Electroanalytical detection of pindolol: comparison of unmodified and reduced graphene oxide modified screen-printed graphite electrodes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Single precursor route to efficient cobalt sulphide counter electrodes for dye sensitized solar cells

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

Gold electrodes from recordable CDs for mercury quantification by flow injection analysis

The development of a new methodology for the construction of very efficient flow cells for mercury detection by potentiometric stripping analysis, employing the thin gold layer of recordable CDs as working electrode is reported. This new source of electrodes (CDtrodes) show very attractive performance, similar to that obtained with commercial gold electrodes, with superior versatility. The low cost of this new source of gold electrodes allows a frequent replacement of the electrode, avoiding cumbersome clean-up treatments. Various experimental parameters have been optimized to yield low detection limits (0.25 ng/mL of mercury for 5 min deposition at 0.3 V) and good precision (standard deviation of 1.9% was obtained for 15 repetitive measurements using 10 ng/mL of mercury). Standard curves were found to be linear over the range of 0.5-100 μg L-1 of mercury. The flow cells developed were used for the quantification of mercury in oceanic and tap water. © Springer-Verlag 2000.

Detection of several carbohydrates using boron-doped diamond electrodes modified with nickel hydroxide nanoparticles

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

Influence of light, temperature and metallic ions on biodiesel degradation and corrosiveness to copper and brass

Corrosion is a relevant issue regarding the problem of biodiesel compatibility with polymers and metals. This work aims to evaluate the influence of the natural light incidence and temperature in the corrosion rate of brass and copper immersed in commercial biodiesel as well as biodiesel degradation after the contact with metallic ions. The characterization of corrosion behavior was performed by weight loss measurements according to ASTM G1 and ASTM G31. The experiments according to ASTM G1 were performed at room temperature in light presence and absence. Experiments were also conducted at 55 degrees C in order to compare with ASTM G31 that is also performed at that temperature. The biodiesel degradation was characterized by water content, oxidation stability, viscosity as well as XRF, IR and Raman spectroscopies. The results of ASTM G1 tests showed that the thickness loss for both metals determined at room temperature is slightly higher when there is light incidence and these values significantly decrease for the highest temperature. The results of ASTM G31 tests indicated that air bubbling along with higher temperature affects mostly immersed samples. Biodiesel in contact with metals shows significant degradation in its properties as evidenced by increasing water content, higher viscosity and lower oxidation stability. (C) 2012 Elsevier Ltd. All rights reserved.

Mechanistic changes observed in heavy water for nitrate reduction reaction on palladium-modified Pt(hkl) electrodes

Reduction of nitrate on palladium-modified platinum single-crystal electrodes has been investigated both voltammetrically and spectroscopically in acidic media (pH = 1). Results obtained in H2O and D2O solvents are compared for the three crystallographic orientations. FTIR and differential electrochemical mass spectrometry (DEMS) results clearly indicate that the isotopic substitution of the solvent has a large effect in the mechanism of the reaction, changing the nature of the detected products. For Pt(111)/Pd and Pt(100)/Pd, N2O is detected as the main product of nitrate reduction when D2O is used as solvent, while no N2O is detected when the reaction is performed in H2O. For Pt(110)/Pd, N2O is detected in both solvents, although the use of D2O clearly favours the preferential formation of this product. The magnitude of voltammetric currents is also affected by the nature of the solvent. This has been analysed considering, in addition to the different product distribution, the existence of different transport numbers and optical constants of the solvent.

STRATEGIES FOR PREPARATION OF MOLECULARLY IMPRINTED POLYMERS MODIFIED ELECTRODES AND THEIR APPLICATION IN ELECTROANALYSIS: A REVIEW

Molecularly imprinted polymers (MIP's) have been applied in several areas of analytical chemistry, including the modification of electrodes. The main purpose of such modification is improving selectivity; however, a gain in sensitivity was also observed in many cases. The most frequent approaches for these modifications are the electrodeposition of polymer films and sol gel deposits, spin and drop coating and self-assembling of films on metal nanoparticles. The preparation of bulk (body) modified composites as carbon pastes and polymer agglutinated graphite have also been investigated. In all cases several analytes including pharmaceuticals, pesticides, and inorganic species, as well as molecules with biological relevance have been successfully used as templates and analyzed with such devices in electroanalytical procedures. Herein, 65 references are presented concerning the general characteristics and some details related to the preparation of MIP's including a description of electrodes modified with MIP's by different approaches. The results using voltammetric and amperometric detection are described.

Borohydride electrooxidation on Au and Pt electrodes

Direct borohydride fuel cells (DBFCs) are attractive energy generators for powering portable electronic devices, mainly due to their high energy density and number of electrons per borohydride ion. However, the lack of a highly efficient electrocatalyst for the borohydride oxidation reaction limits the performance of these devices. The most commonly studied electrocatalysts for this reaction are composed of gold and platinum. Nevertheless, for these metals, the borohydride electrooxidation reaction mechanism (BOR) is not completely understood, and the total oxidation reaction, involving eight electrons per BH4- species, competes with parallel reactions, with a lower number of exchanged electrons and/or with heterogeneous chemical hydrolysis. Considering the above-mentioned issues, this work presents recent advances in the knowledge of the BOR pathways on polycrystalline (bulk) Au and Pt electrocatalysts. It presents the studies of the BOR reaction on Au and Pt electrodes using in situ Fourier Transform Infrared Spectroscopy (FUR), and on-line Differential Electrochemical Mass Spectrometry (DEMS). The spectroscopic and spectrometric data provided physical evidence of intermediate species and the formation of H-2 in the course of the BOR as a function of the electrode potential. These results enabled to advance in the knowledge about the BOR pathways on Au and Pt electrocatalysts. (C) 2012 Elsevier Ltd. All rights reserved.

Development of paper based electrodes: From air-breathing to paintable enzymatic cathodes

This work presents the results from the development of bio-cathodes for the application on paper-based biofuel cells. Our main goal here is to demonstrate the possibility of using different designs of air-breathing bio-cathodes and ink-based bio-cathodes for this new type of paper based electrochemical cell. The electrochemical performance for the bio-electrocatalytic oxygen reduction reaction was studied by using open circuit voltage and amperometry measurements, as well as polarization curves to probe the four-electron reduction reaction of ambient oxygen catalyzed by bilirubin oxidase (BOx). The electrochemical measurements showed that all procedures allowed the direct electron transfer from the active site of the bilirubin oxidase to the electrode surface with a limiting current density of almost 500 mu A cm(-2) for an air-breathing BOx cathode and 150 mu A cm(-2) for an ink based BOx cathode. Under a load of 300 mV a stable current density was obtained for 12 h of continuous operation. (C) 2012 Elsevier Ltd. All rights reserved.

Electrochemical surface modification of Single walled carbon nanotubes and graphene-based electrodes for (bio)sensing applications

Sensors are devices that have shown widespread use, from the detection of gas molecules to the tracking of chemical signals in biological cells. Single walled carbon nanotube (SWCNT) and graphene based electrodes have demonstrated to be an excellent material for the development of electrochemical biosensors as they display remarkable electronic properties and the ability to act as individual nanoelectrodes, display an excellent low-dimensional charge carrier transport, and promote surface electrocatalysis. The present work aims at the preparation and investigation of electrochemically modified SWCNT and graphene-based electrodes for applications in the field of biosensors. We initially studied SWCNT films and focused on their topography and surface composition, electrical and optical properties. Parallel to SWCNTs, graphene films were investigated. Higher resistance values were obtained in comparison with nanotubes films. The electrochemical surface modification of both electrodes was investigated following two routes (i) the electrografting of aryl diazonium salts, and (ii) the electrophylic addition of 1, 3-benzodithiolylium tetrafluoroborate (BDYT). Both the qualitative and quantitative characteristics of the modified electrode surfaces were studied such as the degree of functionalization and their surface composition. The combination of Raman, X-ray photoelectron spectroscopy, atomic force microscopy, electrochemistry and other techniques, has demonstrated that selected precursors could be covalently anchored to the nanotubes and graphene-based electrode surfaces through novel carbon-carbon formation.

Thermally reduced Graphene Oxide: a well promising way to transparent flexible electrodes.

L'elaborato tratta dell'ottimizzazione del processo di riduzione termica dell'ossido di grafene in termini di conduttività e trasmittanza ottica. Definiti gli standard di deposizione tramite spin-coating e riduzione termica, i film prodotti vengono caratterizzati tramite XPS, AFM, UPS, TGA, ne vengono testate la conducibilità, con e senza effetto di gate, e la trasmittanza ottica, ne si misura l'elasticità tramite spettroscopia di forza, tutto al fine di comprendere l'evoluzione del processo termico di riduzione e di individuare i parametri migliori al fine di progredire verso la produzione di elettrodi flessibili e trasparenti a base di grafen ossido ridotto.

A Model to Predict Percolation Threshold and Effective Conductivity of Infiltrated Electrodes for Solid Oxide Fuel Cells

We present a mechanistic modeling methodology to predict both the percolation threshold and effective conductivity of infiltrated Solid Oxide Fuel Cell (SOFC) electrodes. The model has been developed to mirror each step of the experimental fabrication process. The primary model output is the infiltrated electrode effective conductivity which provides results over a range of infiltrate loadings that are independent of the chosen electronically conducting material. The percolation threshold is utilized as a valuable output data point directly related to the effective conductivity to compare a wide range of input value choices. The predictive capability of the model is demonstrated by favorable comparison to two separate published experimental studies, one using strontium molybdate and one using La0.8Sr0.2FeO3-δ as infiltrate materials. Effective conductivities and percolation thresholds are shown for varied infiltrate particle size, pore size, and porosity with the infiltrate particle size having the largest impact on the results.

A Model to Predict Percolation Threshold and Effective Conductivity of Infiltrated Electrodes for Solid Oxide Fuel Cells

We present a mechanistic modeling methodology to predict both the percolation threshold and effective conductivity of infiltrated Solid Oxide Fuel Cell (SOFC) electrodes. The model has been developed to mirror each step of the experimental fabrication process. The primary model output is the infiltrated electrode effective conductivity which provides results over a range of infiltrate loadings that are independent of the chosen electronically conducting material. The percolation threshold is utilized as a valuable output data point directly related to the effective conductivity to compare a wide range of input value choices. The predictive capability of the model is demonstrated by favorable comparison to two separate published experimental studies, one using strontium molybdate and one using La0.8Sr0.2FeO3-delta as infiltrate materials. Effective conductivities and percolation thresholds are shown for varied infiltrate particle size, pore size, and porosity with the infiltrate particle size having the largest impact on the results. (C) 2013 The Electrochemical Society. All rights reserved.