Lúcia Brandão

Improvement of DMFC Electrode Kinetics by Using Nanohorns Catalyst Support

One of the factors limiting direct methanol fuel cells (DMFC) performance is the slow kinetics of methanol oxidation at the anode. The importance of the catalyst support for fuel cells has been recognized and different forms of carbon have been suggested. Single wall nanohorns (SWNH) are a new class of carbon with a similar graphitic structure of carbon nanotubes. They are self-assembling materials that produce aggregates of about 100 nm. In the present study, the comparison of the performance of a DMFC equipped with electrocatalysts supported on a commercial carbon black and on SWNH was carried out. The SWNH were synthesized by the arc discharge method in air. The deposition of the Pt and Pt/Ru catalysts on the carbon supports was accomplished by using ethylene glycol as reducing agent. The synthesized catalyst nanoparticles have a very small diameter size (ca. 2.5 nm) and they are uniformly distributed on both carbon supports. The supported electrode catalysts were tested in a DMFC and results indicate that employing SWNH is very promising showing catalytic activities 60 % higher.

Carbon Nanostructures Produced by an AC Arc Discharge

Carbon nanostructures are under deep investigation due their peculiar properties and possible applications. In particular, development of new methods for the synthesis of these materials and their mechanism of formation represent interesting research fields. Arc discharge allows to produce different forms of carbon nanostructures. The parameters involved in the process, voltage, current density, type and pressure of the surrounding gas can be controlled especially for achieving high quantity of material with enhanced characteristics in terms of purity while the use of transition metal-graphite mixtures has been used to produce single wall structures. Moreover direct current (DC) and alternating current (AC) are suitable for producing carbon nano-materials, but different results can be obtained. In this work the effect of the power frequency in an AC arc discharge technique on the synthesis of carbon nanostructures is reported. Pure graphite electrodes have been arched in air in an homemade apparatus where the material can be collected directly on a cylindrical collector fixed near the arc. In order to avoid the formation of deposits under the arc a symmetrical configuration of the electrodes has been set. The production of carbon soot containing Single Wall Nanohorns (SWNH) and highly convoluted graphene sheets is optimized. The range of power frequencies 32-1000Hz has been investigated and the arcs have been ignited fixing the voltage at 28 V. The materials has been analyzed by field emission scanning electron microscope and high resolution transmission electron microscope. The microstructure of the material synthesized by this apparatus is affected by the power frequency, as the experimental results demonstrate. The samples produced at low frequency presented high amounts of single wall structures, SWNH-type. More compact structures, similar to large onion-like structures, have been found in samples synthesized at high frequency values.

Autonomous electrochemical biosensors: A new vision to direct methanol fuel cells

A new approach to biosensing devices is demonstrated aiming an easier and simpler application in routine health care systems. Our methodology considered a new concept for the biosensor transducing event that allows to obtain, simultaneously, an equipment-free, user-friendly, cheap electrical biosensor. The use of the anode triple-phase boundary (TPB) layer of a passive direct methanol fuel cell (DMFC) as biosensor transducer is herein proposed. For that, the ionomer present in the anode catalytic layer of the DMFC is partially replaced by an ionomer with molecular recognition capability working as the biorecognition element of the biosensor. In this approach, fuel cell anode catalysts are modified with a molecularly imprinted polymer (plastic antibody) capable of protein recognition (ferritin is used as model protein), inserted in a suitable membrane electrode assembly (MEA) and tested, as initial proof-of-concept, in a non-passive fuel cell operation environment. The anchoring of the ionomer-based plastic antibody on the catalyst surface follows a simple one-step grafting from approach through radical polymerization. Such modification increases fuel cell performance due to the proton conductivity and macroporosity characteristics of the polymer on the TPB. Finally, the response and selectivity of the bioreceptor inside the fuel cell showed a clear and selective signal from the biosensor. Moreover, such pioneering transducing approach allowed amplification of the electrochemical response and increased biosensor sensitivity by 2 orders of magnitude when compared to a 3-electrodes configuration system.