsorption and phase formation of pyridine on Au(hkl) and Pt(hkl). We obtained high-quality Raman spectra on these well-defined and structurally carefully characterized single-crystal surfaces. The analysis of the characteristic A1 vibrational modes revealed perfect agreement with the interpretation of single-crystal voltammetric and chronoamperometric experiments. Our study demonstrates that the SHINERS protocol developed in this work qualifies this Raman method as a pioneering approach with unique opportunities for in situ structure and reactivity studies at well-defined electrochemical solid/liquid interfaces.

Expression, purification, and projection structure by single particle electron microscopy of functional human TRPM4 heterologously expressed in Xenopus laevis oocytes

Despite efforts implicating the cationic channel transient receptor potential melastatin member 4 (TRPM4) to cardiac, nervous, and immunological pathologies, little is known about its structure and function. In this study, we optimized the requirements for purification and extraction of functional human TRPM4 protein and investigated its supra-molecular assembly. We selected the Xenopus laevis oocyte expression system because it lacks endogenous TRPM4 expression, it is known to overexpress functional human membrane channels, can be used for structure-function analysis within the same system, and is easily scaled to improve yield and develop moderate throughput capabilities through the use of robotics. Negative-stain electron microscopy (EM) revealed various sized low-resolution particles. Single particle analysis identified the majority of the projections represented the monomeric form with additional oligomeric structures potentially characterized as tetramers. Two-electrode voltage clamp electrophysiology demonstrated that human TRPM4 is functionally expressed at the oocyte plasma membrane. This study opens the door for medium-throughput screening and structure-function determination of this important therapeutically relevant target.