Ti mesh anodes prepared by electrochemical deposition for the direct methanol fuel cell

An anode structure based on Ti mesh has been developed for the direct methanol fuel cell (DMFC). This new anode was prepared by electrochemical deposition of a ~ 3 µ m PtRu catalyst layer on ~ 50 µ m Ti mesh. It has a thinner structure compared to that of a porous carbon-based conventional anode. The Ti mesh anode shows a performance comparable to, and exceeding that, of the conventional anode in a DMFC operating with 0.25 or 0.5 M methanol solution and atmosphere oxygen at 90 C. However, it shows a lower performance of the cell when higher concentrations of methanol was employed. This may be attributed to its thin and open structure, which could facilitate the transport of methanol from the flow field to the anode catalyst layer and carbon dioxide in the opposite direction. © 2006 International Association for Hydrogen Energy.

Electrooxidation of methanol in an alkaline fuel cell: determination of the nature of the initial adsorbate

It is essential to correctly determine the nature of the initial adsorbate in order to calculate the pathway for any given reaction. Recent literature provides conflicting information on the first step in the methanol decomposition pathway. This work sets out to establish what role the solution and the surface have to play in the initial adsorption-deprotonation process. Density functional theory (DFT) calculations, in combination with a cluster-continuum model approach are used to resolve the nature of the adsorbing species. We show that methanol is the dominant species in solution over methoxide, and also has a smaller barrier to adsorption. The nature of the surface species is revealed to be a methanol-OH complex.

The Role of Water and Adsorbed Hydroxyls on Ethanol Electrochemistry on Pd: New Mechanism, Active Centers and Energetics for Direct Ethanol Fuel Cell Running in Alkaline Medium

First principles calculations with molecular dynamics are
utilized to simulate a simplified electrical double layer formed in the
active electric potential region during the electrocatalytic oxidation of
ethanol on Pd electrodes running in an alkaline electrolyte. Our
simulations provide an atomic level insight into how ethanol oxidation
occurs in fuel cells: New mechanisms in the presence of the simplified
electrical double layer are found to be different from the traditional
ones; through concerted-like dehydrogenation paths, both acetaldehyde
and acetate are produced in such a way as to avoid a variety of
intermediates, which is consistent with the experimental data obtained
from in situ FTIR spectroscopy. Our work shows that adsorbed OH on
the Pd electrode rather than Pd atoms is the active center for the
reactions; the dissociation of the C−H bond is facilitated by the
adsorption of an OH− anion on the surface, resulting in the formation
of water. Our calculations demonstrate that water dissociation rather than H desorption is the main channel through which
electrical current is generated on the Pd electrode. The effects of the inner Helmholtz layer and the outer Helmholtz layer are
decoupled, with only the inner Helmholtz layer being found to have a significant impact on the mechanistics of the reaction. Our
results provide atomic level insight into the significance of the simplified electrical double layer in electrocatalysis, which may be
of general importance.

The origin of high activity but low CO2 selectivity on binary PtSn in the direct ethanol fuel cell

The most active binary PtSn catalyst for direct ethanol fuel cell applications has been studied at 20 ^oC and 60 ^oC, using variable temperature electrochemical in-situ FTIR. In comparison with Pt, binary PtSn inhibits ethanol dissociation to CO(a), but promotes partial oxidation to acetaldehyde and acetic acid. Increasing the temperature from 20 ^oC to 60 ^oC facilitates both ethanol dissociation to CO(a) and their further oxidation to CO₂, leading to an increased selectivity towards CO₂; however, acetaldehyde and acetic acid are still the main products. Potential-dependent phase diagrams for surface oxidants of OH(a) formation on Pt(111), Pt(211) and Sn modified Pt(111) and Pt(211) surfaces have been determined using density functional theory (DFT) calculations. It is shown that Sn promotes the formation of OH(a) with a lower onset potential on the Pt(111) surface, whereas an increase in the onset potential is found on modification of the (211) surface. In addition, Sn inhibits the Pt(211) step edge with respect to ethanol C-C bond breaking compared with that found on the pure Pt, which reduces the formation of CO(a). Sn was also found to facilitate ethanol dehydrogenation and partial oxidation to acetaldehyde and acetic acid which, combined with the more facile OH(a) formation on the Pt(111) surface, gives us a clear understanding of the experimentally determined results. This combined electrochemical in-situ FTIR and DFT study, provides, for the first time, an insight into the long-term puzzling features of the high activity but low CO₂ production found on binary PtSn ethanol fuel cell catalysts.

Alkali Activated Fuel Ash and Slag Mixes:Optimization Study from Mortars to Concrete Building Blocks

Alkali activated binders, based on ash and slag, also known as geopolymers, can play a key role in reducing the carbon footprint of the construction sector by replacing ordinary Portland cement in some concretes. Since 1970s, research effort has been ongoing in many research institutions. In this study, pulverized fuel ash (PFA) from a UK power plant, ground granulated blast furnace slag (GGBS) and combinations of the two have been investigated as geopolymer binders for concrete applications. Activators used were sodium hydroxide and sodium silicate solutions. Mortars with sand/binder ratio of 2.75 with several PFA and GGBS combinations have been mixed and tested. The optimization of alkali dosage (defined as the Na2O/binder mass ratio) and modulus (defined as the Na2O/SiO2 mass ratio) resulted in strengths in excess of 70 MPa for tested mortars. Setting time and workability have been considered for the identification of the best combination of PFA/GGBS and alkali activator dosage for different precast concrete products. Geopolymer concrete building blocks have been replicated in laboratory and a real scale factory trial has been successfully carried out. Ongoing microstructural characterization is aiming to identify reaction products arising from PFA/GGBS combinations.

Improving fuel economy application of the organic Rankine Cycle on a hybrid bus

Globally vehicle operators are experiencing rising fuel costs and increased
running expenses as governments around the world attempt to decrease carbon dioxide emissions and fossil fuel consumption, due to global warming and the drive to reduce dependency on fossil fuels. Recent advances in hybrid vehicle design have made great strides towards more efficient operation, with regenerative braking being widely used to capture otherwise lost energy. In this paper a hybrid series bus is developed a step further, by installing another method of energy capture on the vehicle. In this case, it is in the form of the Organic Rankine Cycle (ORC). The waste heat expelled to the exhaust and coolant streams is recovered and converted to electrical energy which is then stored in the hybrid vehicles batteries. The electrical energy can then be used for the auxiliary power circuit or to assist in vehicle propulsion, thus reducing the load on the engine, thereby improving the overall fuel economy of the vehicle and reducing carbon dioxide emissions.

Development of a PtSn bimetallic catalyst for direct fuel cells using bio-butanol fuel

Pt and PtSn catalysts were studied for n-butanol electro-oxidation at various temperatures. PtSn showed a higher activity towards butanol electro-oxidation compared to Pt in acidic media. The onset potential for n-butanol oxidation on PtSn is ~520 mV lower than that found on Pt, and significantly lower activation energy was found for PtSn compared with that for Pt.