Pitahaya aging diagnostic by impedance/capacitance spectroscopy

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

Capacitance spectroscopy and density functional theory

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

Influence of normal and radial contributions of local current density on local electrochemical impedance spectroscopy

A new tri-electrode probe is presented and applied to local electrochemical impedance spectroscopy (LEIS) measurements. As opposed to two-probe systems, the three-probe one allows measurement not only of normal, but also of radial contributions of local current densities to the local impedance values. The results concerning the cases of the blocking electrode and the electrode with faradaic reaction are discussed from the theoretical point of view for a disk electrode. Numerical simulations and experimental results are compared for the case of the ferri/ferrocyanide electrode reaction at the Pt working electrode disk. At the centre of the disk, the impedance taking into account both normal and radial contributions was in good agreement with the local impedance measured in terms of only the normal contribution. At the periphery of the electrode, the impedance taking into account both normal and radial contributions differed significantly from the local impedance measured in terms of only the normal contribution. The radial impedance results at the periphery of the electrode are in good agreement with the usual explanation that the associated larger current density is attributed to the geometry of the electrode, which exhibits a greater accessibility at the electrode edge. (C) 2011 Elsevier Ltd. All rights reserved.

Study on Electrochemical Capacitance using Templated Carbons

The template carbonization technique enables the production of porous carbons and carbon-based composites with precisely designed, controlled pore structures. The resulting templated carbons are therefore useful to investigate and understand the relation between carbon nanostructure and electrocapacitive properties. In this short review paper, we introduce our works on electrochemical capacitance using zeolite-templated carbons and carbon-coated anodic aluminum oxide.

Redox-tagged peptide for capacitive diagnostic assays

Early detection assays play a key role in the successful treatment of most diseases. Redox capacitive biosensors were recently introduced as a potential electroanalytical assay platform for point-of-care applications but alternative surfaces (besides a mixed layer containing ferrocene and antibody receptive component) for recruiting important clinical biomarkers are still needed. Aiming to develop alternative receptive surfaces for this novel electrochemical biosensing platform, we synthesized a ferrocene redoxtagged peptide capable of self-assembly into metallic interfaces, a potentially useful biological surface functionalization for bedside diagnostic assays. As a proof of concept we used C-reactive protein (CRP), as a model biomarker, and compared the obtained results to those of previously reported capacitive assays. The redox-tagged peptide approach shows a limit of detection of 0.8 nmol L 1 (same as 94 ng mL 1 ) and a linear range (R2 ∼98%) with the logarithm of the concentration of the analyte comprising 0.5–10.0 nmol L 1 , within a clinical relevant range for CRP.

Gelatin hydrogel electrolytes and their application to electrochemical supercapacitors

Gelatin hydrogel electrolytes (GHEs) with varying NaCl concentrations have been prepared by cross-linking an aqueous solution of gelatin with aqueous glutaraldehyde and characterized by scanning electron microscopy, differential scanning calorimetry, cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic chronopotentiometry. Glass transition temperatures for GHEs range between 339.6 and 376.9 K depending on the dopant concentration. Ionic conductivity behavior of GHEs was studied with varying concentrations of gelatin, glutaraldehyde, and NaCl, and found to vary between 10(-3) and 10(-1) S cm(-1). GHEs have a potential window of about 1 V. Undoped and 0.25 N NaCl-doped GHEs follow Arrhenius equations with activation energy values of 1.94 and 1.88 x 10(-4) eV, respectively. Electrochemical supercapacitors (ESs) employing these GHEs in conjunction with Black Pearl Carbon electrodes are assembled and studied. Optimal values for capacitance, phase angle, and relaxation time constant of 81 F g(-1), 75 degrees, and 0.03 s are obtained for 3 N NaCl-doped GHE, respectively. ES with pristine GHE exhibits a cycle life of 4.3 h vs 4.7 h for the ES with 3 N NaCl-doped GHE. (c) 2007 The Electrochemical Society.

Supercapacitor studies on globular polypyrrole microstructures developed by a facile electrochemical route

Micrometre-scale polypyrrole (PPy) structures are synthesised for electrochemical supercapacitor applications by a facile electrochemical route. Globular polypyrrole microstructures of size < 5 μm are grown on stainless steel (SS-304) substrate by electro-polymerisation of pyrrole on oxygen microbubble templates electrochemically generated and stabilised in the presence of surfactant/supporting electrolyte/ dopant b-naphthalene sulfonic acid (b-NSA). Microstructures obtained with scan range of 0??1.6 V (against Ag/AgCl) are uniformly distributed over the surface with high coverage density of 5 x 105 to 8 x 10 cm-2. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy revealed that the formed microstructures are of Β-NSA doped PPy. Scanning electron microscopy showed the uniform spread and good coverage of microstructures over the substrate. Supercapacitor properties of PPy films are investigated by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge/discharge methods with 1.0 M KCl as electrolyte in a three-electrode electrochemical cell. Specific capacitance of 583 Fg-1 is obtained, which is greater than the values (350-400 Fg-1 highest) usually reported for this material. Electrochemical impedance spectroscopy proves the superc

Supercapacitor studies on globular polypyrrole microstructures developed by a facile electrochemical route

Micrometre-scale polypyrrole (PPy) structures are synthesised for electrochemical supercapacitor applications by a facile electrochemical route. Globular polypyrrole microstructures of size <5 mu m are grown on stainless steel (SS-304) substrate by electro-polymerisation of pyrrole on oxygen microbubble templates electrochemically generated and stabilised in the presence of surfactant/supporting electrolyte/dopant beta-naphthalene sulfonic acid (beta-NSA). Microstructures obtained with scan range of 0-1.6 V (against Ag/AgCl) are uniformly distributed over the surface with high coverage density of 5 x 10(5) to 8 x 10 cm(-2). Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy revealed that the formed microstructures are of beta-NSA doped PPy. Scanning electron microscopy showed the uniform spread and good coverage of microstructures over the substrate. Supercapacitor properties of PPy films are investigated by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge/discharge methods with 1.0 M KCl as electrolyte in a three-electrode electrochemical cell. Specific capacitance of 583 Fg(-1) is obtained, which is greater than the values (350-400 Fg(-1) highest) usually reported for this material. Electrochemical impedance spectroscopy proves the supercapacitance behaviour and explains the special inductive component of impedance observed in the high-frequency regime because of the globular structures of PPy deposited

Effect of activated carbon xerogel pore size on the capacitance performance of ionic liquid electrolytes

The use of ionic liquid (IL) electrolytes promises to improve the energy density of electrochemical capacitors (ECs) by allowing for operation at higher voltages. Several studies have also shown that the pore size distribution of materials used to produce electrodes is an important factor in determining EC performance. In this research the capacitative, energy and power performance of ILs 1-ethyl-3- methylimidazolium tetrafluoroborate (EMImBF4), 1-ethyl-3-methylimidazolium dicyanamide (EMImN(CN)2), 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide (DMPImTFSI), and 1-butyl-3-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate (BMPyT(F5Et)PF3) were studied and compared with the commercially utilised organic electrolyte 1M tetraethylammonium tetrafluoroborate solution in anhydrous propylene carbonate (Et4NBF4–PC 1 M). To assess the effect of pore size on IL performance, controlled porosity carbons were produced from phenolic resins activated in CO2. The carbon samples were characterised by nitrogen adsorption– desorption at 77 K and the relevant electrochemical behaviour was characterised by cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy. The best capacitance performance was obtained for the activated carbon xerogel with average pore diameter 3.5 nm, whereas the optimum rate performance was obtained for the activated carbon xerogel with average pore diameter 6 nm. When combined in an EC with IL electrolyte EMImBF4 a specific capacitance of 210 F g1 was obtained for activated carbon sample with average pore diameter 3.5 nm at an operating voltage of 3 V. The activated carbon sample with average pore diameter 6 nm allowed for maximum capacitance retention of approximately 70% at 64 mA cm2.

In situ impedance spectroscopy study of the electrochemical corrosion of Ti and Ti-6Al-4V in simulated body fluid at 25 degrees C and 37 degrees C

The corrosion resistance of Ti and Ti-6Al-4V was investigated through electrochemical impedance spectroscopy, EIS, potentiodynamic polarisation curves and UV-Vis spectrophotometry. The tests were done in Hank solution at 25 degrees C and 37 degrees C. The EIS measurements were done at the open circuit potential at specific immersion times. An increase of the resistance as a function of the immersion time was observed, for Ti (at 25 degrees C and 37 degrees C), and for Ti-6Al-4V (at 25 degrees C), which was interpreted as the formation and growth of a passive film on the metallic surfaces. (C) 2009 Elsevier Ltd. All rights reserved.

The Role of Lipopolysaccharide on the Electrochemical Behavior of Titanium

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A Dielectric Model of Self-Assembled Monolayer Interfaces by Capacitive Spectroscopy

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

Elucidating capacitance and resistance terms in confined electroactive molecular layers

Electrochemical analyses on confined electroactive molecular layers, herein exemplified with electroactive self-assembled monolayers, sample current contributions that are significantly influenced by additional nonfaradaic and uncompensated resistance effects that, though unresolved, can strongly distort redox analysis. Prior work has shown that impedance-derived capacitance spectroscopy approaches can cleanly resolve all contributions generated at such films, including those which are related to the layer dipolar/electrostatic relaxation characteristics. We show herein that, in isolating the faradaic and nonfaradaic contributions present within an improved equivalent circuit description of such interfaces, it is possible to accurately simulate subsequently observed cyclic voltammograms (that is, generated current versus potential patterns map accurately onto frequency domain measurements). Not only does this enable a frequency-resolved quantification of all components present, and in so doing, a full validation of the equivalent circuit model utilized, but also facilitates the generation of background subtracted cyclic voltammograms remarkably free from all but faradaic contributions. © 2012 American Chemical Society.

Comparing label free electrochemical impedimetric and capacitive biosensing architectures

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