Deactivation resistant PdSb/C catalysts for direct formic acid fuel cells

Formic acid oxidation at novel carbon supported PdSb alloy catalysts has been studied in a multi-anode direct formic acid fuel cell with supporting mechanistic studies in a conventional electrochemical cell. The optimized PdSb/C catalysts show better high voltage and long term performances than a comparable commercial Pd/C catalyst and much better resistance to poisoning (deactivation). Electrochemical stripping voltammograms show that the presence of Sb lowers the potential required for CO oxidation, and greatly decreases the accumulation of CO on the catalyst surface during formic acid oxidation.     

Ru oxide/carbon fabric composites for supercapacitors

Ru oxide/carbon fabric composites (Ru oxide/CF) were prepared by impregnating carbon fabric (CF) with a hydrous RuO₂ suspension. Their properties were characterized by scanning electron microscopy, impedance spectroscopy, cyclic voltammetry, and constant current discharging. Specific capacitance increased with increasing loading of Ru oxide. The apparent average specific capacitance of the Ru oxide component reached 1,085 F g⁻¹ for a 9.15% loading, with a peak of 1,984 F g⁻¹ at approximately 0.3 V vs Ag/AgCl. The presence of Ru oxide decreases the ionic resistance of the CF and appears to increase its specific capacitance by generating additional electroactive surface functionality.     

Mechanistic study of the deactivation of carbon supported Pd during formic acid oxidation

Palladium is an attractive anode catalyst for direct formic acid fuel cells (DFAFC) because of its high activity relative to Pt, but it suffers significant activity losses during operation of the DFAFC. The deactivation mechanism of a Pd/C catalyst during oxidation of formic acid has been studied by means of electrochemical stripping voltammetry. The stripping characteristics of the anode poison are virtually the same as those of adsorbed CO, and adsorbed CO has a similar poisoning effect. It is therefore proposed that a gradual build-up of adsorbed CO causes the deactivation of Pd in DFAFCs.     

Lingos, finite state machines, and fast similarity searching

We apply a recently published method of text-based molecular similarity searching (LINGO) to standard data sets for the purpose of quantifying the accuracy of the approach. Our implementation is based on a pattern-matching finite state machine (FSM) which results in fast search times. The accuracy of LINGO is demonstrated to be comparable to that of a path-based fingerprint and offers a simple yet effective method for similarity searching.     

The kinetics of charging and discharging of iridium oxide films in aqueous and non-aqueous media

Cyclic voltammetry and chronocoulometry have been used to investigate the kinetics of oxidation and reduction of electrochenucally generated Ir oxide films in H₂SO₄(aq), basic aqueous LiClO₄ solutions and LiClO₄ + acetonitrile solutions. In acidic aqueous solutions, the scan rate at which the main anodic peak potential begins to shift positively in cyclic voltammetry experiments has been used as a parameter to assess the charging and discharging kinetics of Ir oxide films grown under various conditions. In acidic and basic aqueous solutions, chronocoulometric measurements indicate that electron transport through the oxide is rate limiting for the main redox wave, whereas ion transport probably limits the charging/discharging kinetics in LiClO₄ + CH₃CN solutions. In this non-aqueous medium, it appears that ca. 35% of the oxide sites charge and discharge approximately an order of magnitude more rapidly than the remaining sites.     

Electron transport in conjugated metallopolymers

Superexchange interactions between metal centers coordinated to various conjugated polymer backbones have been shown to enhance the rate of electron transport through the polymer. Results for Ru and Os bipyridine moieties complexed to polybenzimidzoles and poly(bithiophene-co-bithiazole)s are reviewed. The evidence for superexchange mediated electron transport, and the factors that influence the rate of electron hopping between metal centers, are discussed.     

An analysis of dynamic linear response properties at RPA level

A separation of the dynamic linear response is developed, which distinguishes between the one- and two-electron contributions to the molecular response, by partitioning the RPA equation. The derivation of the partitioning is given in both an RPA , equation of motion, type approach and using the alternative, but equivalent, density matrix method. Three physically distinct contributions are obtained, called the direct, interaction, and back contributions. The direct term is composed entirely of one-electron effects, while the interaction and back terms account for the electron-interaction contributions to the response. Results for the dynamic dipole polarizability suggest that while the one-electron contribution is dominant in the zero-frequency limit, the two-electron contribution becomes increasingly important as the frequency of the perturbation increases. This implies that approximation of the linear response by only one-electron contributions is acceptable for the static case, but is less relevant for the dynamic case. The ramifications of this observation, for the scaling of sum-over-states-type calculations of large molecular systems, is briefly discussed, as is the application of our partitioning method to the higher polarizabilities. © 1995 John Wiley & Sons, Inc.     

Generalized overlap amplitudes and transition spin-orbitals

The generalized overlap amplitude for a direct ionization process is identified with a renormalized transition spin-orbital thus providing a computational scheme for the former and an interpretation for the latter.     

A fluorescence lifetime-based fibre-optic glucose sensor using glucose/galactose-binding protein

Alternative, non-electrochemistry-based technologies for continuous glucose monitoring are needed for eventual use in diabetes mellitus. As part of a programme investigating fluorescent glucose sensors, we have developed fibre-optic biosensors using glucose/galactose binding protein (GBP) labelled with the environmentally sensitive fluorophore, Badan. GBP-Badan was attached via an oligohistidine-tag to the surface of Ni-nitrilotriacetic acid (NTA)-functionalized agarose or polystyrene beads. Fluorescence lifetime increased in response to glucose, observed by fluorescence lifetime imaging microscopy of the GBP-Badan-beads. Either GBP-Badan agarose or polystyrene beads were loaded into a porous chamber at the end of a multimode optical fibre. Fluorescence lifetime responses were recorded using pulsed laser excitation, high speed photodiode detection and time-correlated single-photon counting. The maximal response was at 100 mM glucose with an apparent K(d) of 13 mM (agarose) and 20 mM (polystyrene), and good working-day stability was demonstrated. We conclude that fluorescence lifetime fibre-optic glucose sensors based on GBP-Badan are suitable for development as clinical glucose monitors.