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.

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.

The electro-oxidations of methanol and formic acid at the Ru(0001) electrode as a function of temperature:In-situ FTIR studies

The electro-oxidations of methanol and formic acid at a Ru(0001) electrode in perchloric acid solution have been investigated as functions of temperature, potential and time using in-situ FTIR spectroscopy, and the results compared to those obtained during our previous studies on the adsorption and electro-oxidation of CO under the same conditions. It was found that no dissociative adsorption or electro-oxidation of methanol takes place at the Ru(0001) at potentials 1000 mV, the oxidation of formic acid to CO was significantly increased, and the oxidation of methanol to CO and methyl formate was observed, both of which were attributed to the formation of an active RuO phase on the Ru(0001) surface.

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.

A biogeography-based optimization algorithm with mutation strategies for model parameter estimation of solar and fuel cells

Mathematical models are useful tools for simulation, evaluation, optimal operation and control of solar cells and proton exchange membrane fuel cells (PEMFCs). To identify the model parameters of these two type of cells efficiently, a biogeography-based optimization algorithm with mutation strategies (BBO-M) is proposed. The BBO-M uses the structure of biogeography-based optimization algorithm (BBO), and both the mutation motivated from the differential evolution (DE) algorithm and the chaos theory are incorporated into the BBO structure for improving the global searching capability of the algorithm. Numerical experiments have been conducted on ten benchmark functions with 50 dimensions, and the results show that BBO-M can produce solutions of high quality and has fast convergence rate. Then, the proposed BBO-M is applied to the model parameter estimation of the two type of cells. The experimental results clearly demonstrate the power of the proposed BBO-M in estimating model parameters of both solar and fuel cells.

Investigation into the effect of molybdenum-site substitution on the performance of Sr2Fe1.5Mo0.5O6-δ for intermediate temperature solid oxide fuel cells

In this paper, niobium doping is evaluated as a means of enhancing the electrochemical performance of a Sr₂Fe_1.5Mo_0.5O_6-δ (SFM) perovskite structure cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs) applications. As the radius of Nb approximates that of Mo and exhibits +4/+5 mixed valences, its substitution is expected to improve material performance. A series of Sr₂Fe_1.5Mo_0.5-xNb_xO_6-δ (x = 0.05, 0.10, 0.15, 0.20) cathode materials are prepared and the phase structure, chemical compatibility, microstructure, electrical conductivity, polarization resistance and power generation are systematically characterized. Among the series of samples, Sr₂Fe_1.5Mo_0.4Nb_0.10O_6-δ (SFMNb_0.10) exhibits the highest conductivity value of 30 S cm^-1 at 550°C, and the lowest area specific resistance of 0.068 Ω cm² at 800°C. Furthermore, an anode-supported single cell incorporating a SFMNb_0.10 cathode presents a maximum power density of 1102 mW cm^-2 at 800°C. Furthermore no obvious performance degradation is observed over 15 h at 750°C with wet H₂(3% H₂O) as fuel and ambient air as the oxidant. These results demonstrate that SFMNb shows great promise as a novel cathode material for IT-SOFCs.

Methanol electro-oxidation on platinum modified tungsten carbides in direct methanol fuel cells: a DFT study

In exploration of low-cost electrocatalysts for direct methanol fuel cells (DMFCs), Pt modified tungsten carbide (WC) materials are found to be great potential candidates for decreasing Pt usage whilst exhibiting satisfactory reactivity. In this work, the mechanisms, onset potentials and activity for electrooxidation of methanol were studied on a series of Pt-modified WC catalysts where the bare W-terminated WC(0001) substrate was employed. In the surface energy calculations of a series of Pt-modified WC models, we found that the feasible structures are mono- and bi-layer Pt-modified WCs. The tri-layer Pt-modified WC model is not thermodynamically stable where the top layer Pt atoms tend to accumulate and form particles or clusters rather than being dispersed as a layer. We further calculated the mechanisms of methanol oxidation on the feasible models via methanol dehydrogenation to CO involving C-H and O-H bonds dissociating subsequently, and further CO oxidation with the C-O bond association. The onset potentials for the oxidation reactions over the Pt-modified WC catalysts were determined thermodynamically by water dissociation to surface OH* species. The activities of these Pt-modified WC catalysts were estimated from the calculated kinetic data. It has been found that the bi-layer Pt-modified WC catalysts may provide a good reactivity and an onset oxidation potential comparable to pure Pt and serve as promising electrocatalysts for DMFCs with a significant decrease in Pt usage.

Anodes for protonic ceramic fuel cells (PCFCs)

One of the more promising possibilities for future “green” electrical energy generation is the protonic ceramic fuel cell (PCFC). PCFCs offer a low-pollution technology to generate electricity electrochemically with high efficiency. Reducing the operating temperature of solid oxide fuel cells (SOFCs) to the 500-700°C range is desirable to reduce fabrication costs and improve overall longevity. This aim can be achieved by using protonic ceramic fuel cells (PCFCs) due to their higher electrolyte conductivity at these temperatures than traditional ceramic oxide-ion conducting membranes. This thesis deals with the state of the art Ni-BaZr0.85Y0.15O3-δ cermet anodes for PCFCs. The study of PCFCs is in its initial stage and currently only a few methods have been developed to prepare suitable anodes via solid state mechanical mixing of the relevant oxides or by combustion routes using nitrate precursors. This thesis aims to highlight the disadvantages of these traditional methods of anode preparation and to, instead, offer a novel, efficient and low cost nitrate free combustion route to prepare Ni-BaZr0.85Y0.15O3-δ cermet anodes for PCFCs. A wide range of techniques mainly X-ray diffraction (XRD), scanning electron microscopy (SEM), environmental scanning electron microscopy, (ESEM) and electrochemical impedance spectroscopy (EIS) were employed in the cermet anode study. The work also offers a fundamental examination of the effect of porosity, redox cycling behaviour, involvement of proton conducting oxide phase in PCFC cermet anodes and finally progresses to study the electrochemical performance of a state of the art anode supported PCFC. The polarisation behaviour of anodes has been assessed as a function of temperature (T), water vapour (pH2O), hydrogen partial pressures (pH2) and phase purity for electrodes of comparable microstructure. The impedance spectra generally show two arcs at high frequency R2 and low frequency R3 at 600 °C, which correspond to the electrode polarisation resistance. Work shows that the R2 and R3 terms correspond to proton transport and dissociative H2 adsorption on electrode surface, respectively. The polarization resistance of the cermet anode (Rp) was shown to be significantly affected by porosity, with the PCFC cermet anode with the lowest porosity exhibiting the lowest Rp under standard operating conditions. This result highlights that porogens are not required for peak performance in PCFC anodes, a result contrary to that of their oxide-ion conducting anode counterparts. In-situ redox cycling studies demonstrate that polarisation behaviour was drastically impaired by redox cycling. In-situ measurements using an environmental scanning electron microscopy (ESEM) reveal that degradation proceeds due to volume expansion of the Ni-phase during the re-oxidation stage of redox cycling.The anode supported thin BCZY44 based protonic ceramic fuel cell, formed using a peak performing Ni-BaZr0.85Y0.15O3-δ cermet anode with no porogen, shows promising results in fuel cell testing conditions at intermediate temperatures with good durability and an overall performance that exceeds current literature data.

Contribution of direct electron transfer mechanisms to overall electron transfer in microbial fuel cells utilising Shewanella oneidensis as biocatalyst

Objectives To investigate the contribution of direct electron transfer mechanisms to electricity production in microbial fuel cells by physically retaining Shewanella oneidensis cells close to or away from the anode electrode. Results A maximum power output of 114 ± 6 mWm−2 was obtained when cells were retained close to the anode using a dialysis membrane. This was 3.5 times more than when the cells were separated away from the anode. Without the membrane the maximum power output was 129 ± 6 mWm−2. The direct mechanisms of electron transfer contributed significantly to overall electron transfer from S. oneidensis to electrodes, a result that was corroborated by another experiment where S. oneidensis cells were entrapped in alginate gels. Conclusion S. oneidensis transfers electrons primarily by direct electron transfer as opposed to mediated electron transfer.

Large amplitude motions in the S1 state of formic acid /

A detailed theoretical investigation of the large amplitude motions in the S, excited electronic state of formic acid (HCOOH) was done. This study focussed on the the S, «- So electronic band system of formic acid (HCOOH). The torsion and wagging large amplitude motions of the S, were considered in detail. The potential surfaces were simulated using RHF/UHF ab-initio calculations for the two electronic states. The energy levels were evaluated by the variational method using free rotor basis functions for the torsional coordinates and harmonic oscillator basis functions for the wagging coordinates. The simulated spectrum was compared to the slit-jet-cooled fluorescence excitation spectrum allowing for the assignment of several vibronic bands. A rotational analysis of certain bands predicted that the individual bands are a mixture of rotational a, b and c-type components.The electronically allowed transition results in the c-type or Franck-Condon band and the electronically forbidden, but vibronically allowed transition creates the a/b-type or Herzberg-Teller components. The inversion splitting between these two band types differs for each band. The analysis was able to predict the ratio of the a, b and c-type components of each band.

Miniature Wulff-type generator for improving feed to fuel cells /|nT.-S. Tan. -- 260 St. Catharines, Ont. : [s. n.],

The original objective of this work was to provide a simple generator w.hich would produce hydrogen torLfuel-cell feed and which could be operated under remote or northern conditions. A secondary objective was to maximize the yield of hydrogen and carbon monoxide from available feed-stocks. A search of the patent literature has indicated that the concept of a small Wulff-type generator is essentially sound and that hydrogen may be recovered from a wide variety of hydrocarbon feed-stocks. A simple experimental set-up has been devised, patterned after ~~t originally used by R. G. Wulff for producing acetylene. This provides a supply of feed-stock, with or Without a carrier gas, which may be passed directly through a heated tube, which may contain a catalyst. A suitable procedure has been devised for analysi~ effluent gases for hydrogen, oxygen, nitrogen, methane and carbon monoxide by gas chromatography with the column packed with .Molecular .:>ieve .5 4. Athanol with air a.s carrier gas and at the same time as oxidant o was thermolyzed at temperatures in the ra~e 700-1100 C, with or Wi~lout catalyst. Methanol with or without nitrogen as a carrier gas was also cracked with • the same type of reactor refractory tube, but the temperature range was lower t down to ,300 " C when a catalyst was used. The problems of converting methane to hydrogen and carbon monoxide effiCiently, using air and/or water as oxidants were also studied.