Nafion-based composite electrolytes for proton exchange membrane fuel cells operating above 120C with titania nanoparticles and nanotubes as fillers

FAPESP:5150

Flow injection analysis of paracetamol using a biomimetic sensor as a sensitive and selective amperometric detector

This work describes the coupling of a biomimetic sensor to a flow injection system for the sensitive determination of paracetamol. The sensor was prepared as previously described in the literature (M. D. P. T. Sotomayor, A. Sigoli, M. R. V. Lanza, A. A. Tanaka and L. T. Kubota, J. Braz. Chem. Soc., 2008, 19, 734) by modifying a glassy carbon electrode surface with a Nafion (R) membrane doped with iron tetrapyridinoporphyrazine (FeTPyPz), a biomimetic catalyst of the P450 enzyme. The performance of the sensor for paracetamol detection was investigated and optimized in a flow injection system (FIA) using a wall jet electrochemical cell. Under optimized conditions a wide linear response range (1.0 x 10(-5) to 5.0 x 10(-2) mol L(-1)) was obtained, with a sensitivity of 2579 (+/- 129) mu A L mu mol(-1). The detection and quantification limits of the sensor for paracetamol in the FIA system were 1.0 and 3.5 mu mol L(-1), respectively. The analytical frequency was 51 samples h(-1), and over a period of five days (320 determinations) the biosensor maintained practically the same response. The system was successfully applied to paracetamol quantification in seven pharmaceutical formulations and in water samples from six rivers in Sao Paulo State, Brazil.

A novel electrocatalyst support with proton conductive properties for polymer electrolyte membrane fuel cell applications

The objective of this study is to graft the Surface of carbon black, by chemically introducing polymeric chains (Nafion (R) like) with proton-conducting properties. This procedure aims for a better interaction of the proton-conducting phase with the metallic catalyst particles, as well as hinders posterior support particle agglomeration. Also loss of active surface call be prevented. The proton conduction between the active electrocatalyst site and the Nafion (R) ionomer membrane should be enhanced, thus diminishing the ohmic drop ill the polymer electrolyte membrane fuel cell (PEMFC). PtRu nanoparticles were supported on different carbon materials by the impregnation method and direct reduction with ethylene glycol and characterized using amongst others FTIR, XRD and TEM. The screen printing technique was used to produce membrane electrode assemblies (MEA) for single cell tests in H(2)/air(PEMFC) and methanol operation (DMFC). In the PEMFC experiments, PtRu supported on grafted carbon shows 550 mW cm(-2) gmetal(-1) power density, which represents at least 78% improvement in performance, compared to the power density of commercial PtRu/C ETEK. The DMFC results of the grafted electrocatalyst achieve around 100% improvement. The polarization Curves results clearly show that the main Cause of the observed effect is the reduction in ohmic drop, caused by the grafted polymer. (C) 2009 Elsevier B.V. All rights reserved.

Functionalisation of nanoparticles as electrolytes in fuel cells

Inorganic metal oxide materials are generally poor proton conductors as conductivities are lower than 10-5-10-6 S.cm-1. However, by functionalising Silica, Zirconia or Titania, proton conduction increases by up to 5 orders of magnitude. Hence, functionalised nanomaterials are becoming very competitive against conventional electrolyte materials such as Nafion. In this work, sol-gel processes are employed to produce silica phosphate, zirconia phosphate and titania phosphate functionalised nanoparticles. Furthermore, conductivities at hydrate conditions are investigated, and nanoparticle formation and functionalisation effects on proton conductivity are discussed. Results show conductivities up to 10-1 S.cm-1 (95% RH). Proton conduction increases with the functionalisation content, however heat treatment of nanoparticles locks the functionality in the crystal phase, thus inhibiting proton conduction. Controlling the mesopore phase allows for high proton conduction at hydrated conditions, clearly indicating facilitated ion transport through the pore channels.

Nanocomposite Polymer Electrolyte Membranes: Methanol Crossover and Conductivity

Commercial Nafion® 117 membranes were successfully modified by in-situ reactions (sol-gel of TEOS and/or polymerization of aniline) within Nafion structures. Water-methanol permeability and proton conductivity were investigated in order to determine the potential performance of these membranes for DMFC systems. Silica-polyaniline modification resulted in 84% methanol crossover reduction, from 2.45x10^-5 cm2.s^-1 for conventional Nafion membranes to 3.71x10^-6 cm2.s^-1 for the modified silica-polyaniline composite membrane at 75 degrees C. In addition, conductivity was not hindered, as the polyaniline-Nafion membrane increased from 12.2 to 15 mS.cm^-1 as compared to Nafion, while a reduction of 11% was observed for silica-polyaniline-Nafion composite membrane. The results in this work strongly suggest the potential of polyaniline nanocomposites to enhance the performance of DMFCs.

Embracing ligands. A synthetic strategy towards new nitrogen-thioether multidentate ligands and characterization of the cobalt(III) complexes

The synthesis of the hexadentate ligand 2,2,9,9-tetra(methyleneamine)-4,7-dithiadecane (EtN(4)S(2)amp) is reported. The ligand is of a type in which bifurcations of the chain occur at atoms other than donor atoms. The cobalt(III) complex [Co(EtN(4)S(2)amp)](3+) (1) was isolated and characterized. The synthetic methodology also results in a number of by-products, notably 2,9,9-tris(methyleneamine)-9-methylenehydroxy-4,7-dithiadecane (Et(HO)N(3)S(2)amp) and an eleven-membered pendant arm macrocyclic ligand 6,10-dimethyl-6,10-bis(methyleneamine)-1,4-dithia-8-azaacycloundec-7- ene (dmatue). The complexes [Co(Et(HO)N(3)S(2)amp)](3+) (2), in which the alcohol is coordinated to the metal ion, and [Co(dmatue)Cl](2+) (4) were isolated and characterized. Et(HO)N(3)S(2)amp also undergoes complexation with cobalt(III) to produce two isomers endo-[Co(Et(HO) N(3)S(2)amp)Cl](2+) (endo-3) and exo-[Co(Et(HO) N(3)S(2)amp)Cl](2+) (exo-3), both with an uncoordinated alcohol group. endo- 3 has the alcohol positioned cis, and exo-3 trans, to the sixth metal coordination site. Reaction of 1 with isobutyraldehyde, paraformaldehyde and base in dimethylformamide results in the encapsulated complex [Co(1,5,5,9,13,13-hexamethyl-18,21-dithia-3,7,11,15-tetraazabicyclo[7.7.6]docosa- 3,14-diene)](ClO4)(3) . 2H(2)O ([Co(Me(6)docosadieneN(4)S(2))](3+) ( 5). All complexes have been characterized by single crystal X-ray study. The low-temperature (11 K) absorption spectrum of 1 has been measured in Nafion films with spin-allowed (1)A(1g) --> T-1(1g) and (1)A(1g) --> T-1(2g) and spin forbidden (1)A(1g) --> T-3(1g) and (1)A(1g) --> T-3(2g) bands observed. The octahedral ligand-field parameters were determined (10Dq = 22570 cm(-1), B = 551 cm(-1); C = 3500 cm(-1)). For 5 10Dq and B were determined (20580 cm(-1); 516 cm(-1), respectively) and compared with those for similar expanded cavity complexes [Co(Me(8)tricosatrieneN(6))](3+) and [Co(Me(5)tricosatrieneN(6))](3+).