Low content cerium oxide nanoparticles on carbon for hydrogen peroxide electrosynthesis

A comparative study using different proportions of CeO2/C (4%, 9% and 13% CeO2) was performed to produce H2O2, a reagent used in the oxidation of organic pollutants and in electro-Fenton reactions for the production of the hydroxyl radical (OH center dot), a strong oxidant agent used in the electrochemical treatment of aqueous wastewater. The CeO2/C materials were prepared by a modified polymeric precursor method (PPM). X-ray diffraction analysis of the CeO2/C prepared by the PPM identified two phases. CeO2 and CeO2. The average size of the crystallites in these materials was close to 7 nm. The kinetics of the oxygen reduction reaction (ORR) were evaluated by the rotating ring-disk electrode technique. The results showed that the 4% CeO2/C prepared by the PPM was the best composite for the production of H2O2 in a 1 mol L-1 NaOH electrolyte solution. For this material, the number of electrons transferred and the H2O2 percentage efficiency were 3.1 and 44%, respectively. The ring-current of the 4% CeO2/C was higher than that of Vulcan carbon, the reference material for H2O2 production, which produced 41% H2O2 and transferred 3.1 electrons per molecule of oxygen. The overpotential for this reaction on the ceria-based catalyst was substantially lower (approximately 200 mV), demonstrating the higher catalytic performance of this material. Gas diffusion electrodes (GDE) containing the catalyst were used to evaluate the real amount of H2O2 produced during exhaustive electrolysis. The 4% CeO2/C GDE produced 871 mg L-1 of H2O2, whereas the Vulcan carbon GDE produced a maximum amount of only 407 mg L-1. Thus, the 4% CeO2/C electrocatalyst prepared by the PPM is a promising material for H2O2 electrogeneration in alkaline media. (C) 2011 Elsevier B.V. All rights reserved.

The impact of the alkali cation on the mechanism of the electro-oxidation of ethylene glycol on Pt

By means of in situ IR spectroscopy we investigate the effect of dissolved alkali cations on the electro-oxidation of ethylene glycol on platinum in alkaline media. The results revealed that the increase in the oxidation currents (Li(+) < Na(+) < K(+)) is reflected in the increase in the ratio between carbonate and oxalate produced.

Electrocatalytic performance of environmentally friendly synthesized gold nanoparticles towards the borohydride electro-oxidation reaction

In this paper we report a simple and environmentally friendly synthesis of gold nanoparticles (AuNps) and their electrocatalytic activity for borohydride oxidation reaction (BOR). Ultraviolet spectroscopy (UV- vis) and transmission electron microscopy (TEM) confirmed the formation of poly(vinyl pyrrolidone)protected colloidal AuNps through direct reduction of Au3+ by glycerol in alkaline medium at room temperature. For the BOR tests the AuNps were directly produced onto carbon to yield the Au/C catalyst. Levich plots revealed that the process occured via 7.2 electrons, therefore near the theoretical value of 8 electrons. When compared to bulk Au, the gold nanoparticles presented enhanced catalytic properties since the onset potential for BOR was shifted 200 mV towards negative potentials. (C) 2012 Elsevier B.V. All rights reserved.

Interference of inorganic ions on phenol degradation by the Fenton reaction

The addition of Cu2+ ions to the classical Fenton reaction (Fe2+ plus H2O2 at pH 3) is found to accelerate the degradation of organic compounds. This synergic effect causes an approximately 15 % additional reduction of the total organic carbon (TOC), representing an overall improvement of the efficiency of the mineralization of phenol. Although Fe2+ exhibits a high initial rate of degradation, the degradation is not complete due to the formation of compounds refractory to the hydroxyl radical. The interference of copper ions on the degradation of phenol by the Fenton reaction was investigated. In the presence of Cu2+, the degradation is slower, but results in a greater reduction of TOC at the end of the reaction (t = 120 min). In the final stages of the reaction, when the Fe3+ in the solution is complexed in the form of ferrioxalate, the copper ions assume the role of the main catalyst of the degradation.

Photo-Fenton oxidation of phenol and organochlorides (2,4-DCP and 2,4-D) in aqueous alkaline medium with high chloride concentration

A highly concentrated aqueous saline-containing solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2.4-DCP) was treated by the photo-Fenton process in a system composed of an annular reactor with a quartz immersion well and a medium-pressure mercury lamp (450 W). The study was conducted under special conditions to minimize the costs of acidification and neutralization, which are usual steps in this type of process. Photochemical reactions were carried out to investigate the influence of some process variables such as the initial concentration of Fe2+ ([Fe2+](0)) from 1.0 up to 2.5 mM, the rate in mmol of H2O2 fed into the system (F-H2O2,F-in) from 3.67 up to 7.33 mmol of H2O2/min during 120 min of reaction time, and the initial pH (pH(0)) from 3.0 up to 9.0 in the presence and absence of NaCl (60.0 g/L). Although the optimum pH for the photo-Fenton process is about 3.0, this particular system performed well in experimental conditions starting at alkaline and neutral pH. The results obtained here are promising for industrial applications, particularly in view of the high concentration of chloride, a known hydroxyl radical scavenger and the main oxidant present in photo-Fenton processes. (C) 2012 Elsevier Ltd. All rights reserved.

Investigation of a Pt3Sn/C Electro-Catalyst in a Direct Ethanol Fuel Cell Operating at Low Temperatures for Portable Applications

A 20% Pt3Sn/C catalyst was prepared by reduction with formic acid and used in a direct ethanol fuel cell at low temperatures. The electro-catalytic activity of this bimetallic catalyst was compared to that of a commercial 20% Pt/C catalyst. The PtSn catalyst showed better results in the investigated temperature range (30 degrees-70 degrees C). Generally, Sn promotes ethanol oxidation by adsorption of OH species at considerably lower potentials compared to Pt, allowing the occurrence of a bifunctional mechanism. The bimetallic catalyst was physico-chemically characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses. The presence of SnO2 in the bulk and surface of the catalyst was observed. It appears that SnO2 can enhance the ethanol electro-oxidation activity at low potentials due to the supply of oxygen-containing species for the oxidative removal of CO and CH3CO species adsorbed on adjacent Pt active sites.

Electrocatalytic Activity of Pd, Pt, and Rh for the Electro-oxidation of Ethanol in Alkaline Electrolyte: An Online DEMS Study

The electro-oxidation of ethanol was investigated on electrodeposited layers of Pd, Pt, and Rh in alkaline electrolyte. The reaction products were monitored by experiments of online differential electrochemical mass spectrometry (DEMS). Potentiodynamic curves for the ethanol electro-oxidation catalyzed by these three different metal electrocatalysts showed similar onset potentials, but the highest Faradaic current peak was observed for the Pt electrocatalyst. Online DEMS experiments evidenced similar amounts of CO2 for the three different materials, but Pd presented the higher production of ethylacetate (acetic acid). This indicated that the electrochemical oxidation of ethanol on the Pd surface occurred to a higher extent. The formation of methane, which was observed for Pt and Rh, after potential excursions to lower potentials, was absent for Pd. On the basis of the obtained results, it was stated that, on Pt and Rh, the formation of CO2 occurs mainly via oxidation of CO and CH (x,ad) species formed after dissociative adsorption of ethanol or ethoxy species that takes place only at low potentials. This indicates that the dissociative adsorption of ethanol or ethoxy species is inhibited at higher potentials on Pt and Rh. On the other hand, on the Pd electrocatalyst, the reaction may occur via nondissociative adsorption of ethanol or ethoxy species at lower potentials, followed by oxidation to acetaldehyde and, after that, by a further oxidation step to acetic acid on the electrocatalyst surface. Additionally, in a parallel route, the acetaldehyde molecules adsorbed on the Pd surface can be deprotonated, yielding a reaction intermediate in which the carbon-carbon bond is less protected, and therefore, it can be dissociated on the Pd surface, producing CO2, after potential excursions to higher potentials.

Hydrogen peroxide monitoring in Fenton reaction by using a ruthenium oxide hexacyanoferrate/multiwalled carbon nanotubes modified electrode

A novel amperometric sensor based on the incorporation of ruthenium oxide hexacyanoferrate (RuOHCF) into multiwalled carbon nanotubes (MWCNTs) immobilized on a glassy carbon electrode is described. Cyclic voltammetry experiments indicated that the cathodic reduction of hydrogen peroxide at the RuOHCF/MWCNTs100/GC modified electrode is facilitated, occurring at 0.0 V vs. Ag/AgCl/KCl(sat). Following the optimization of the experimental conditions, the proposed sensor presented excellent analytical properties for hydrogen peroxide determination, with a low limit of detection (4.7 mu mol L-1), a large dynamic concentration range (0.1-10 mmol L-1) and a sensitivity of 1280 mu A mmol(-1) L cm(-2). The usefulness of the RuOHCF/MWCNTs100/GC electrochemical sensor was confirmed by monitoring the consumption of hydrogen peroxide during the degradation of phenol by the Fenton reaction. (C) 2012 Elsevier B.V. All rights reserved.

Electro-oxidation of ethanol on Pt/C, Rh/C, and Pt/Rh/C-based electrocatalysts investigated by on-line DEMS

The ethanol electro-oxidation reaction was studied on carbon-supported Pt, Rh, and on Pt overlayers deposited on Rh nanoparticles. The synthesized electrocatalysts were characterized by TEM and XRD. The reaction products were monitored by on-line DEMS experiments. Potentiodynamic curves showed higher overall reaction rate for Pt/C when compared to that for Rh/C. However, on-line DEMS measurements revealed higher average current efficiencies for complete ethanol electro-oxidation to CO2 on Rh/C. The average current efficiencies for CO2 formation increased with temperature and with the decrease in the ethanol concentration. The total amount of CO2, on the other hand, was slightly affected by the temperature and ethanol concentration. Additionally, the CO2 signal was observed only in the positive-going scan, none being observed in the negative-going scan, evidencing that the C-C bond breaking occurs only at lower potentials. Thus, the formation of CO2 mainly resulted from oxidative removal of adsorbed CO and CHx,ad species generated at the lower potentials, instead of the electrochemical oxidation of bulk ethanol molecules. The acetaldehyde mass signal, however, was greatly favored after increasing the ethanol concentration from 0.01 to 0.1 mol L-1, on both electrocatalysts, indicating that it is the major reaction product. For the Pt/Rh/C-based electrocatalysts, the Faradaic current and the conversion efficiency for CO2 formation was increased by adjusting the amount of Pt on the surface of the Rh/C nanoparticles. The higher conversion efficiency for CO2 formation on the Pt1Rh/C material was ascribed to its faster and more extensive ethanol deprotonation on the Pt-Rh sites, producing adsorbed intermediates in which the C-C bond cleavage is facilitated. (C) 2012 Elsevier B.V. All rights reserved.

The dual pathway in action: decoupling parallel routes for CO2 production during the oscillatory electro-oxidation of methanol

As in the case of most small organic molecules, the electro-oxidation of methanol to CO2 is believed to proceed through a so-called dual pathway mechanism. The direct pathway proceeds via reactive intermediates such as formaldehyde or formic acid, whereas the indirect pathway occurs in parallel, and proceeds via the formation of adsorbed carbon monoxide (COad). Despite the extensive literature on the electro-oxidation of methanol, no study to date distinguished the production of CO2 from direct and indirect pathways. Working under, far-from-equilibrium, oscillatory conditions, we were able to decouple, for the first time, the direct and indirect pathways that lead to CO2 during the oscillatory electro-oxidation of methanol on platinum. The CO2 production was followed by differential electrochemical mass spectrometry and the individual contributions of parallel pathways were identified by a combination of experiments and numerical simulations. We believe that our report opens some perspectives, particularly as a methodology to be used to identify the role played by surface modifiers in the relative weight of both pathways-a key issue to the effective development of catalysts for low temperature fuel cells.

Mechanistic Implications of Zinc(II) Ions on the Degradation of Phenol by the Fenton Reaction

A study of the interference of Zn2+ ions on phenol degradation by Fenton reaction (Fe2+/Fe3(+) + H2O2) is reported. One of the first intermediates formed in the reaction, catechol, can reduce Fe3+ to Fe2+ and, in the presence of H2O2 initiates an efficient catalytic redox cycle. In the initial stages of the reaction, this catechol-mediated cycle becomes the principal route of thermal degradation of phenol and its oxidation products. The Zn2+ ion addition enhances the persistence time of catechol, probably by stabilization of the corresponding semiquinone radical via complexation.

The influence of different co-catalysts in Pt-based ternary and quaternary electro-catalysts on the electro-oxidation of methanol and ethanol in acid media

One of the key objectives in fuel cell technology is to reduce Pt loading by the improvement of its catalytic activity towards alcohol oxidation. Here, a sol-gel based method was used to prepare ternary and quaternary carbon supported nanoparticles by combining Pt-Ru with Mo, Ta, Pb, Rh or Ir, which were used as electro-catalysts for the methanol and ethanol oxidation reactions in acid medium. Structural characterization performed by XRD measurements revealed that crystalline structures with crystallites ranging from 2.8 to 4.1 nm in size and with different alloy degrees were produced. Tantalum and lead deposited as a heterogeneous mixture of oxides with different valences resulting in materials with complex structures. The catalysts activities were evaluated by cyclic voltammetry and by Tafel plots and the results showed that the activity towards methanol oxidation was highly dependent of the alloy degree, while for ethanol the presence of a metal capable to promote the break of C-C bond, such as Rh, was necessary for a good performance. Additionally, the catalysts containing of TaOx or PbOx resulted in the best materials due to different effects: the hi-functional mechanism promoted by TaOx and a better dispersion of the catalysts constituents promoted by PbOx. (C) 2012 Elsevier B.V. All rights reserved.

Delivery Levels of Support Competencies to Organizational Eco-efficiency: a case study in an electro-electronics sector industry

This article aims to develop and implement a search tool which, through the perception of its respondents, allows assessing how eco-efficient an organization is based on the identification of delivery levels of support competencies to organizational eco-efficiency. A mixed (qualitative and quantitative) exploratory-descriptive research was conducted, from a case study in an 'ISE Company'. A semi-structured interview and pictures of verification were used as data collection instruments. The data were analyzed via documentary analysis and triangulation of information collected. It was inferred that at the 'ISE Company' professionals at the high-level of the organizational hierarchy recognize, in part, the growth of organizational actions that contribute to sustainability, which is not fully consistent with national publications on the subject. The result of the research showed that organizational strategies addressing eco-efficiency are partially aligned with the professional performance of the organization.

Chemical Selectivity during the Electro-Oxidation of Ethanol on Unsupported Pt Nanoparticles

In this paper we present results on the electro-oxidation of ethanol on unsupported (carbon free) platinum nanoparticles, considering the effects of the alcohol concentration. The case of the so-called dual pathway mechanism during the electro-oxidation of ethanol showed to be influenced by the surface coverage of adsorbed carbon monoxide (COad) at unsupported platinum. The influences of adsorbed intermediates were followed by in situ infrared spectroscopy (FTIR) and by electrochemical experiments. Unsupported platinum showed that the reaction leads to the formation of CO2 and acetic acid as main products at low concentrations of ethanol (0.01 to 0.1 mol L-1). At least in this case of 0.01 mol L-1 ethanol, most formation of CO2 occurred via COad (indirect pathway). At higher concentration of ethanol, however, most CO2 was formed via a reactive intermediate such as acetaldehyde (direct pathway). In addition, in this higher concentration of ethanol, the acetic acid was produced via formation of adsorbed acetaldehyde (via acetate) at higher overpotentials. In case of the acetic acid formation, a dual pathway was identified during the electro-oxidation of ethanol at low alcohol concentrations, whereas a parallel pathway occurred without the formation of adsorbed acetate intermediates at low overpotentials. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.101203jes] All rights reserved.

Amitriptyline prolongs the antihyperalgesic effect of 2- or 100-Hz electro-acupuncture in a rat model of post-incision pain

The mechanisms through which electro-acupuncture (EA) and tricyclic antidepressants produce analgesia seem to be complementary: EA inhibits the transmission of noxious messages by activating supraspinal serotonergic and noradrenergic neurons that project to the spinal cord, whereas tricyclic antidepressants affect pain transmission by inhibiting the reuptake of norepinephrine and serotonin at the spinal level. This study utilized the tail-flick test and a model of post-incision pain to compare the antihyperalgesic effects of EA at frequencies of 2 or 100 Hz in rats treated with intraperitoneal or intrathecal amitriptyline (a tricyclic antidepressant). A gradual increase in the tail-flick latency (TFL) occurred during a 20-min period of EA. A strong and long-lasting reduction in post-incision hyperalgesia was observed after stimulation; the effect after 2 Hz lasting longer than after 100-Hz EA. Intraperitoneal or intrathecal amitriptyline potentiated the increase in TFL in the early moments of 2- or 100-Hz EA, and the intensity of the antihyperalgesic effect of 100-Hz EA in both the incised and non-incised paw. In contrast, it did not significantly change the intensity of the antihyperalgesic effect of 2-Hz EA. The EA-induced antihyperalgesic effects lasted longer after intraperitoneal or intrathecal amitriptyline than after saline, with this effect of amitriptyline being more evident after 100-than after 2-Hz EA. The synergetic effect of amitriptyline and EA against post-incision pain shown here may therefore represent an alternative for prolonging the efficacy of EA in the management of post-surgical clinical pain.