Development of a PtSn bimetallic catalyst for direct fuel cells using bio-butanol fuel

Pt and PtSn catalysts were studied for n-butanol electro-oxidation at various temperatures. PtSn showed a higher activity towards butanol electro-oxidation compared to Pt in acidic media. The onset potential for n-butanol oxidation on PtSn is ~520 mV lower than that found on Pt, and significantly lower activation energy was found for PtSn compared with that for Pt.

Estudo dos processos eletroquímicos: eletrooxidação e eletrocoagulação

O tratamento físico-químico de águas residuais, de origem industrial, mais comum é o tratamento baseado na adição de coagulante e floculante a um efluente. No entanto, o tratamento eletroquímico é um tipo de tratamento que tem vindo a ser explorado e estudado com mais ênfase ao longo dos últimos anos. O tratamento eletroquímico é uma tecnologia AOP (Processos de Oxidação Avançada) e divide-se em eletrólise direta (oxidação e redução) e indireta (eletrocoagulação-flotação e eletrooxidação). A eletrocoagulação e eletrooxidação divergem apenas pelo tipo de reações que ocorrem, devido ao material que constitui os elétrodos. São processos complexos com uma multiplicidade de mecanismos que operam sinergicamente para remover poluentes da água. Tendo em conta a sua complexidade e ainda dificuldade de compreensão, existem na literatura diferentes versões acerca de quais os mecanismos chave, assim como diversas configurações geométricas de reatores e elétrodos. Atualmente, este tipo de tratamento tem vindo a evoluir, tornando-se num método economicamente viável para o tratamento de uma grande variedade de águas residuais, nomeadamente, aquelas que possuem compostos recalcitrantes na sua composição. O presente trabalho foi realizado nas instalações da VentilAQUA S.A. e, tendo em conta a sua área de especialidade, o trabalho exposto focou-se no desenvolvimento de soluções técnicas de AOP, nomeadamente na área eletroquímica (eletrocoagulação e eletrooxidação),para estudo dos parâmetros operacionais numa nova configuração geométrica para os elétrodos. Tendo por base os contributos da revisão bibliográfica, o estudo incidiu num reator tubular, com elétrodos de inox dispostos de forma concêntrica, à mesma distância entre si. Com este reator foram executados variados testes, com diferentes efluentes, que permitiram obter resultados operacionais de otimização de funcionamento, tendo em vista a remoção de poluentes. O estudo financeiro associado permitiu concluir que a eletrooxidação é significativamente mais económica que o tratamento físico-químico, nas condições operacionais e para os efluentes tratados. Relativamente ao Acompanhamento e Gestão de ETAR’s (Capítulo 4) foi possível verificar que todos os casos em estudo apresentam uma boa eficiência de remoção de matéria orgânica, permitindo a descarga do seu efluente com uma carga poluente que cumpre com os requisitos legais de descarga em meio hídrico.

Electrochemical determination of antioxidant capacities in flavored waters by guanine and adenine biosensors

The immobilization and electro-oxidation of guanine and adenine asDNA bases on glassy carbon electrode are evaluated by square wave voltammetric analysis. The influence of electrochemical pretreatments, nature of supporting electrolyte, pH, accumulation time and composition of DNA nucleotides on the immobilization effect and the electrochemical mechanism are discussed. Trace levels of either guanine or adenine can be readily detected following short accumulation time with detection limits of 35 and 40 ngmL−1 for guanine and adenine, respectively. The biosensors of guanine and adenine were employed for the voltammetric detection of antioxidant capacity in flavored water samples. The method relies on monitoring the changes of the intrinsic anodic response of the surface-confined guanine and adenine species, resulting from its interaction with free radicals from Fenton-type reaction in absence and presence of antioxidant. Ascorbic acid was used as standard to evaluate antioxidant capacities of samples. Analytical data was compared with that of FRAP method.

The influence of acetic acid on the ethanol electrooxidation on a platinum electrode

In the presented work, the evaluation of the influence of acetic acid in the electrochemical environment on the ethanol electro-oxidation reaction on a polycrystalline platinum electrode is presented for the first time. Using cyclic voltammetry. chronoamperometry and in situ Fourier Transformed IR spectroscopy (FTIR) it was demonstrated that an inhibition of the ethanol oxidation reaction occurs for bulk acetic acid concentrations of the order 0.1 mu mol L(-1) -5 mmol L(-1). This inhibition effect is related to the decrease of CO(2) and acetaldehyde production as confirmed by spectroscopic results. (C) 2011 Elsevier B.V. All rights reserved.

Evidence for diffusional coupling in electrochemical thin layers: implications for surface coverage calibration via electrochemical infrared spectroscopy

The time dependence of the concentration of CO2 in an electrochemical thin layer cavity is studied with Fourier transform infrared spectroscopy (FTIR) in order to evaluate the extent to which the thin layer cavity is diffusionally decoupled from the surrounding bulk electrolyte. For the model system of CO on Pt(111) in 0.1 M HClO4, it is found that the concentration of CO2, formed by electro-oxidation of CO, equilibrates rapidly with the surrounding bulk electrolyte. This rapid equilibration indicates that there is diffusion out of the thin layer, even on the short time scales of typical infrared experiments (1-3 min). However, since the measured CO2 absorbance intensity as a function of time is reproducible to within 10%, a new time-dependent method for surface coverage calibration using solution-phase species is proposed.

Electrochemical Behavior of Verapamil at Graphite-Polyurethane Composite Electrodes: Determination of Release Profiles in Pharmaceutical Samples

A solid graphite-polyurethane composite electrode has been used to determine release profiles of verapamil, a calcium-channel blocker. The electro-oxidation process was characterized by cyclic voltammetry and electrochemical impedance spectroscopy and showed no adsorption of analyte or oxidation products, unlike at other carbon-based electrodes. Quantification gave linear ranges up to 40molL-1 with cyclic voltammetry and detection limits of 0.7molL-1 by differential pulse and square-wave voltammetry. Commercial product samples were successfully analyzed with results equal to those from spectrophotometry. Because no electrode surface renewal is needed, this electrode material has many advantages.

Hidróxido de níquel suportado em carbono: um catalisador de baixo custo para a eletro-oxidação de alcoóis em meio alcalino

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electrocatalytic study of an electrode modified with Reactive Blue 4 dye covalently immobilized on amine-functionalized silica

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Altering the adsorptive and electronic properties of Pt through poly(vinyl alcohol) adsorption

In the present paper we investigated the effect of adsorbed PVA on Pt electrodes on classic electrochemical processes such as hydrogen UPD, oxygen reduction and CO electro-oxidation. Upon adsorption PVA blocks roughly 50% of the hydrogen sites and can not be removed from the Pt surface through cycling in the potential range of 0.05-1.0 V vs. RHE. Potentiodynamic experiments under controlled hydrodynamic conditions provided by rotating disk electrode experiments showed a negative impact of the adsorbed PVA on the oxygen reduction reaction (ORR). Cyclic-voltammetry results revealed that not even CO was able to remove PVA from the Pt surface. Regarding the oxidation of CO, the adsorbed polymer positively shifted the CO oxidation peak potential, therefore higher potentials are required to free the Pt surface from CO poisoning. In situ Fourier transform infrared spectroscopy evidenced that the presence of PVA shifted the linearly bound CO frequency toward higher wavenumbers, a process found to be independent of the Pt surface orientation. In situ electrochemical X-ray absorption spectroscopy results showed that PVA also impacted the electronic properties of platinum by decreasing the occupancy of the Pt conducting 5d band. Our findings clearly support the efforts toward understanding the nature of the interaction between polymers and metallic surfaces as well as the impact on technological applications (e.g. in PEMFCs). © 2013 Elsevier Ltd. All rights reserved.

Sugars Electrooxidation at Glassy Carbon Electrode Decorate with Multi-Walled Carbon Nanotubes with Nickel Oxy-Hydroxide

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

Synthesis and characterization of alpha-nickel (II) hydroxide particles on organic-inorganic matrix and its application in a sensitive electrochemical sensor for vitamin D determination

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

Síntese de nanopartículas de prata suportadas sobre nanotubos de carbono de paredes múltiplas para eletrooxidação de benzeno

Silver nanoparticles (Ag) were deposited on multi-walled carbon nanotube by eletroless. The hybrid Ag/MWCNT was used in the modification of glassy carbon electrode (GC) surface. The electrochemical characterization confirmed the presence of Ag in the nanocomposite has been showed that the synthesis was successful. The GC electrode modified with Ag/MWCNT film was evaluated for electro-oxidation of benzene. The electrochemical behavior presented an improvement on the catalytic surface in relation to non-modified GC electrode. The anodic peak current increased the magnitude in three times when compared with the CG electrode modified only with MWCNT

Development and application of a screen-printed electrode modified with MWCNT for the electrocatalytic detection of thiram

Interest in the electronic properties of carbon nanotubes has increased in recent years. These materials can be used in the development of electrochemical sensors for the measurement and monitoring of analytes of environmental interest, such as pharmaceuticals, dyes, and pesticides. This work describes the use of homemade screen-printed electrodes modified with multi-walled carbon nanotubes (MWCNT) for the electrochemical detection of the fungicide thiram. The electrochemical characteristics of the proposed system were evaluated using cyclic voltammetry, with investigation of the electrochemical behavior of the sensor in the presence of the analyte, and estimation of electrochemical parameters including the diffusion coefficient, electron transfer coefficient (α), and number of electrons transferred in the catalytic electro-oxidation. The sensor response was optimized using amperometry. The best sensor performance was obtained in 0.1 mol L-1 phosphate buffer solution at pH 8.0, where a detection limit of 7.9 x 10-6 mol L-1 was achieved. Finally, in order to improve the sensitivity of the sensor, square wave voltammetry (SWV) was used for thiram quantification, instead of amperometry. Using SWV, a response range for thiram from 9.9 x 10-6 to 9.1 x 10-5 mol L-1 was obtained, with a sensitivity of 30948 µA mol L-1, and limits of detection and quantification of 1.6 x 10-6 and 5.4 x 10-6 mol L-1, respectively. The applicability of this efficient new alternative methodology for thiram detection was demonstrated using analyses of enriched soil samples.

Potentiodynamic behaviour of CuA1Ag alloys in NaOH: a comparative study related to the pure metals electrochemistry

The mechanism of electrochemical oxidation of surface reformed CuA1Ag alloys having different composition of heat treatment, in 0.5 M NaOH was studied by means of cyclic polarization, constant potential electrolysis, ICP, AA, SEM and EDX. The surface reformation consisted of a repetitive triangular potential sweep (RTPS) between H 2 and O 2 evolution at 100 mV s -1 in the working solution itself, performed in order to increase the electrode roughness and obtain a quasi-stationary I/E profile in which the potentiodynamic behaviour of copper and silver was clearly revealed. The alloys suffer aluminum dealloying after such an RTPS. The quasi-stationary cyclic polarization curve exhibits a multiplicity of current peaks which have been related to the electrochemical reactions involving the pure alloying elements. Complex potential perturbation programmes in regions having different anodic and cathodic limits allowed the study of the mechanism of the electrochemical oxidation of the surface reformed alloys and the compare with that corresponding to the pure metals. The basic differences between the electro-oxidation processes of the surface reformed CuA1Ag alloys with respect to those established for the high purity alloying metals are the splitting of the peaks corresponding to the formation of the Cu(I) and Ag(I) species. © 1991.

A label-free impedimetric immunosensor for direct determination of the textile dye Disperse Orange 1

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