Amino-functionalized multiwalled carbon nanotubes (MWCNT-NH2) were modified with Fe phthalocyanine (FePc) and perchlorinated Fe phthalocyanine (16(Cl)FePc) and deposited on glassy carbon electrodes (GCE). The electrocatalytic activity of these hybrid electrodes was examined for the reduction of molecular oxygen in alkaline media (0.2 M NaOH) using stationary and rotating disk electrodes. Electrodes containing 16(Cl)FePc are more active than those containing FePc. Electrodes containing CNTs are more active than electrodes without CNTs but the higher activity can be attributed to a greater real surface area, compared CGEs and not necessarily to a catalytic effect.

Multiwalled carbon nanotububes functionalized with amino groups (MWCNT-NH2) and further modified with copper-phthalocyaninetetrasulphonate (4ß(SO3) CuPc) were used for preparing a hybrid electrode [MWCNT-NH2/4ß(SO3)CuPc/GC] using glassy carbon (GC) as a support. This hybrid electrode was tested for the detection of dopamine (DA) in the presence of ascorbic acid (AA) and uric acid (UA) in a PBS buffer solution at pH 6.8. The presence of the macrocyclic increased the resolution of the oxidation signals of AA, DA and UA into three very well distinct oxidation peaks. This effect was enhanced when the complex is adsorbed on multiwalled carbon nanotubes. In addition, the hybrid films provide a simple method for selective detection of DA, AA and UA in biological samples. The calibration curves for DA were obtained over the range of 1x10-6-1x10-3M, obtaining a good selectivity and sensitivity.

Electrodes prepared from overoxidized pyrrole, multi-walled carbon nanotubes (MWCNT) and cobalt phthalocyanine (CoPc) exhibit a clear catalytic activity for the electrooxidation of L-cysteine and reduced gluthatione. The electrodes are more stable than the ones modified by simple adsorption of CoPc and/or MW-CNT. Therefore, these materials offer a good alternative for the development of electrocatalytic applications and thiols detection in biological interest.

A oxidação eletrocatalítica de hidrazina foi estudada sobre um eletrodo de grafite pirolítico ordinário modificado com tetrapiridinoporfirazina de ferro (FeTPyPz) com as técnicas de voltametria cíclica e de eletrodo de disco rotatório. Análise dos voltamogramas registrados a diferentes velocidades de varredura do potencial e das curvas de polarização para diferentes velocidades de rotação do eletrodo mostraram que a reação de eletroxidação de hidrazina sobre FeTPyPz processa-se de acordo com um mecanismo envolvendo 4 elétrons e com a formação de N2 como principal produto. Os parâmetros cinéticos sugerem que a segunda etapa de transferência de carga é a etapa determinante da velocidade da reação. A atividade eletrocatalítica do complexo FeTPyPz depende do potencial formal do processo redox Fe(II)/Fe(I), que apresentou bom ajuste num gráfico do tipo vulcano formado por diferentes ftalocianinas de ferro, indicando que este potencial formal é um bom indicador da reatividade destes complexos.

The electrocatalytic oxidation of hydrazine was studied using an ordinary pyrolytic graphite electrode modified with iron tetrapyridinoporphyrazine complex (FeTPyPz), employing cyclic voltammetry and rotating disk electrode techniques. Analyses of the voltammograms recorded at different potential scan rates and the polarization curves at different electrode rotation rates showed that the reaction of electrooxidation of hydrazine on FeTPyPz occurs via 4-electrons with the formation of N2 as main product. The kinetic parameters suggest that the second electron transfer step is rate controlling. The activity of FeTPyPz depends on its Fe(II)/Fe(I) formal potential and fits well in a volcano plot that includes several iron phthalocyanines, indicating that such formal potential is a good reactivity index for these complexes.

Methanol oxidation on Pt-Rh alloys of different compositions in sulfuric acid solution was studied by cyclic voltammetry (CV). Rh increases the activity of Pt electrodes for methanol oxidation, specially for the 87-13 Pt-Rh alloy. This enhancement is discussed and attributed to a bifunctional mechanism

En el presente trabajo se estudia, mediante voltametría cíclica (CV), la oxidación de metanol sobre aleaciones Pt-Rh con diferente composición. Los resultados indican que Rh aumenta la actividad electrocatalítica del Pt para la oxidación de metanol, especialmente la aleación con un contenido de Rh del 13%. Los resultados son discutidos en el texto y se atribuyen a un mecanismo bifuncional

The effect of ageing the electrode on the mass response was studied by two approaches, namely: i) ageing the Pt deposits on the Au/Q substrate and ii) ageing the Au/Q substrate and then examining the response of the Pt deposit on the aged Au/Q. Mass changes in the H-region are observed in both cases, which are attributed to an increase in water adsorption/desorption on the Pt surface, due to changes in the structure of the Pt deposit. These changes are not visible in CV curves

En el presente trabajo se estudia el efecto del envejecimiento de electro-depósitos de platino en la respuesta deltam/E obtenidas con la electrobalanza de cristal de cuarzo (EQCM). Dos tipos de electrodos fueron estudiados: i) envejecimiento de depósitos de platino sobre Au/Q electrodos y ii) estudio del comportamiento de electrodepósitos de platino obtenidos sobre Au/Q electrodos previamente envejecidos. En ambos casos se observan cambios de masa en la zona de potenciales de adsorción-reducción de hidrógeno, las cuales se atribuyen a un aumento en la cantidad de agua adsorbida/desorbida en la superficie del electrodo, como consecuencia de cambios estructurales en el depósito de platino. Estos cambios no son visibles por voltametría cíclica

We have investigated the potentiometric response of ordinary pyrolytic graphite electrodes (OPG) modified with cobalt phthalocyanine (Co-Pc) for thiols (R-SH) 2-mercaptoethanol, L-cysteine and their corresponding disulfides (R-SS-R). Stable potentials are achieved after a few seconds of additions of different amounts of thiols to aqueous solutions of pH values between 11 and 4. Plots of potential vs. log [R-SH] give straight lines for all cases with slopes ca. -0.060 V with concentrations of the thiol varying from 10-5 up to 10-2 M. These measurements were conducted in the presence of air or oxygen. Under nitrogen, the slopes increase to -0.14 V. The potential response of OPG/Co-Pc is independent of disulfide concentration, which shows that these modified electrodes are only sensitive to the thiol. Graphite electrodes without modification are not sensitive to the concentration of thiols in the solution and the potential response is erratic.

Se ha investigado la respuesta potenciométrica the electrodos de grafito pirolítico ordinario (OPG) modificados con ftalocianina de cobalto (Co-Pc) frente a los tioles (R-SH) 2-mecaptoetanol y L-cisteína y los correspondientes disulfuros (R-SS-R). Al agregar pequeñas cantidades de estos tioles a soluciones acuosas con pH en el rango 11-4, se obtienen respuestas en potencial estables dentro de unos pocos segundos despues de las adiciones. Gráficas de potencial vs. log [R-SH] dan rectas para todos los casos, con pendientes cercanas a -0,060 V para concentraciones del tiol en el rango de 10-5 a 10-2 M. Estas medidas se efectuaron en presencia de aire u oxígeno. En atmósfera de nitrógeno, las pendientes de las gráficas suben a -0,14 V. El potencial de circuito abierto de los electrodos OPG/Co-Pc resultó ser independiente de la concentración de los disulfuros lo que indica que el potencial del electrodo modificado es sólo sensible al tiol. Los electrodos de grafito sin modificar frente a los tioles dan respuestas en potencial irreproducibles, lo que muestra la importancia de la presencia Co-Pc para obtener respuestas potenciométricas estables