Pt-WO3 supported on carbon nanotubes as possible anodes for direct methanol fuel cells

The carbon nanotube (CNT) synthesised by the template carbonisation of polypyrrole on alumina membrane has been used as the support for Pt-WO₃, Pt-Ru, and Pt. These materials have been used as the electrodes for methanol oxidation in acid medium in comparison with E-TEK 20 wt% Pt and Pt-Ru on Vulcan XC72R carbon. The higher electrochemical surface of the carbon nanotube (as evaluated by cyclic voltammetry) has been effectively used to disperse the catalytic particles. The morphology of the supported and unsupported CNT has been characterised by scanning electron micrograph and high-resolution transmission electron micrograph. The particle size of Pt, Pt-Ru, and Pt-WO₃ loaded CNT was found to be 1.2, 2, and 5 nm, respectively. The X-ray photoelectron spectra indicated that Pt and Ru are in the metallic state and W is in the +VI oxidation state. The electrochemical activity of the methanol oxidation electrode has been evaluated using cyclic voltammetry. The activity and stability (evaluated from chronoamperometric response) of the electrodes for methanol oxidation follows the order: GC/CNT-Pt-WO₃-Nafion>GC/E-TEK 20% Pt-Ru/Vulcan Carbon-Nafion>GC/CNT-Pt-Nafion>GC/E-TEK 20% Pt/Vulcan carbon-Nafion>Bulk Pt. The amount of nitrogen in the CNT plays an important role as observed by the increase in activity and stability of methanol oxidation with N₂ content, probably due to the hydrophilic nature of the CNT.     

Synthesis of Pt and Pd nanosheaths on multi-walled carbon nanotubes as potential electrocatalysts of low temperature fuel cells

Pt and Pd nanosheaths are successfully synthesized on multi-walled carbon nanotubes (MWCNTs) using the non-covalent poly(diallyldimethylammonium chloride) (PDDA) functionalization and seed-mediated growth methods. In this method, negatively charged Pt or Pd metal precursors are self-assembled with positively charged PDDA-functionalized MWCNTs, forming uniformly distributed Pt or Pd nanoseeds on MWCNTs supports. The contiguous and highly porous Pt and Pd nanosheath structured catalysts are then formed by the seed-mediated growth in corresponding metal precursors using ascorbic acid as the reducing agent. The essential role of uniformly dispersed Pt and Pd nanoseeds on PDDA-MWCNTs is demonstrated. The results indicate that both Pt and Pd nanosheaths show an enhanced catalytic activity for the methanol and formic acid oxidation reaction in acid solution, respectively, as compared with conventional Pt/C and Pd/C catalysts. The enhanced activities are most likely due to the reduced oxophilicity, which results in a weakened chemisorption energy with oxygen-containing species such as CO_ad, and the increased reactive sites due to the large number of grain boundaries of the Pt and Pd nanosheath structured electrocatalysts.     

Nanocomposite electrodes based on pre-synthesized organically capped platinum nanoparticles and carbon nanotubes. Part I: Tuneable low platinum loadings, specific H upd feature and evidence for oxygen reduction

A bottom-up approach is used here to combine carbon nanotubes synthesized by CVD and organically capped platinum nanoparticles electrocatalyst exhibiting a direct electrochemical activity towards oxygen reduction. Both nano-objects are handled in liquid suspension and are associated together in a controlled way. The nanocomposite liquid dispersions can be precisely controlled in terms of platinum nanoparticles to carbon nanotubes weight ratios (NP/NT) which correspond to different coverages of nanotubes by nanoparticles. Electrodes with low to ultra-low platinum loadings can then be prepared on porous fuel cell carbon supports by filtration. The direct electrochemical activity towards aqueous oxygen reduction reaction (ORR) of electrodes with platinum loadings ranging from about 1 to 60 μg/cm² is reported without any activation step in order to keep the features of the nanoparticles intact. Before that, we studied the responses obtained when impregnating our hydrophobic electrodes by a voltamperometric gas consumption procedure. These responses are also dependent of the composition of our electrodes. Whereas our results are of particular interest with respect to the optimization of platinum loading in fuel cell electrodes, the specific behaviour of these capped platinum nanoparticles towards proton adsorption-desorption reveals the difficulty to determine reliable active surface area with related regard to the platinum loading and point to the necessity to determine other characteristic parameters for the electrodes.