On-line FTIR spectroscopic investigations of methanol oxidation in a direct methanol fuel cell

A real-time Fourier transform infrared spectroscopy (FTIRS) analysis of the products of methanol oxidation in a prototype direct-methanol fuel cell operating at high temperatures (150 to 185°C) is reported here. The methanol oxidation products on platinum black and platinum-ruthenium catalyst surfaces were determined as a function of the fuel cell operating temperature, current density, and methanol/water mole ratio. Neither formaldehyde nor formic acid was detected in anode exhaust gas at all cell operating conditions. The product distributions of methanol oxidation obtained by on-line FTIRS are consistent with our previous results obtained by on-line mass spectroscopy under similar conditions. With pure methanol in anode feed, methanaldimethylacetal was found to be the main product, methyl formate and CO were also found. However, when water was present in the anode feed, the main product was CO , and the formation of methanaldimethylacetal and methyl formate decreased significantly with increase of the water/methanol mole ratio. Increase of cell operating temperature enhanced the formation of CO and decreased the formation of methanaldimethylacetal and methyl formate. Pt/Ru catalyst is more active for methanol oxidation and has a higher selectivity toward CO formation than Pt-black. Nearly complete methanol oxidation, i.e., the product was almost exclusively CO , was achieved using a Pt/Ru catalyst and a water/methanol mole ratio of 2 or higher in the anode feed at a temperature of 185°C or above.

Trimethoxymethane as an alternative fuel for a direct oxidation PBI polymer electrolyte fuel cell

The oxidation of trimethoxymethane (TMM) (trimethyl orthoformate) in a direct oxidation PBI fuel cell was examined by on-line mass spectroscopy and on-line FTIR spectroscopy. The results show that TMM was almost completely hydrolyzed in a direct oxidation fuel cell which employs an acid doped polymer electrolyte to form a mixture of methylformate, methanol and formic acid. It also found that TMM was hydrolyzed in the presence of water at 120°C even without acidic catalyst. The anode performance improves in the sequence of methanol, TMM, formic acid/methanol, and methylformate solutions. Since formic acid is electrochemically more active than methanol, these results suggest that formic acid is probably a key factor for the improvement of the anode performance by using TMM instead of methanol under these conditions. © 1998 Elsevier Science Ltd. All rights reserved.

PtRuO/Ti anodes with a varying Pt:Ru ratio for direct methanol fuel cells

PtRuO/Ti anodes with a varying Pt:Ru ratio were prepared by thermal deposition of a PtRuO catalyst layer onto a Ti mesh for the direct methanol fuel cell (DMFC). The morphology and structure of the catalyst layers were analyzed by SEM, EDX, and XRD. The catalyst coating layers became porous with increase of the Ru content, and showed oxide and alloy characteristics. The relative activities of the PtRuO/Ti electrodes were assessed and compared using half-cell tests and single DMFC experiments. The results showed that these electrodes were very active for the methanol oxidation and that the optimum Ru surface coverage was ca. 38% for a DMFC operating at 20-60 °C. © 2006 Elsevier B.V. All rights reserved.

PtRu/Ti anodes with varying Pt:Ru ratio prepared by electrodeposition for the direct methanol fuel cell

PtRu/Ti anodes with varying Pt : Ru ratio were prepared by electrodeposition of a thin PtRu catalyst layer onto Ti mesh for a direct methanol fuel cell (DMFC). The morphology and structure of the catalyst layers were analyzed by SEM, EDX and XRD. The catalyst coating layer shows an alloy character. The relative activities of the PtRu/Ti electrodes were assessed and compared in half cell and single DMFC experiments. The results show that these electrodes are very active for the methanol oxidation and that the optimum Ru surface coverage was ca. 9 at.% for DMFC operating at 20°C and 11 at.% at 60°C. The PtRu/Ti anode shows a performance comparable to that of the conventional carbon-based anode in a DMFC operating with 0.25 M or 0.5 M methanol solution and atmosphere oxygen gas at 90°C. © the Owner Societies 2006.

Preparation and characterization of new anodes based on Ti mesh for direct methanol fuel cells

A novel anode structure based on Ti mesh for the direct methanol fuel cell (DMFC) has been prepared by thermal deposition of ~5 µm PtRuO2 catalyst layer on ~50 µm Ti mesh. The preparation procedures and the main characteristics of the anode were studied by half-cell testing, scanning electron microscopy analysis, energy-dispersive X-ray measurement, and single-cell testing. The optimum calcination temperature is 450°C, calcination time is 90- 120 min, PtRuO2 catalyst loading is 5.0 mg cm-2, Pt precursor concentration range of solution is 0.14- 0.4 M, and solution aging time is 1 day. The performances of the anodes prepared using the solution kept within 20 days showed no significant difference. When it was used in DMFC feed with low-concentration methanol solution at 90°C, this new anode shows better performance than that of the conventional anode, because its thin hydrophilic structure is a benefit to the transport of methanol and carbon dioxide. However, due to its opening structure, when higher concentration methanol was employed, the performance of the cell with new anode became worse. © 2006 The Electrochemical Society. All rights reserved.

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 effect of nozzle geometry on the flow characteristics of small water jets

A wide variety of processes make use of plain orifice nozzles. Fuel injectors for internal combustion engines incorporate these nozzles to generate finely atomized sprays. Processes such as jet cutting, jet cleaning, and hydroentanglement, on the other hand, use similar nozzles, but require coherent jets. The spray or jet characteristics depend on the stability of the flow emerging from the orifice. This problem has been extensively researched for nozzles with diameters above 300 μm. Much less is known about the characteristics of jets produced by nozzles with smaller diameters, where viscous effects and small geometric variations due to manufacturing tolerances are likely to play an increasing role. Results are presented of a wide-ranging investigation of geometry effects on the flow parameters and jet characteristics of nozzles with diameters between 120 and 170 μm. Nozzles with circular cross-section and conical, cone-capillary and capillary axial designs were investigated. For conical and cone-capillary nozzles, the effect of cone angle and effects due to interactions between adjacent nozzles in the multi-hole cone-capillary nozzles were studied. For capillary nozzles, the effects of diameter variations and inlet edge roundness for capillary nozzles were considered. Furthermore, the effect of varying the aspect ratio (ratio of major and minor axes) of elliptical nozzles was studied. Flowrate and jet impact force measurements were carried out to determine the discharge coefficient C, velocity coefficient C, and contraction coefficient C of the nozzles for supply pressures between 3 and 12 MPa. Visualizations of the jet flow were carried out in the vicinity of the nozzle exit in order to identify near-nozzle flow regimes and to study jet coherence. The relationship between nozzle geometry, discharge characteristics, and jet coherence is examined. © IMechE 2006.

Impact of nitrogen seeding on confinement and power load control of a high-triangularity JET ELMy H-mode plasma with a metal wall

This paper reports the impact on confinement and power load of the high-shape 2.5 MA ELMy H-mode scenario at JET of a change from all carbon plasma-facing components to an all metal wall. In preparation to this change, systematic studies of power load reduction and impact on confinement as a result of fuelling in combination with nitrogen seeding were carried out in JET-C and are compared with their counterpart in JET with a metallic wall. An unexpected and significant change is reported on the decrease in the pedestal confinement but is partially recovered with the injection of nitrogen.

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.