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Sample records for direct methanol liquid

  1. The JPL Direct Methanol Liquid-feed PEM Fuel Cell

    Halpert, G.; Surampudi, S.

    1994-01-01

    Recently, there has been a breakthrough in fuel cell technology in the Energy Storage Systems Group at the Jet Propulsion Laboratory with the develpment of a direct methanol, liquid-feed, solid polymer electrolyte membrane (PEM) fuel cell... The methanol liquid-feed, solid polymer electrolyte (PEM) design has numerous system level advantages over the gas-feed design. These include:...

  2. Studies on Methanol Crossover in Liquid-Feed Direct Methanol Pem Fuel Cells

    Narayanan, S. R.

    1995-01-01

    The performance of liquid feed direct methanol fuel cells using various types of Nafion membranes as the solid polymer electrolyte have been studied. The rate of fuel crossover and electrical performance has been measured for cells with Nafion membranes of various thicknesses and equivalent weights. The crossover rate is found to decrease with increasing thickness and applied current. The dependence of crossover rate on current density can be understood in terms of a simple linear diffusion model which suggests that the crossover rate can be influenced by the electrode structure in addition to the membrane. The studies suggest that Nafion EW 1500 is a very promising alternate to Nafion EW 1100 for direct methanol fuel cells.

  3. Recent Studies on Methanol Crossover in Liquid-Feed Direct Methanol Fuel Cells

    Valdez, T. I.; Narayanan, S. R.

    2000-01-01

    In this work, the effects of methanol crossover and airflow rates on the cathode potential of an operating direct methanol fuel cell are explored. Techniques for quantifying methanol crossover in a fuel cell and for separating the electrical performance of each electrode in a fuel cell are discussed. The effect of methanol concentration on cathode potential has been determined to be significant. The cathode is found to be mass transfer limited when operating on low flow rate air and high concentrations of methanol. Improvements in cathode structure and operation at low methanol concentration have been shown to result in improved cell performance.

  4. The Direct Methanol Liquid-Feed Fuel Cell

    Halpert, Gerald

    1997-01-01

    Until the early 1990's the idea of a practical direct methanol fuel cell from transportation and other applications was just that, an idea. Several types of fuel cells that operate under near ambient conditions were under development.

  5. Performance of PEM Liquid-Feed Direct Methanol-Air Fuel Cells

    Narayanan, S. R.

    1995-01-01

    A direct methanol-air fuel cell operating at near atmospheric pressure, low-flow rate air, and at temperatures close to 60oC would tremendously enlarge the scope of potential applications. While earlier studies have reported performance with oxygen, the present study focuses on characterizing the performance of a PEM liquid feed direct methanol-air cell consisting of components developed in house. These cells employ Pt-Ru catalyst in the anode, Pt at the cathode and Nafion 117 as the PEM. The effect of pressure, flow rate of air and temperature on cell performance has been studied. With air, the performance level is as high as 0.437 V at 300 mA/cm2 (90oC, 20 psig, and excess air flow) has been attained. Even more significant is the performance level at 60oC, 1 atm and low flow rates of air (3-5 times stoichiometric), which is 0.4 V at 150 mA/cm2. Individual electrode potentials for the methanol and air electrode have been separated and analyzed. Fuel crossover rates and the impact of fuel crossover on the performance of the air electrode have also been measured. The study identifies issues specific to the methanol-air fuel cell and provides a basis for improvement strategies.

  6. Relating Direct Methanol Fuel Cell Performance to Measurements in a Liquid Half Cell

    Pedersen, Christoffer Mølleskov; Tynelius, Oskar; Lund-Olesen, Torsten

    2015-01-01

    Direct methanol fuel cells (DMFC) could act as a replacement for batteries in low power electronics. For instance, micro—DMFC’s could be used to power hearing instruments[1]. The power output of a DMFC is limited by the sluggish kinetics of both the methanol oxidation reaction (MOR) on the anode ...... Cells Bull. 2012 (2012) 12–16. doi:10.1016/S1464-2859(12)70367-X....

  7. Real-time monitoring of methanol concentration using a shear horizontal surface acoustic wave sensor for direct methanol fuel cell without reference liquid measurement

    Tada, Kyosuke; Nozawa, Takuya; Kondoh, Jun

    2017-07-01

    In recent years, there has been an increasing demand for sensors that continuously measure liquid concentrations and detect abnormalities in liquid environments. In this study, a shear horizontal surface acoustic wave (SH-SAW) sensor is applied for the continuous monitoring of liquid concentrations. As the SH-SAW sensor functions using the relative measurement method, it normally needs a reference at each measurement. However, if the sensor is installed in a liquid flow cell, it is difficult to measure a reference liquid. Therefore, it is important to establish an estimation method for liquid concentrations using the SH-SAW sensor without requiring a reference measurement. In this study, the SH-SAW sensor is installed in a direct methanol fuel cell to monitor the methanol concentration. The estimated concentration is compared with a conventional density meter. Moreover, the effect of formic acid is examined. When the fuel temperature is higher than 70 °C, it is necessary to consider the influence of liquid conductivity. Here, an estimation method for these cases is also proposed.

  8. On the effect of operating conditions in liquid-feed direct methanol fuel cells: A multiphysics modeling approach

    García-Salaberri, Pablo A.; Vera, Marcos

    2016-01-01

    A multiphysics model for liquid-feed Direct Methanol Fuel Cells is presented. The model accounts for two-dimensional (2D) across-the-channel anisotropic mass and charge transport in the anode and cathode Gas Diffusion Layers (GDLs), including the effect of GDL assembly compression and electrical contact resistances at the Bipolar Plate (BPP) and membrane interfaces. A one-dimensional (1D) across-the-membrane model is used to describe local species diffusion through the microporous layers, methanol/water crossover, proton transport, and electrochemical reactions, thereby coupling both GDL sub-models. The 2D/1D model is extended to the third dimension and supplemented with 1D descriptions of the flow channels to yield a 3D/1D + 1D model that is successfully validated. A parametric study is then conducted on the 2D/1D model to examine the effect of operating conditions on cell performance. The results show that an optimum methanol concentration exists that maximizes power output due to the trade-off between anode polarization and cathode mixed overpotential. For fixed methanol concentration, cell performance is largely affected by the oxygen supply rate, cell temperature, and liquid/gas saturation levels. There is also an optimal GDL compression due to the trade-off between ohmic and concentration losses, which strongly depends on BPP material and, more weakly, on the actual operating conditions. - Highlights: • A multiphysics model for liquid-feed DMFCs is presented. • GDL anisotropic transport, assembly compression, and ohmic contact resistances are considered. • The model is successfully validated against previous experimental data. • Optimum methanol concentrations, GDL compressions, and operating temperatures are reported. • Oxygen-starved conditions with spontaneous hydrogen evolution in the anode are also considered.

  9. Direct Methanol Fuel Cell, DMFC

    Amornpitoksuk, P.

    2003-09-01

    Full Text Available Direct Methanol Fuel Cell, DMFC is a kind of fuel cell using methanol as a fuel for electric producing. Methanol is low cost chemical substance and it is less harmful than that of hydrogen fuel. From these reasons it can be commercial product. The electrocatalytic reaction of methanol fuel uses Pt-Ru metals as the most efficient catalyst. In addition, the property of membrane and system designation are also effect to the fuel cell efficient. Because of low power of methanol fuel cell therefore, direct methanol fuel cell is proper to use for the energy source of small electrical devices and vehicles etc.

  10. Development of methanol evaporation plate to reduce methanol crossover in a direct methanol fuel cell

    Zhang, Ruiming

    This research focuses on methanol crossover reduction in direct methanol fuel cells (DMFC) through separating the methanol vapor from its liquid phase and feeding the vapor passively at low temperature range. Membrane electrode assemblies (MEAs) were fabricated by using commercial available membrane with different thickness at different anode catalyst loading levels, and tested under the operating conditions below 100°C in cell temperature and cathode exit open to ambient pressure. Liquid methanol transport from the anode through the membrane into cathode ("methanol crossover") is identified as one of the major efficiency losses in a DMFC. It is known that the methanol crossover rate in the vapor phase is much lower than in liquid phase. Vapor feed can be achieved by heating the liquid methanol to elevated temperatures (>100°C), but other issues limit the performance of the cell when operating above 100°C. High temperature membranes and much more active cathode catalyst structures are required, and a complex temperature control system must be employed. However, methanol vapor feed can also occur at a lower temperature range (evaporation through a porous body. The methanol crossover with this vapor feed mode is lower compared with the direct liquid methanol feed. A new method of using a methanol evaporation plate (MEP) to separate the vapor from its liquid phase to reduce the liquid methanol crossover at low temperature range is developed. A MEP plays the roles of liquid/vapor methanol phase separation and evaporation in a DMFC. The goal of this study is to develop a MEP with the proper properties to achieve high methanol phase separation efficiency and fast methanol evaporation rate over a wide range of temperature, i.e., from room temperature up to near boiling temperature (100°C). MEP materials were selected and characterized. MEPs made from three different types were tested extensively with different MEA and porous back layer configurations. The benefits of

  11. Design and Operation of an Electrochemical Methanol Concentration Sensor for Direct Methanol Fuel Cell Systems

    Narayanan, S. R.; Valdez, T. I.; Chun, W.

    2000-01-01

    The development of a 150-Watt packaged power source based on liquid feed direct methanol fuel cells is being pursued currently at the Jet propulsion Laboratory for defense applications. In our studies we find that the concentration of methanol in the fuel circulation loop affects the electrical performance and efficiency the direct methanol fuel cell systems significantly. The practical operation of direct methanol fuel cell systems, therefore, requires accurate monitoring and control of methanol concentration. The present paper reports on the principle and demonstration of an in-house developed electrochemical sensor suitable for direct methanol fuel cell systems.

  12. Recent Advances in High-Performance Direct Methanol Fuel Cells

    Narayanan, S. R.; Chun, W.; Valdez, T. I.; Jeffries-Nakamura, B.; Frank, H.; Surumpudi, S.; Halpert, G.; Kosek, J.; Cropley, C.; La Conti, A. B.; hide

    1996-01-01

    Direct methanol fuel cells for portable power applications have been advanced significantly under DARPA- and ARO-sponsored programs over the last five years. A liquid-feed, direct methanol fuel cell developed under these programs, employs a proton exchange membrane as electrolyte and operates on aqueous solutions of methanol with air or oxygen as the oxidant.

  13. Advances in direct oxidation methanol fuel cells

    Surampudi, S.; Narayanan, S. R.; Vamos, E.; Frank, H.; Halpert, G.; Laconti, Anthony B.; Kosek, J.; Prakash, G. K. Surya; Olah, G. A.

    1993-01-01

    Fuel cells that can operate directly on fuels such as methanol are attractive for low to medium power applications in view of their low weight and volume relative to other power sources. A liquid feed direct methanol fuel cell has been developed based on a proton exchange membrane electrolyte and Pt/Ru and Pt catalyzed fuel and air/O2 electrodes, respectively. The cell has been shown to deliver significant power outputs at temperatures of 60 to 90 C. The cell voltage is near 0.5 V at 300 mA/cm(exp 2) current density and an operating temperature of 90 C. A deterrent to performance appears to be methanol crossover through the membrane to the oxygen electrode. Further improvements in performance appear possible by minimizing the methanol crossover rate.

  14. Liquid methanol under a static electric field

    Cassone, Giuseppe, E-mail: giuseppe.cassone@impmc.upmc.fr [Sorbonne Universités, UPMC Univ Paris 06, UMR 7590, IMPMC, F-75005 Paris (France); CNRS, UMR 7590, IMPMC, F-75005 Paris (France); Università degli Studi di Messina, Dipartimento di Fisica e di Scienze della Terra, Contrada Papardo, 98166 Messina (Italy); CNR-IPCF, Viale Ferdinando Stagno d’Alcontres 37, 98158 Messina (Italy); Giaquinta, Paolo V., E-mail: paolo.giaquinta@unime.it [Università degli Studi di Messina, Dipartimento di Fisica e di Scienze della Terra, Contrada Papardo, 98166 Messina (Italy); Saija, Franz, E-mail: saija@ipcf.cnr.it [CNR-IPCF, Viale Ferdinando Stagno d’Alcontres 37, 98158 Messina (Italy); Saitta, A. Marco, E-mail: marco.saitta@impmc.upmc.fr [Sorbonne Universités, UPMC Univ Paris 06, UMR 7590, IMPMC, F-75005 Paris (France); CNRS, UMR 7590, IMPMC, F-75005 Paris (France)

    2015-02-07

    We report on an ab initio molecular dynamics study of liquid methanol under the effect of a static electric field. We found that the hydrogen-bond structure of methanol is more robust and persistent for field intensities below the molecular dissociation threshold whose value (≈0.31 V/Å) turns out to be moderately larger than the corresponding estimate obtained for liquid water. A sustained ionic current, with ohmic current-voltage behavior, flows in this material for field intensities above 0.36 V/Å, as is also the case of water, but the resulting ionic conductivity (≈0.40 S cm{sup −1}) is at least one order of magnitude lower than that of water, a circumstance that evidences a lower efficiency of proton transfer processes. We surmise that this study may be relevant for the understanding of the properties and functioning of technological materials which exploit ionic conduction, such as direct-methanol fuel cells and Nafion membranes.

  15. Methods of conditioning direct methanol fuel cells

    Rice, Cynthia; Ren, Xiaoming; Gottesfeld, Shimshon

    2005-11-08

    Methods for conditioning the membrane electrode assembly of a direct methanol fuel cell ("DMFC") are disclosed. In a first method, an electrical current of polarity opposite to that used in a functioning direct methanol fuel cell is passed through the anode surface of the membrane electrode assembly. In a second method, methanol is supplied to an anode surface of the membrane electrode assembly, allowed to cross over the polymer electrolyte membrane of the membrane electrode assembly to a cathode surface of the membrane electrode assembly, and an electrical current of polarity opposite to that in a functioning direct methanol fuel cell is drawn through the membrane electrode assembly, wherein methanol is oxidized at the cathode surface of the membrane electrode assembly while the catalyst on the anode surface is reduced. Surface oxides on the direct methanol fuel cell anode catalyst of the membrane electrode assembly are thereby reduced.

  16. Liquid-Feed Methanol Fuel Cell With Membrane Electrolyte

    Surampudi, Subbarao; Narayanan, S. R.; Halpert, Gerald; Frank, Harvey; Vamos, Eugene

    1995-01-01

    Fuel cell generates electricity from direct liquid feed stream of methanol/water solution circulated in contact with anode, plus direct gaseous feed stream of air or oxygen in contact with cathode. Advantages include relative simplicity and elimination of corrosive electrolytic solutions. Offers potential for reductions in size, weight, and complexity, and for increases in safety of fuel-cell systems.

  17. Fast Measurement of Methanol Concentration in Ionic Liquids by Potential Step Method

    Michael L. Hainstock

    2015-01-01

    Full Text Available The development of direct methanol fuel cells required the attention to the electrolyte. A good electrolyte should not only be ionic conductive but also be crossover resistant. Ionic liquids could be a promising electrolyte for fuel cells. Monitoring methanol was critical in several locations in a direct methanol fuel cell. Conductivity could be used to monitor the methanol content in ionic liquids. The conductivity of 1-butyl-3-methylimidazolium tetrafluoroborate had a linear relationship with the methanol concentration. However, the conductivity was significantly affected by the moisture or water content in the ionic liquid. On the contrary, potential step could be used in sensing methanol in ionic liquids. This method was not affected by the water content. The sampling current at a properly selected sampling time was proportional to the concentration of methanol in 1-butyl-3-methylimidazolium tetrafluoroborate. The linearity still stood even when there was 2.4 M water present in the ionic liquid.

  18. Numerical modelling of methanol liquid pool fires

    Prasad, Kuldeep; Li, Chiping; Kailasanath, K.; Ndubizu, Chuka; Ananth, Ramagopal; Tatem, P. A.

    1999-12-01

    The focus of this paper is on numerical modelling of methanol liquid pool fires. A mathematical model is first developed to describe the evaporation and burning of a two-dimensional or axisymmetric pool containing pure liquid methanol. Then, the complete set of unsteady, compressible Navier-Stokes equations for reactive flows are solved in the gas phase to describe the convection of the fuel gases away from the pool surface, diffusion of the gases into the surrounding air and the oxidation of the fuel into product species. Heat transfer into the liquid pool and the metal container through conduction, convection and radiation are modelled by solving a modified form of the energy equation. Clausius-Clapeyron relationships are invoked to model the evaporation rate of a two-dimensional pool of pure liquid methanol. The governing equations along with appropriate boundary and interface conditions are solved using the flux-corrected transport algorithm. Numerical results exhibit a flame structure that compares well with experimental observations. Temperature profiles and burning rates were found to compare favourably with experimental data from single- and three-compartment laboratory burners. The model predicts a puffing frequency of approximately 12 Hz for a 1 cm diameter methanol pool in the absence of any air co-flow. It is also observed that increasing the air co-flow velocity helps in stabilizing the diffusion flame, by pushing the vortical structures away from the flame region.

  19. Methanol, Ethanol and Propanol in EHD liquid bridging

    Fuchs, Elmar C; Wexler, Adam D; Agostinho, Luewton L F; Ramek, Michael; Woisetschläger, Jakob

    2011-01-01

    When a high-voltage direct-current is applied to two beakers filled with water or polar liquid dielectrica, a horizontal bridge forms between the two beakers. In this work such bridges made of methanol, ethanol, 1-propanol and 2-propanol are investigated with polarimetry and thermography. Whereas methanol, ethanol and 1-propanol bridges become warm like a water bridge, a 2-propanol bridge cools down relative to the surroundings. It is shown how the different stability of the primary and secondary alcoholate ions and the resulting small difference in conductivity between 1-propanol and 2-propanol is responsible for this novel effect.

  20. Modeling and Simulation of the Direct Methanol Fuel Cell

    Wohr, M.; Narayanan, S. R.; Halpert, G.

    1996-01-01

    From intro.: The direct methanol liquid feed fuel cell uses aqueous solutions of methanol as fuel and oxygen or air as the oxidant and uses an ionically conducting polymer membrane such as Nafion(sup r)117 and the electrolyte. This type of direct oxidation cell is fuel versatile and offers significant advantages in terms of simplicity of design and operation...The present study focuses on the results of a phenomenological model based on current understanding of the various processed operating in these cells.

  1. Improved Flow-Field Structures for Direct Methanol Fuel Cells

    Gurau, Bogdan [Nuvant Systems Inc., Crown Point, IN (United States)

    2013-05-31

    The direct methanol fuel cell (DMFC) is ideal if high energy-density liquid fuels are required. Liquid fuels have advantages over compressed hydrogen including higher energy density and ease of handling. Although state-of-the-art DMFCs exhibit manageable degradation rates, excessive fuel crossover diminishes system energy and power density. Although use of dilute methanol mitigates crossover, the concomitant lowering of the gross fuel energy density (GFED) demands a complex balance-of-plant (BOP) that includes higher flow rates, external exhaust recirculation, etc. An alternative approach is redesign of the fuel delivery system to accommodate concentrated methanol. NuVant Systems Inc. (NuVant) will maximize the GFED by design and assembly of a DMFC that uses near neat methanol. The approach is to tune the diffusion of highly concentrated methanol (to the anode catalytic layer) to the back-diffusion of water formed at the cathode (i.e. in situ generation of dilute methanol at the anode layer). Crossover will be minimized without compromising the GFED by innovative integration of the anode flow-field and the diffusion layer. The integrated flow-field-diffusion-layers (IFDLs) will widen the current and potential DMFC operating ranges and enable the use of cathodes optimized for hydrogen-air fuel cells.

  2. Methanol Oxidation on Pt3Sn(111) for Direct Methanol Fuel Cells: Methanol Decomposition.

    Lu, Xiaoqing; Deng, Zhigang; Guo, Chen; Wang, Weili; Wei, Shuxian; Ng, Siu-Pang; Chen, Xiangfeng; Ding, Ning; Guo, Wenyue; Wu, Chi-Man Lawrence

    2016-05-18

    PtSn alloy, which is a potential material for use in direct methanol fuel cells, can efficiently promote methanol oxidation and alleviate the CO poisoning problem. Herein, methanol decomposition on Pt3Sn(111) was systematically investigated using periodic density functional theory and microkinetic modeling. The geometries and energies of all of the involved species were analyzed, and the decomposition network was mapped out to elaborate the reaction mechanisms. Our results indicated that methanol and formaldehyde were weakly adsorbed, and the other derivatives (CHxOHy, x = 1-3, y = 0-1) were strongly adsorbed and preferred decomposition rather than desorption on Pt3Sn(111). The competitive methanol decomposition started with the initial O-H bond scission followed by successive C-H bond scissions, (i.e., CH3OH → CH3O → CH2O → CHO → CO). The Brønsted-Evans-Polanyi relations and energy barrier decomposition analyses identified the C-H and O-H bond scissions as being more competitive than the C-O bond scission. Microkinetic modeling confirmed that the vast majority of the intermediates and products from methanol decomposition would escape from the Pt3Sn(111) surface at a relatively low temperature, and the coverage of the CO residue decreased with an increase in the temperature and decrease in partial methanol pressure.

  3. Experimental investigation two phase flow in direct methanol fuel cells

    Mat, M. D.; Kaplan, Y.; Celik, S.; Oeztural, A.

    2007-01-01

    Direct methanol fuel cells (DMFC) have received many attentions specifically for portable electronic applications since it utilize methanol which is in liquid form in atmospheric condition and high energy density of the methanol. Thus it eliminates the storage problem of hydrogen. It also eliminates humidification requirement of polymeric membrane which is a problem in PEM fuel cells. Some electronic companies introduced DMFC prototypes for portable electronic applications. Presence of carbon dioxide gases due to electrochemical reactions in anode makes the problem a two phase problem. A two phase flow may occur at cathode specifically at high current densities due to the excess water. Presence of gas phase in anode region and liquid phase in cathode region prevents diffusion of fuel and oxygen to the reaction sites thus reduces the performance of the system. Uncontrolled pressure buildup in anode region increases methanol crossover through membrane and adversely effect the performance. Two phase flow in both anode and cathode region is very effective in the performance of DMYC system and a detailed understanding of two phase flow for high performance DMFC systems. Although there are many theoretical and experimental studies available on the DMFC systems in the literature, only few studies consider problem as a two-phase flow problem. In this study, an experimental set up is developed and species distributions on system are measured with a gas chromatograph. System performance characteristics (V-I curves) is measured depending on the process parameters (temperature, fuel ad oxidant flow rates, methanol concentration etc)

  4. Temperature dependence on mutual solubility of binary (methanol + limonene) mixture and (liquid + liquid) equilibria of ternary (methanol + ethanol + limonene) mixture

    Tamura, Kazuhiro; Li Xiaoli; Li Hengde

    2009-01-01

    Mutual solubility data of the binary (methanol + limonene) mixture at the temperatures ranging from 288.15 K close to upper critical solution temperature, and ternary (liquid + liquid) equilibrium (tie-lines) of the (methanol + ethanol + limonene) mixture at the temperatures (288.15, 298.15, and 308.15) K have been obtained. The experimental results have been represented accurately in terms of the extended and modified UNIQUAC models with binary parameters, compared with the UNIQUAC model. The temperature dependence of binary and ternary (liquid + liquid) equilibrium for the binary (methanol + limonene) and ternary (methanol + ethanol + limonene) mixtures could be calculated successfully using the extended and modified UNIQUAC model

  5. Selectivity of Direct Methanol Fuel Cell Membranes

    Antonino S. Aricò

    2015-11-01

    Full Text Available Sulfonic acid-functionalized polymer electrolyte membranes alternative to Nafion® were developed. These were hydrocarbon systems, such as blend sulfonated polyetheretherketone (s-PEEK, new generation perfluorosulfonic acid (PFSA systems, and composite zirconium phosphate–PFSA polymers. The membranes varied in terms of composition, equivalent weight, thickness, and filler and were investigated with regard to their methanol permeation characteristics and proton conductivity for application in direct methanol fuel cells. The behavior of the membrane electrode assemblies (MEA was investigated in fuel cell with the aim to individuate a correlation between membrane characteristics and their performance in a direct methanol fuel cell (DMFC. The power density of the DMFC at 60 °C increased according to a square root-like function of the membrane selectivity. This was defined as the reciprocal of the product between area specific resistance and crossover. The power density achieved at 60 °C for the most promising s-PEEK-based membrane-electrode assembly (MEA was higher than the benchmark Nafion® 115-based MEA (77 mW·cm−2 vs. 64 mW·cm−2. This result was due to a lower methanol crossover (47 mA·cm−2 equivalent current density for s-PEEK vs. 120 mA·cm−2 for Nafion® 115 at 60 °C as recorded at OCV with 2 M methanol and a suitable area specific resistance (0.15 Ohm cm2 for s-PEEK vs. 0.22 Ohm cm2 for Nafion® 115.

  6. Selectivity of Direct Methanol Fuel Cell Membranes.

    Aricò, Antonino S; Sebastian, David; Schuster, Michael; Bauer, Bernd; D'Urso, Claudia; Lufrano, Francesco; Baglio, Vincenzo

    2015-11-24

    Sulfonic acid-functionalized polymer electrolyte membranes alternative to Nafion(®) were developed. These were hydrocarbon systems, such as blend sulfonated polyetheretherketone (s-PEEK), new generation perfluorosulfonic acid (PFSA) systems, and composite zirconium phosphate-PFSA polymers. The membranes varied in terms of composition, equivalent weight, thickness, and filler and were investigated with regard to their methanol permeation characteristics and proton conductivity for application in direct methanol fuel cells. The behavior of the membrane electrode assemblies (MEA) was investigated in fuel cell with the aim to individuate a correlation between membrane characteristics and their performance in a direct methanol fuel cell (DMFC). The power density of the DMFC at 60 °C increased according to a square root-like function of the membrane selectivity. This was defined as the reciprocal of the product between area specific resistance and crossover. The power density achieved at 60 °C for the most promising s-PEEK-based membrane-electrode assembly (MEA) was higher than the benchmark Nafion(®) 115-based MEA (77 mW·cm(-2) vs. 64 mW·cm(-2)). This result was due to a lower methanol crossover (47 mA·cm(-2) equivalent current density for s-PEEK vs. 120 mA·cm(-2) for Nafion(®) 115 at 60 °C as recorded at OCV with 2 M methanol) and a suitable area specific resistance (0.15 Ohm cm² for s-PEEK vs. 0.22 Ohm cm² for Nafion(®) 115).

  7. Effect of pervaporation plate thickness on the rate of methanol evaporation in a passive vapor-feed direct methanol fuel cell

    Fauzi, N. F. I.; Hasran, U. A.; Kamarudin, S. K.

    2015-09-01

    In a passive vapor-feed direct methanol fuel cell (DMFC), methanol vapor is typically obtained using a pervaporation plate in a process by which liquid methanol contained in the fuel reservoir undergoes a phase change to vapor in the anodic vapor chamber. This work investigates the effect of pervaporation plate thickness on the rate of methanol evaporation using a three-dimensional simulation model developed by varying the plate thickness. A. The rate of methanol evaporation was measured using Darcy's law. The rate of methanol evaporation was found to be inversely proportional to the plate thickness, where the decrease in thickness inevitably lowers the resistance along the plate and consequently increases the methanol transport through the plate. This shows that the plate thickness has a significant influence on the rate of methanol evaporation and thereby plays an important role in improving the performance of the passive vapor-feed direct methanol fuel cell.

  8. Effect of pervaporation plate thickness on the rate of methanol evaporation in a passive vapor-feed direct methanol fuel cell

    Fauzi, N F I; Hasran, U A; Kamarudin, S K

    2015-01-01

    In a passive vapor-feed direct methanol fuel cell (DMFC), methanol vapor is typically obtained using a pervaporation plate in a process by which liquid methanol contained in the fuel reservoir undergoes a phase change to vapor in the anodic vapor chamber. This work investigates the effect of pervaporation plate thickness on the rate of methanol evaporation using a three-dimensional simulation model developed by varying the plate thickness. A. The rate of methanol evaporation was measured using Darcy's law. The rate of methanol evaporation was found to be inversely proportional to the plate thickness, where the decrease in thickness inevitably lowers the resistance along the plate and consequently increases the methanol transport through the plate. This shows that the plate thickness has a significant influence on the rate of methanol evaporation and thereby plays an important role in improving the performance of the passive vapor-feed direct methanol fuel cell. (paper)

  9. Effect of sorbed methanol, current, and temperature on multicomponent transport in nafion-based direct methanol fuel cells.

    Rivera, Harry; Lawton, Jamie S; Budil, David E; Smotkin, Eugene S

    2008-07-24

    The CO2 in the cathode exhaust of a liquid feed direct methanol fuel cell (DMFC) has two sources: methanol diffuses through the membrane electrode assembly (MEA) to the cathode where it is catalytically oxidized to CO2; additionally, a portion of the CO2 produced at the anode diffuses through the MEA to the cathode. The potential-dependent CO2 exhaust from the cathode was monitored by online electrochemical mass spectrometry (ECMS) with air and with H2 at the cathode. The precise determination of the crossover rates of methanol and CO2, enabled by the subtractive normalization of the methanol/air to the methanol/H2 ECMS data, shows that methanol decreases the membrane viscosity and thus increases the diffusion coefficients of sorbed membrane components. The crossover of CO2 initially increases linearly with the Faradaic oxidation of methanol, reaches a temperature-dependent maximum, and then decreases. The membrane viscosity progressively increases as methanol is electrochemically depleted from the anode/electrolyte interface. The crossover maximum occurs when the current dependence of the diffusion coefficients and membrane CO2 solubility dominate over the Faradaic production of CO2. The plasticizing effect of methanol is corroborated by measurements of the rotational diffusion of TEMPONE (2,2,6,6-tetramethyl-4-piperidone N-oxide) spin probe by electron spin resonance spectroscopy. A linear inverse relationship between the methanol crossover rate and current density confirms the absence of methanol electro-osmotic drag at concentrations relevant to operating DMFCs. The purely diffusive transport of methanol is explained in terms of current proton solvation and methanol-water incomplete mixing theories.

  10. Response of a direct methanol fuel cell to fuel change

    Leo, T.J. [Dpto de Sistemas Oceanicos y Navales- ETSI Navales, Univ. Politecnica de Madrid, Avda Arco de la Victoria s/n, 28040 Madrid (Spain); Raso, M.A.; de la Blanca, E. Sanchez [Dpto de Quimica Fisica I- Fac. CC. Quimicas, Univ. Complutense de Madrid, Avda Complutense s/n, 28040 Madrid (Spain); Navarro, E.; Villanueva, M. [Dpto de Motopropulsion y Termofluidodinamica, ETSI Aeronauticos, Univ. Politecnica de Madrid, Pza Cardenal Cisneros 3, 28040 Madrid (Spain); Moreno, B. [Instituto de Ceramica y Vidrio, Consejo Superior de Investigaciones Cientificas, C/Kelsen 5, Campus de la UAM, 28049 Cantoblanco, Madrid (Spain)

    2010-10-15

    Methanol and ethanol have recently received much attention as liquid fuels particularly as alternative 'energy-vectors' for the future. In this sense, to find a direct alcohol fuel cell that able to interchange the fuel without losing performances in an appreciable way would represent an evident advantage in the field of portable applications. In this work, the response of a in-house direct methanol fuel cell (DMFC) to the change of fuel from methanol to ethanol and its behaviour at different ambient temperature values have been investigated. A corrosion study on materials suitable to fabricate the bipolar plates has been carried out and either 316- or 2205-duplex stainless steels have proved to be adequate for using in direct alcohol fuel cells. Polarization curves have been measured at different ambient temperature values, controlled by an experimental setup devised for this purpose. Data have been fitted to a model taking into account the temperature effect. For both fuels, methanol and ethanol, a linear dependence of adjustable parameters with temperature is obtained. Fuel cell performance comparison in terms of open circuit voltage, kinetic and resistance is established. (author)

  11. Novel electrode structure for DMFC operated with liquid methanol

    Shao, Z.-G.; Lin, W.; Christensen, P.A.; Zhu, F.; Slowinski, G.; Amini, M.K.; Scott, K.

    2004-01-01

    'Full text:' Up to now, the electrodes for direct methanol fuel cell (DMFC) were developed mostly on the basis of the gas diffusion electrodes employed in proton exchange membrane fuel cells. Typically, the structure of such electrodes comprises a catalyst layer and a diffusion layer, the latter being carbon cloth or carbon paper. However, unlike other fuel cells, the liquid feed DMFC suffers from mass transport limitations predominantly at the anode due to the low diffusion coefficient of methanol in water. In addition, carbon paper is fragile and expensive and carbon cloth is soft compared with metal material, such materials are not as versatile as metals. In our present work, new structures of the anode and cathode have been developed. The preparation procedures and the main characteristics of the anodes and cathodes have been studied and will be reported. (author)

  12. Lightweight Stacks of Direct Methanol Fuel Cells

    Narayanan, Sekharipuram; Valdez, Thomas

    2004-01-01

    An improved design concept for direct methanol fuel cells makes it possible to construct fuel-cell stacks that can weigh as little as one-third as much as do conventional bipolar fuel-cell stacks of equal power. The structural-support components of the improved cells and stacks can be made of relatively inexpensive plastics. Moreover, in comparison with conventional bipolar fuel-cell stacks, the improved fuel-cell stacks can be assembled, disassembled, and diagnosed for malfunctions more easily. These improvements are expected to bring portable direct methanol fuel cells and stacks closer to commercialization. In a conventional bipolar fuel-cell stack, the cells are interspersed with bipolar plates (also called biplates), which are structural components that serve to interconnect the cells and distribute the reactants (methanol and air). The cells and biplates are sandwiched between metal end plates. Usually, the stack is held together under pressure by tie rods that clamp the end plates. The bipolar stack configuration offers the advantage of very low internal electrical resistance. However, when the power output of a stack is only a few watts, the very low internal resistance of a bipolar stack is not absolutely necessary for keeping the internal power loss acceptably low.

  13. Silicon Based Direct Methanol Fuel Cells

    Larsen, Jackie Vincent

    The purpose of this project has been to investigate and fabricate small scale Micro Direct Methanol Fuel Cells (μDMFC). They are investigated as a possible alternative for Zinc-air batteries in small size consumer devices such as hearing aids. In such devices the conventional rechargeable batteries...... such as lithium-ion batteries have insufficiently low energy density. Methanol is a promising fuel for such devices due to the high energy density and ease of refueling compared to charging batteries, making μDMFC a suitable replacement energy source. In this Ph.D. dissertation, silicon micro fabrication...... techniques where utilized to build μDMFCs with the purpose of engineering the structures, both on the micro and nano scales in order to realize a high level of control over the membrane and catalyst components. The work presents four different monolithic fuel cell designs. The primary design is based...

  14. Micropump Fuel Mix Control for Novel Miniature Direct Methanol Fuel Cells, Phase I

    National Aeronautics and Space Administration — The Energies and Power Densities of Direct Methanol Fuel Cells (DMFCs) are limited by the size and weight associated with the liquid pump, which must circulate the...

  15. Improved Direct Methanol Fuel Cell Stack

    Wilson, Mahlon S.; Ramsey, John C.

    2005-03-08

    A stack of direct methanol fuel cells exhibiting a circular footprint. A cathode and anode manifold, tie-bolt penetrations and tie-bolts are located within the circular footprint. Each fuel cell uses two graphite-based plates. One plate includes a cathode active area that is defined by serpentine channels connecting the inlet and outlet cathode manifold. The other plate includes an anode active area defined by serpentine channels connecting the inlet and outlet of the anode manifold, where the serpentine channels of the anode are orthogonal to the serpentine channels of the cathode. Located between the two plates is the fuel cell active region.

  16. Development of new membrane materials for direct methanol fuel cells

    Yildirim, M.H.

    2009-01-01

    Development of new membrane materials for direct methanol fuel cells Direct methanol fuel cells (DMFCs) can convert the chemical energy of a fuel directly into electrical energy with high efficiency and low emission of pollutants. DMFCs can be used as the power sources to portable electronic devices

  17. Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

    Zhu, Yimin; Zelenay, Piotr

    2006-03-21

    A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of a platinum-chromium alloy so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

  18. Integrated anode structure for passive direct methanol fuel cells with neat methanol operation

    Wu, Huijuan; Zhang, Haifeng; Chen, Peng; Guo, Jing; Yuan, Ting; Zheng, Junwei; Yang, Hui

    2014-02-01

    A microporous titanium plate based integrated anode structure (Ti-IAS) suitable for passive direct methanol fuel cells (DMFCs) fueled with neat methanol is reported. This anode structure incorporates a porous titanium plate as a methanol mass transfer barrier and current collector, pervaporation film for passively vaporizing methanol, vaporous methanol cavity for evenly distributing fuel, and channels for carbon dioxide venting. With the effective control of methanol delivery rate, the Ti-IAS based DMFC allows the direct use of neat methanol as the fuel source. In the meantime, the required water for methanol-oxidation reaction at the anode can also be fully recovered from the cathode with the help of the highly hydrophobic microporous layer in the cathode. DMFCs incorporating this new anode structure exhibit a power density as high as 40 mW cm-2 and a high volumetric energy density of 489 Wh L-1 operating with neat methanol and at 25 °C. Importantly, no obvious performance degradation of the passive DMFC system is observed after more than 90 h of continuous operation. The experimental results reveal that the compact DMFC based on the Ti-IAS exhibits a substantial potential as power sources for portable applications.

  19. Review on utilization of the pervaporation membrane for passive vapor feed direct methanol fuel cell

    Fauzi, N F I; Hasran, U A; Kamarudin, S K

    2013-01-01

    The Direct Methanol Fuel Cell (DMFC) is a promising portable power source for mobile electronic devices because of its advantages including easy fuel storage, high energy density, low temperature operation and compact structure. In DMFC, methanol is used as a fuel source where it can be fed in liquid or vapor phase. However, the vapor feed DMFC has an advantage over the liquid feed system as it has the potential to have a higher operating temperature to increase the reaction rates and power outputs, to enhance the mass transfers, to reduce methanol crossover, reliable for high methanol concentration and it can increase the fuel cell performance. Methanol vapor can be delivered to the anode by using a pervaporation membrane, heating the liquid methanol or another method that compatible. Therefore, this paper is a review on vapor feed DMFC as a better energy source than liquid feed DMFC, the pervaporation membrane used to vaporize methanol feed from the reservoir and its applications in vapor feed DMFC

  20. Power generation in fuel cells using liquid methanol and hydrogen peroxide

    Narayanan, Sekharipuram R. (Inventor); Valdez, Thomas I. (Inventor); Chun, William (Inventor)

    2002-01-01

    The invention is directed to an encapsulated fuel cell including a methanol source that feeds liquid methanol (CH.sub.3 OH) to an anode. The anode is electrical communication with a load that provides electrical power. The fuel cell also includes a hydrogen peroxide source that feeds liquid hydrogen peroxide (H.sub.2 O.sub.2) to the cathode. The cathode is also in communication with the electrical load. The anode and cathode are in contact with and separated by a proton-conducting polymer electrolyte membrane.

  1. A selective electrocatalyst-based direct methanol fuel cell operated at high concentrations of methanol.

    Feng, Yan; Liu, Hui; Yang, Jun

    2017-06-01

    Owing to the serious crossover of methanol from the anode to the cathode through the polymer electrolyte membrane, direct methanol fuel cells (DMFCs) usually use dilute methanol solutions as fuel. However, the use of high-concentration methanol is highly demanded to improve the energy density of a DMFC system. Instead of the conventional strategies (for example, improving the fuel-feed system, membrane development, modification of electrode, and water management), we demonstrate the use of selective electrocatalysts to run a DMFC at high concentrations of methanol. In particular, at an operating temperature of 80°C, the as-fabricated DMFC with core-shell-shell Au@Ag 2 S@Pt nanocomposites at the anode and core-shell Au@Pd nanoparticles at the cathode produces a maximum power density of 89.7 mW cm -2 at a methanol feed concentration of 10 M and maintains good performance at a methanol concentration of up to 15 M. The high selectivity of the electrocatalysts achieved through structural construction accounts for the successful operation of the DMFC at high concentrations of methanol.

  2. A selective electrocatalyst–based direct methanol fuel cell operated at high concentrations of methanol

    Feng, Yan; Liu, Hui; Yang, Jun

    2017-01-01

    Owing to the serious crossover of methanol from the anode to the cathode through the polymer electrolyte membrane, direct methanol fuel cells (DMFCs) usually use dilute methanol solutions as fuel. However, the use of high-concentration methanol is highly demanded to improve the energy density of a DMFC system. Instead of the conventional strategies (for example, improving the fuel-feed system, membrane development, modification of electrode, and water management), we demonstrate the use of selective electrocatalysts to run a DMFC at high concentrations of methanol. In particular, at an operating temperature of 80°C, the as-fabricated DMFC with core-shell-shell Au@Ag2S@Pt nanocomposites at the anode and core-shell Au@Pd nanoparticles at the cathode produces a maximum power density of 89.7 mW cm−2 at a methanol feed concentration of 10 M and maintains good performance at a methanol concentration of up to 15 M. The high selectivity of the electrocatalysts achieved through structural construction accounts for the successful operation of the DMFC at high concentrations of methanol. PMID:28695199

  3. Characterisation of micro direct methanol fuel cells with silicon plate supported integrated ionomer membranes

    Larsen, Jackie Vincent; Dalslet, Bjarke Thomas; Kallesee, C.

    2013-01-01

    This work deals with the investigation and fabrication of Micro Direct Methanol Fuel Cells (μDMFC). They are investigated as a possible alternative for zinc-air batteries in small size consumer devices such as hearing aids. In such devices the conventional rechargeable batteries such as lithium......-ion batteries have insufficiently low energy density in the range 240 Wh/L to 300 Wh/L Methanol is a promising fuel for such devices due to the high energy density, with pure methanol having an energy density of 4400 Wh/L. Using a liquid fuel also allows refueling, which can be achieved much faster than battery...

  4. Towards neat methanol operation of direct methanol fuel cells: a novel self-assembled proton exchange membrane.

    Li, Jing; Cai, Weiwei; Ma, Liying; Zhang, Yunfeng; Chen, Zhangxian; Cheng, Hansong

    2015-04-18

    We report here a novel proton exchange membrane with remarkably high methanol-permeation resistivity and excellent proton conductivity enabled by carefully designed self-assembled ionic conductive channels. A direct methanol fuel cell utilizing the membrane performs well with a 20 M methanol solution, very close to the concentration of neat methanol.

  5. Environmental information volume: Liquid Phase Methanol (LPMEOH{trademark}) project

    NONE

    1996-05-01

    The purpose of this project is to demonstrate the commercial viability of the Liquid Phase Methanol Process using coal-derived synthesis gas, a mixture of hydrogen and carbon monoxide. This report describes the proposed actions, alternative to the proposed action, the existing environment at the coal gasification plant at Kingsport, Tennessee, environmental impacts, regulatory requirements, offsite fuel testing, and DME addition to methanol production. Appendices include the air permit application, solid waste permits, water permit, existing air permits, agency correspondence, and Eastman and Air Products literature.

  6. Environmental information volume: Liquid Phase Methanol (LPMEOH trademark) project

    1996-05-01

    The purpose of this project is to demonstrate the commercial viability of the Liquid Phase Methanol Process using coal-derived synthesis gas, a mixture of hydrogen and carbon monoxide. This report describes the proposed actions, alternative to the proposed action, the existing environment at the coal gasification plant at Kingsport, Tennessee, environmental impacts, regulatory requirements, offsite fuel testing, and DME addition to methanol production. Appendices include the air permit application, solid waste permits, water permit, existing air permits, agency correspondence, and Eastman and Air Products literature

  7. Sensing methanol concentration in direct methanol fuel cell with total harmonic distortion: Theory and application

    Mao Qing; Krewer, Ulrike

    2012-01-01

    The nonlinear frequency response of a direct methanol fuel cell (DMFC) is studied by analyzing the total harmonic distortion (THD) spectra. The dependence of the THD spectra on methanol concentration and methanol oxidation kinetics is investigated by means of both simulation and experiment. Simulation using a continuous stirred tank reactor network model suggests that the methanol concentration profile in the anode has a strong impact on the THD spectra. The experimentally observed nonlinear behavior of the DMFC anode can be qualitatively reproduced with a model containing a three-step methanol oxidation mechanism with Kauranen–Frumkin/Temkin kinetics. Both experiment and simulation results show that THD value has a monotonic correlation with methanol concentration at certain frequencies and its sensitivity to concentration is improved with increased current amplitude. The monotonic relationship enables the THD to sense the methanol concentration level by the DMFC itself, which is of mayor interest for the portable application as an external sensor for the system can be omitted.

  8. Isotopic quantum correction to liquid methanol at -30 C

    Benmore, C J; Egelstaff, P A; Neuefeind, J

    2002-01-01

    Hydrogen/deuterium (H/D) substitution of molecular liquids in neutron diffraction is a powerful tool for structure determination. However, recent high-energy X-ray studies have found observable differences in the structures of many H and D liquids at the same temperature. In some cases this isotopic quantum effect can be corrected for by measuring the D sample at a slightly different temperature to the H sample. The example of hydroxyl isotopic substitution in liquid methanol at -30 C is presented. The magnitude of the quantum effect is shown to be significant when compared to the size of the first-order isotopic neutron-difference function. (orig.)

  9. High performance direct methanol fuel cell with thin electrolyte membrane

    Wan, Nianfang

    2017-06-01

    A high performance direct methanol fuel cell is achieved with thin electrolyte membrane. 320 mW cm-2 of peak power density and over 260 mW cm-2 at 0.4 V are obtained when working at 90 °C with normal pressure air supply. It is revealed that the increased anode half-cell performance with temperature contributes primarily to the enhanced performance at elevated temperature. From the comparison of iR-compensated cathode potential of methanol/air with that of H2/air fuel cell, the impact of methanol crossover on cathode performance decreases with current density and becomes negligible at high current density. Current density is found to influence fuel efficiency and methanol crossover significantly from the measurement of fuel efficiency at different current density. At high current density, high fuel efficiency can be achieved even at high temperature, indicating decreased methanol crossover.

  10. Macroscopic Modeling of Transport Phenomena in Direct Methanol Fuel Cells

    Olesen, Anders Christian

    An increasing need for energy efficiency and high energy density has sparked a growing interest in direct methanol fuel cells for portable power applications. This type of fuel cell directly generates electricity from a fuel mixture consisting of methanol and water. Although this technology...... surpasses batteries in important areas, fundamental research is still required to improve durability and performance. Particularly the transport of methanol and water within the cell structure is difficult to study in-situ. A demand therefore exist for the fundamental development of mathematical models...... for studying their transport. In this PhD dissertation the macroscopic transport phenomena governing direct methanol fuel cell operation are analyzed, discussed and modeled using the two-fluid approach in the computational fluid dynamics framework of CFX 14. The overall objective of this work is to extend...

  11. Direct methanol feed fuel cell and system

    Surampudi, Subbarao (Inventor); Frank, Harvey A. (Inventor); Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Jeffries-Nakamura, Barbara (Inventor); Kindler, Andrew (Inventor); Halpert, Gerald (Inventor)

    2009-01-01

    Improvements to non acid methanol fuel cells include new formulations for materials. The platinum and ruthenium are more exactly mixed together. Different materials are substituted for these materials. The backing material for the fuel cell electrode is specially treated to improve its characteristics. A special sputtered electrode is formed which is extremely porous. The fuel cell system also comprises a fuel supplying part including a meter which meters an amount of fuel which is used by the fuel cell, and controls the supply of fuel based on said metering.

  12. Aerosol feed direct methanol fuel cell

    Kindler, Andrew (Inventor); Narayanan, Sekharipuram R. (Inventor); Valdez, Thomas I. (Inventor)

    2002-01-01

    Improvements to fuel cells include introduction of the fuel as an aerosol of liquid fuel droplets suspended in a gas. The particle size of the liquid fuel droplets may be controlled for optimal fuel cell performance by selection of different aerosol generators or by separating droplets based upon size using a particle size conditioner.

  13. Modelling and experimental studies on a direct methanol fuel cell working under low methanol crossover and high methanol concentrations

    Oliveira, V.B.; Pinto, A.M.F.R. [Centro de Estudos de Fenomenos de Transporte, Departamento de Eng. Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Rangel, C.M. [Instituto Nacional de Energia e Geologia, Fuel Cells and Hydrogen, Estrada do Paco do Lumiar, 1649-038 Lisboa (Portugal)

    2009-08-15

    A number of issues need to be resolved before DMFC can be commercially viable such as the methanol crossover and water crossover which must be minimised in portable DMFCs. The main gain of this work is to systematically vary commercial MEA materials and check their influence on the cell performance of a direct methanol fuel cell operating at close to room temperature. A detailed experimental study on the performance of an <> developed DMFC with 25 cm{sup 2} of active membrane area, working near the ambient conditions is described. Tailored MEAs (membrane-electrode assemblies), with different structures and combinations of gas diffusion layers (GDLs), were designed and tested in order to select optimal working conditions at high methanol concentration levels without sacrificing performance. The experimental polarization and power density curves were successfully compared with the predictions of a steady state, one-dimensional model accounting for coupled heat and mass transfer, along with the electrochemical reactions occurring in the DMFC recently developed by the same authors. The influence of the anode gas diffusion layer media, the membrane thickness and the MEA properties on the cell performance are explained under the light of the predicted methanol crossover rate across the membrane. A tailored MEA build-up with the common available commercial materials was proposed to achieve relatively low methanol crossover, operating at high methanol concentrations. The use of adequate materials for the gas diffusion layers (carbon paper at the anode GDL and carbon cloth at the cathode GDL) enables the use of thinner membranes enhancing the water back diffusion which is essential to work at high methanol concentrations. (author)

  14. Novel Materials for High Efficiency Direct Methanol Fuel Cells

    Carson, Stephen [Arkema Inc.; Mountz, David [Arkema Inc.; He, Wensheng [Arkema Inc.; Zhang, Tao [Arkema Inc.

    2013-12-31

    Direct methanol fuel cell membranes were developed using blends of different polyelectrolytes with PVDF. The membranes showed complex relationships between polyelectrolyte chemistry, morphology, and processing. Although the PVDF grade was found to have little effect on the membrane permselectivity, it does impact membrane conductivity and methanol permeation values. Other factors, such as varying the polyelectrolyte polarity, using varying crosslinking agents, and adjusting the equivalent weight of the membranes impacted methanol permeation, permselectivity, and areal resistance. We now understand, within the scope of the project work completed, how these inter-related performance properties can be tailored to achieve a balance of performance.

  15. Experimental analysis of methanol cross-over in a direct methanol fuel cell

    Casalegno, Andrea [Dipartimento di Energetica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy)]. E-mail: andrea.casalegno@polimi.it; Grassini, Paolo [Dipartimento di Energetica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy)]. E-mail: PGrassini@seal.it; Marchesi, Renzo [Dipartimento di Energetica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy)]. E-mail: renzo.marchesi@polimi.it

    2007-03-15

    Methanol cross-over through the polymeric membrane is one of the main causes limiting direct methanol fuel cell performances. It causes fuel wasting and enhances cathode overpotential. A repeatable and reproducible measurement system, that assures the traceability of the measurement to international reference standards, is necessary to compare different fuel cell construction materials. In this work a method to evaluate methanol cross-over rate and operating condition influence is presented and qualified in term of measurement uncertainty. In the investigated range, the methanol cross-over rate results mainly due to diffusion through the membrane, in fact it is strongly affected by temperature. Moreover the cross-over influence on fuel utilization and fuel cell efficiency is investigated. The methanol cross-over rate appears linearly proportional to electrochemical fuel utilization and values, obtained by measurements at different anode flow rate but constant electrochemical fuel utilization, are roughly equal; methanol wasting, due to cross-over, is considerable and can still be higher than electrochemical utilization. The fuel recirculation effect on energy efficiency has been investigated and it was found that fuel recirculation gives more advantage at low temperature, but fuel cell energy efficiency results are in any event higher at high temperature.

  16. Experimental analysis of methanol cross-over in a direct methanol fuel cell

    Casalegno, Andrea; Grassini, Paolo; Marchesi, Renzo

    2007-01-01

    Methanol cross-over through the polymeric membrane is one of the main causes limiting direct methanol fuel cell performances. It causes fuel wasting and enhances cathode overpotential. A repeatable and reproducible measurement system, that assures the traceability of the measurement to international reference standards, is necessary to compare different fuel cell construction materials. In this work a method to evaluate methanol cross-over rate and operating condition influence is presented and qualified in term of measurement uncertainty. In the investigated range, the methanol cross-over rate results mainly due to diffusion through the membrane, in fact it is strongly affected by temperature. Moreover the cross-over influence on fuel utilization and fuel cell efficiency is investigated. The methanol cross-over rate appears linearly proportional to electrochemical fuel utilization and values, obtained by measurements at different anode flow rate but constant electrochemical fuel utilization, are roughly equal; methanol wasting, due to cross-over, is considerable and can still be higher than electrochemical utilization. The fuel recirculation effect on energy efficiency has been investigated and it was found that fuel recirculation gives more advantage at low temperature, but fuel cell energy efficiency results are in any event higher at high temperature

  17. Reactivity descriptors for direct methanol fuel cell anode catalysts

    Ferrin, Peter; Nilekar, Anand Udaykumar; Greeley, Jeff

    2008-01-01

    oxidation to CO2 are investigated: an indirect mechanism that goes through a CO intermediate and a direct mechanism where methanol is oxidized to CO2 without the formation of a CO intermediate. For the direct mechanism, we find that, because of CO poisoning, only a small current will result on all non......We have investigated the anode reaction in direct methanol fuel cells using a database of adsorption free energies for 16 intermediates on 12 close-packed transition metal surfaces calculated with periodic, self-consistent, density functional theory (DFT-GGA). This database, combined with a simple...... electrokinetic model of the methanol electrooxidation reaction, yields mechanistic insights that are consistent with previous experimental and theoretical studies on Pt, and extends these insights to a broad spectrum of other transition metals. In addition, by using linear scaling relations between...

  18. Structural Study of Reduced Graphene Oxide/ Polypyrrole Composite as Methanol Sensor in Direct Methanol Fuel Cell

    Mumtazah Atiqah Hassan; Siti Kartom Kamarudin; Siti Kartom Kamarudin

    2016-01-01

    Density functional theory (DFT) computations were performed on the optimized geometric and electronic properties of reduced graphene oxide/polypyrole (rGO/ PPy) composite in comparison with pure graphene and graphene oxide structures. Incorporation of both reduced GO (rGO) and PPy will form a good composite which have advantages from both materials such as good mechanical strength and excellent electrical conductivity. These composite would be very suitable in fabrication of methanol sensor in direct methanol fuel cell (DMFC). The HOMO-LUMO energy (eV) was also calculated. These computations provide a theoretical explanation for the good performance of rGO/ PPy composite as electrode materials in methanol sensor. (author)

  19. Comparison of the renewable transportation fuels, liquid hydrogen and methanol, with gasoline - energetic and economic aspects

    Specht, M.; Staiss, F.; Bandi, A.; Weimer, T.

    1998-01-01

    In this paper, the renewable energy vectors liquid hydrogen (LH 2 ) and methanol generated from atmospheric CO 2 are compared with the conventional crude oil-gasoline system. Both renewable concepts, liquid hydrogen and methanol, lead to a drastic CO 2 reduction compared to the fossil-based system. The comparison between the LH 2 and methanol vector for the transport sector shows nearly the same fuel cost and energy efficiency but strong infrastructure advantages for methanol. (author)

  20. Recent progresses in materials for the direct methanol fuel cell

    Lamy, C; Leger, J M [Centre National de la Recherche Scientifique (CNRS), 86 - Poitiers (France)

    1998-12-31

    Research programs are being conducted worldwide to develop a clean, zero emissions electric vehicle. However, even with the most advanced batteries, such as nickel/metal hydride, or lithium ion batteries, the driving range is limited and the recharging time is long. Only fuel cells which can convert chemical energy directly into electrical energy can compete with internal combustion engines. This paper reviewed the recent progress made in the development of a direct methanol fuel cell using the concept developed for the proton exchange membrane fuel cell (PEMFC). It was noted that the electrode materials, at the methanol anode and oxygen cathode need to be improved by using multifunctional electrocatalysts. The development of new temperature resistant proton exchange membranes with good ionic conductivity and low methanol cross-over, which resulted from the need to increase operating temperatures above 100 degrees C was also reviewed. 35 refs., 1 tab., 2 figs.

  1. Evaporation and condensation at a liquid surface. II. Methanol

    Matsumoto, Mitsuhiro; Yasuoka, Kenji; Kataoka, Yosuke

    1994-11-01

    The rates of evaporation and condensation of methanol under the vapor-liquid equilibrium condition at the temperature of 300 and 350 K are investigated with a molecular dynamics computer simulation. Compared with the argon system (reported in part I), the ratio of self-reflection is similar (˜10%), but the ratio of molecule exchange is several times larger than the argon, which suggests that the conventional assumption of condensation as a unimolecular process completely fails for associating fluids. The resulting total condensation coefficient is 20%-25%, and has a quantitative agreement with a recent experiment. The temperature dependence of the evaporation-condensation behavior is not significant.

  2. Directed line liquids

    Kamien, R.D.

    1992-01-01

    This thesis is devoted to the study of ensembles of dense directed lines. These lines are principally to be thought of as polymers, though they also have the morphology of flux lines in high temperature superconductors, strings of colloidal spheres in electrorheological fluids and the world lines of quantum mechanical bosons. The authors discuss how directed polymer melts, string-like formations in electrorheological and ferro-fluids, flux lines in high temperature superconductors and the world lines of quantum mechanical bosons all share similar descriptions. They study a continuous transition in all of these systems, and then study the critical mixing properties of binary mixtures of directed polymers through the renormalization group. They predict the exponents for a directed polymer blend consolute point and a novel two-phase superfluid liquid-gas critical point

  3. The Pore Structure of Direct Methanol Fuel Cell Electrodes

    Lund, Peter Brilner

    2005-01-01

    The pore structure and morphology of direct methanol fuel cell electrodes are characterized using mercury intrusion porosimetry and scanning electron microscopy. It is found that the pore size distributions of printed primer and catalyst layers are largely dictated by the powders used to make...

  4. On direct and indirect methanol fuel cells for transportation applications

    Gottesfield, S.

    1996-04-01

    Research on direct oxidation methanol fuel cells (DMFCs) and polymer electrolyte fuel cells (PEFCs) is discussed. Systems considered for transportation applications are addressed. The use of platinum/ruthenium anode electrocatalysts and platinum cathode electrocatalysts in polymer electrolyte DMFCs has resulted in significant performance enhancements.

  5. Mixed ionic liquids/graphene-supported platinum nanoparticles as an electrocatalyst for methanol oxidation

    Shi, Guoyu; Wang, Zonghua; Xia, Jianfei; Bi, Sai; Li, Yue; Zhang, Feifei; Xia, Lin; Li, Yanhui; Xia, Yanzhi; Xia, Linhua

    2014-01-01

    Graphical abstract: A kind of mixed ionic liquids (ILs) of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4], IL1) and hexafluorophosphate ([bmim][PF6], IL2) was introduced to the functionalization of graphene (GN) nanosheets, which was used to the synthesis of platinum nanoparticles (Pt NPs) to obtain the Pt/IL1-IL2/GN nanocomposite. The as-prepared Pt/IL1-IL2/GN composites exhibited highly electrocatalytic activity (764.3 mA mg − 1Pt at 0.6 V vs. SCE) and stability toward methanol oxidation, demonstrating their promising potential as the anode catalyst for direct methanol fuel cells (DMFCs). - Highlights: • Pt/mixed ionic liquids/graphene composite catalyst was easily synthesized. • The special phase equilibrium characteristics exerted by the peculiar interactions between different ILs can promote the homogeneous growth of small Pt nanoparticles. • The as-made catalyst exhibited enhanced electro-catalytic performance for methanol oxidation. - Abstract: A kind of mixed ionic liquids (ILs) of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF 4 ], IL 1 ) and hexafluorophosphate ([bmim][PF 6 ], IL 2 ) was introduced to the functionalization of graphene (GN) nanosheets, which was used to the synthesis of platinum nanoparticles (Pt NPs) to obtain the Pt/IL 1 -IL 2 /GN nanocomposite. The interaction between mixed ILs and GN achieved a stable performance due to the excellent electronic and interfacial property of the fabricated nanocomposites, which was favorable for effective loading of Pt NPs on the IL 1 -IL 2 /GN support. The as-prepared Pt/IL 1 -IL 2 /GN composites exhibited highly electrocatalytic activity (764.3 mA mg −1 Pt at 0.6 V vs. SCE) and stability toward methanol oxidation, demonstrating their promising potential as the anode catalyst for direct methanol fuel cells (DMFCs)

  6. Effects of dimethyl ether on the performance characteristics of a direct methanol fuel cell

    Seo, Sang Hern; Lee, Chang Sik

    2013-01-01

    Highlights: • Activation loss is significantly reduced in fuel cell with DME-methanol. • DME crossover through the membrane reduces. • The open circuit voltage of DME-methanol the fuel cell increases. • The overall efficiency of the mixed fuel cell is higher than that of DMFC. - Abstract: The objective of this study was to determine the effects of dimethyl ether (DME) on the performance characteristics of a direct methanol fuel cell. Impedance and crossover experiments were performed in order to investigate the performance losses such as ohmic loss, activation loss and crossover loss accurately. The DME was pressurized to 5 bar to supply with liquid phase was and blended with an aqueous methanol solution. In this experiment, the membrane electrode assembly (MEA) was composed of Nafion 115, anode catalyst loaded Pt–Ru and cathode catalyst loaded Pt-Black. Experimental results showed that fuel cells with DME-methanol enhanced performance when compared to fuel cells with methanol only. Such performance enhancement was due to a decrease in activation losses by DME oxidation reactions. As the DME crossover through the membrane was reduced, the open circuit voltage (OCV) of the fuel cell increased. Other output characteristics are also discussed

  7. Evaporation and condensation at a liquid methanol surface

    Matsumoto, Mitsuhiro; Yasuoka, Kenji; Kataoka, Yosuke

    1994-07-01

    The dynamics of evaporation and condensation at a flat liquid surface of methanol were studied under the liquidvapor equilibrium condition at room temperature with molecular dynamics computer simulation techniques. Analysis of molecular trajectories shows that the condensation coefficient is 89%. It suggests that only a tenth of incident vapor molecules are reflected at the liquid surface, contrary to a prediction of a classical transition state theory. To investigate the potential barrier of the evaporation-condensation process, a particle insertion method was applied and the local chemical potential near the surface was evaluated. The calculated chemical potential is constant in the whole region including the surface layer and no potential barrier is observed in the vincinity of the surface, which casts strong doubt on the explanation of a transition state theory.

  8. Fuel and power coproduction: The Liquid Phase Methanol (LPMEOH{trademark}) process demonstration at Kingsport

    Drown, D.P.; Brown, W.R.; Heydorn, E.C.; Moore, R.B.; Schaub, E.S.; Brown, D.M.; Jones, W.C.; Kornosky, R.M.

    1997-12-31

    The Liquid Phase Methanol (LPMEOH{trademark}) process uses a slurry bubble column reactor to convert syngas (primarily a mixture of carbon monoxide and hydrogen) to methanol. Because of its superior heat management, the process is able to be designed to directly handle the carbon monoxide (CO)-rich syngas characteristic of the gasification of coal, petroleum coke, residual oil, wastes, or of other hydrocarbon feedstocks. When added to an integrated gasification combined cycle (IGCC) power plant, the LPMEOH{trademark} process converts a portion of the CO-rich syngas produced by the gasifier to methanol, and the remainder of the unconverted gas is used to fuel the gas turbine combined-cycle power plant. The LPMEOH{trademark} process has the flexibility to operate in a daily electricity demand load-following manner. Coproduction of power and methanol via IGCC and the LPMEOH{trademark} process provides opportunities for energy storage for electrical demand peak shaving, clean fuel for export, and/or chemical methanol sales.

  9. Long Term Performance Study of a Direct Methanol Fuel Cell Fed with Alcohol Blends

    Teresa J. Leo; Miguel A. Raso; Emilio Navarro; Eleuterio Mora

    2013-01-01

    The use of alcohol blends in direct alcohol fuel cells may be a more environmentally friendly and less toxic alternative to the use of methanol alone in direct methanol fuel cells. This paper assesses the behaviour of a direct methanol fuel cell fed with aqueous methanol, aqueous ethanol and aqueous methanol/ethanol blends in a long term experimental study followed by modelling of polarization curves. Fuel cell performance is seen to decrease as the ethanol content rises, and subsequent opera...

  10. A Nafion-Ceria Composite Membrane Electrolyte for Reduced Methanol Crossover in Direct Methanol Fuel Cells

    Parthiban Velayutham

    2017-02-01

    Full Text Available An alternative Nafion composite membrane was prepared by incorporating various loadings of CeO2 nanoparticles into the Nafion matrix and evaluated its potential application in direct methanol fuel cells (DMFCs. The effects of CeO2 in the Nafion matrix were systematically studied in terms of surface morphology, thermal and mechanical stability, proton conductivity and methanol permeability. The composite membrane with optimum filler content (1 wt. % CeO2 exhibits a proton conductivity of 176 mS·cm−1 at 70 °C, which is about 30% higher than that of the unmodified membrane. Moreover, all the composite membranes possess a much lower methanol crossover compared to pristine Nafion membrane. In a single cell DMFC test, MEA fabricated with the optimized composite membrane delivered a peak power density of 120 mW·cm−2 at 70 °C, which is about two times higher in comparison with the pristine Nafion membrane under identical operating conditions.

  11. Microwave Plasma Enhanced Chemical Vapor Deposition of Diamond in Vapor of Methanol-Based Liquid Solutions

    Tzeng, Yonhua

    2000-01-01

    .... Liquid solutions are prepared by mixing methanol with other carbon containing liquid compounds which contain a greater than one ratio of carbon to oxygen such as acetone, ethanol, and iso-propanol...

  12. Extending EV Range with Direct Methanol Fuel Cells

    Steckmann, Kai

    2009-01-01

    Electric cars are the vehicles of the future, and there is a proven hybrid system for extending their mileage. Direct methanol fuel cells (DMFCs) provide safe, lightweight, onboard battery charging that can free car owners from worry about running out of power. The hybrid system includes a DMFC fuel cell, fuel cell cartridge and electric vehicle batteries. The fuel cell operates almost silently with virtually no exhaust, it is immune to extreme weather and the convenient fuel cartridges featu...

  13. Direct methanol feed fuel cell with reduced catalyst loading

    Kindler, Andrew (Inventor)

    1999-01-01

    Improvements to direct feed methanol fuel cells include new protocols for component formation. Catalyst-water repellent material is applied in formation of electrodes and sintered before application of ionomer. A membrane used in formation of an electrode assembly is specially pre-treated to improve bonding between catalyst and membrane. The improved electrode and the pre-treated membrane are assembled into a membrane electrode assembly.

  14. Design and Fabrication of the First Commercial-Scale Liquid Phase Methanol (LPMEOH) Reactor

    None

    1998-12-21

    The Liquid Phase Methanol (LPMEOHT) process uses a slurry bubble column reactor to convert synthesis gas (syngas), primarily a mixture of carbon monoxide and hydrogen, to methanol. Because of its superior heat management the process can utilize directly the carbon monoxide (CO)-rich syngas characteristic of the gasification of coal, petroleum coke, residual oil, wastes, or other hydrocarbon feedstocks. The LPMEOHM Demonstration Project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P., a partnership between Air Products and Chemicals, Inc. and Eastman Chemical Company, to produce methanol from coal-derived syngas. Construction of the LPMEOH~ Process Demonstration Plant at Eastman's chemicals-from-coal complex in Kingsport was completed in January 1997. Following commissioning and shakedown activities, the fwst production of methanol from the facility occurred on April 2, 1997. Nameplate capacity of 260 short tons per day (TPD) was achieved on April 6, 1997, and production rates have exceeded 300 TPD of methanol at times. This report describes the design, fabrication, and installation of the Kingsport LPMEOEFM reactor, which is the first commercial-scale LPMEOEPM reaetor ever built. The vessel is 7.5 feet in diameter and 70 feet tall with design conditions of 1000 psig at 600 `F. These dimensions represent a significant scale-up from prior experience at the DOE-owned Alternative Fuels Development Unit in LaPorte, Texas, where 18-inch and 22-inch diameter reactors have been tested successfidly over thousands of hours. The biggest obstacles discovered during the scale- up, however, were encountered during fabrication of the vessel. The lessons learned during this process must be considered in tailoring the design for future sites, where the reactor dimensions may grow by yet another factor of two.

  15. Development of Anodic Flux and Temperature Controlling System for Micro Direct Methanol Fuel Cell

    Li, M M; Liu, C; Liang, J S; Wu, C B; Xu, Z

    2006-01-01

    Micro Direct Methanol Fuel Cell (μDMFC) is a kind of newly developed power sources, which effective apparatus for its performance evaluation is still in urgent need at present. In this study, a testing system was established for the purpose of testing the continuous working performance such as micro flux and temperature of μDMFC. In view of the temperature controlling for micro-flux liquid fuel, a heating block with labyrinth-like single pass channel inside for heating up the methanol solution was fabricated. A semiconductorrefrigerating chip was utilized to heat and cool the liquid flow during testing procedures. On the other hand, the two channels of a high accuracy double-channel syringe pump that can suck and pump in turn so as to transport methanol solution continuously was adopted. Based on the requirements of wide-ranged temperature and micro flux controlling, the solenoid valves and the correlative component were used. A hydraulic circuit, which can circulate the fed methanol cold to hot in turn, has also been constructed to test the fatigue life of the μDMFC. The automatic control was actualized by software module written with Visual C++. Experimental results show that the system is perfect in stability and it may provide an important and advanced evaluation apparatus to satisfy the needs for real time performance testing of μDMFC

  16. A gradient activation method for direct methanol fuel cells

    Liu, Guicheng; Yang, Zhaoyi; Halim, Martin; Li, Xinyang; Wang, Manxiang; Kim, Ji Young; Mei, Qiwen; Wang, Xindong; Lee, Joong Kee

    2017-01-01

    Highlights: • A gradient activation method was reported firstly for direct methanol fuel cells. • The activity recovery of Pt-based catalyst was introduced into the novel activation process. • The new activation method led to prominent enhancement of DMFC performance. • DMFC performance was improved with the novel activation step by step within 7.5 h. - Abstract: To realize gradient activation effect and recover catalytic activity of catalyst in a short time, a gradient activation method has firstly been proposed for enhancing discharge performance and perfecting activation mechanism of the direct methanol fuel cell (DMFC). This method includes four steps, i.e. proton activation, activity recovery activation, H_2-O_2 mode activation and forced discharging activation. The results prove that the proposed method has gradually realized replenishment of water and protons, recovery of catalytic activity of catalyst, establishment of transfer channels for electrons, protons, and oxygen, and optimization of anode catalyst layer for methanol transfer in turn. Along with the novel activation process going on, the DMFC discharge performance has been improved, step by step, to more than 1.9 times higher than that of the original one within 7.5 h. This method provides a practicable activation way for the real application of single DMFCs and stacks.

  17. Update on status of direct methanol fuel cells

    Reeve, R.W.

    2002-07-01

    This report reviews the progress in direct methanol fuel cell (DMFC) technology since 1995 and examines the opportunities for this technology in various market sectors. The report is divided into two parts. Part A describes the state-of-the-art of DMFC technology, developments in electrocatalysis relevant to DMFCs, single cell and stack performance, and polymer electrolyte membranes. Part B discusses the viability of current DMFCs for portable and automotive applications, and examines some niche markets, eg for remote power applications. Market opportunities, technical issues, applications and competing technologies are summarised. The report draws attention to the outstanding technical issues and recommends further development in a number of areas (eg inexpensive membranes with lower rates of methanol crossover, membranes with lower rates of water permeation, improved power density and methods to ensure solutions do not freeze in cold climates).

  18. Combinatorial discovery of new methanol-tolerant non-noble metal cathode electrocatalysts for direct methanol fuel cells.

    Yu, Jong-Sung; Kim, Min-Sik; Kim, Jung Ho

    2010-12-14

    Combinatorial synthesis and screening were used to identify methanol-tolerant non-platinum cathode electrocatalysts for use in direct methanol fuel cells (DMFCs). Oxygen reduction consumes protons at the surface of DMFC cathode catalysts. In combinatorial screening, this pH change allows one to differentiate active catalysts using fluorescent acid-base indicators. Combinatorial libraries of carbon-supported catalyst compositions containing Ru, Mo, W, Sn, and Se were screened. Ternary and quaternary compositions containing Ru, Sn, Mo, Se were more active than the "standard" Alonso-Vante catalyst, Ru(3)Mo(0.08)Se(2), when tested in liquid-feed DMFCs. Physical characterization of the most active catalysts by powder X-ray diffraction, gas adsorption, and X-ray photoelectron spectroscopy revealed that the predominant crystalline phase was hexagonal close-packed (hcp) ruthenium, and showed a surface mostly covered with oxide. The best new catalyst, Ru(7.0)Sn(1.0)Se(1.0), was significantly more active than Ru(3)Se(2)Mo(0.08), even though the latter contained smaller particles.

  19. New ETFE-based membrane for direct methanol fuel cell

    Saarinen, V.; Kallio, T.; Paronen, M.; Tikkanen, P.; Rauhala, E.; Kontturi, K.

    2005-01-01

    The investigated membranes are based on 35-bar μ m thick commercial poly(ethylene-alt-tetrafluoroethylene) (ETFE) films. The films were made proton conductive by means of irradiation treatment followed by sulfonation. These membranes have exceptionally low water uptake and excellent dimensional stability. The new membranes are investigated widely in a laboratory-scale direct methanol fuel cell (DMFC). The temperature range used in the fuel cell tests was 30-85-bar o C and the measurement results were compared to those of the Nafion ( R)115 membrane. Also methanol permeability through the ETFE-based membrane was measured as a function of temperature, resulting in values less than 10% of the corresponding values for Nafion ( R)115, which was considerably thicker than the experimental membrane. Methanol crossover was reported to decrease when the thickness of the membrane increases, so the ETFE-based membrane compares favourably to Nafion ( R) membranes. The maximum power densities achieved with the experimental ETFE-based membrane were about 40-65% lower than the corresponding values of the Nafion ( R)115 membrane, because of the lower conductivity and noticeably higher IR-losses. Chemical and mechanical stability of the ETFE-based membrane appeared to be promising since it was tested over 2000-bar h in the DMFC without any performance loss

  20. New Catalysts for Direct Methanol Oxidation Fuel Cells

    Adzic, Radoslav

    1998-08-01

    A new class of efficient electrocatalytic materials based on platinum - metal oxide systems has been synthetized and characterized by several techniques. Best activity was found with NiWO{sub 4}-, CoWO{sub 4}-, and RuO{sub 2}- sr¡pported platinum catalysts. A very similar activity at room temperature was observed with the electrodes prepared with the catalyst obtained from International Fuel Cells Inc. for the same Pt loading. Surprisingly, the two tungstates per se show a small activity for methanol oxidation without any Pt loading. Synthesis of NiWO{sub 4} and CoWO{sub 4} were carried out by solid-state reactions. FTIR spectroscopy shows that the tungstates contain a certain amount of physically adsorbed water even after heating samples at 200{degrees}C. A direct relationship between the activity for methanol oxidation and the amount of adsorbed water on those oxides has been found. The Ru(0001) single crystal shows a very small activity for CO adsorption and oxidation, in contrast to the behavior of polycrystalline Ru. In situ extended x-ray absorption fine structure spectroscopy (EXAFS) and x-ray absorption near edge spectroscopy (XANES) showed that the OH adsorption on Ru in the Pt-Ru alloy appears to be the limiting step in methanol oxidation. This does not occur for Pt-RuO{SUB 2} electrocatalyst, which explains its advantages over the Pt-Ru alloys. The IFCC electrocatalyst has the properties of the Pt-Ru alloy.

  1. Novel Anode Catalyst for Direct Methanol Fuel Cells

    S. Basri

    2014-01-01

    Full Text Available PtRu catalyst is a promising anodic catalyst for direct methanol fuel cells (DMFCs but the slow reaction kinetics reduce the performance of DMFCs. Therefore, this study attempts to improve the performance of PtRu catalysts by adding nickel (Ni and iron (Fe. Multiwalled carbon nanotubes (MWCNTs are used to increase the active area of the catalyst and to improve the catalyst performance. Electrochemical analysis techniques, such as energy dispersive X-ray spectrometry (EDX, X-ray diffraction (XRD, field emission scanning electron microscopy (FESEM, and X-ray photoelectron spectroscopy (XPS, are used to characterize the kinetic parameters of the hybrid catalyst. Cyclic voltammetry (CV is used to investigate the effects of adding Fe and Ni to the catalyst on the reaction kinetics. Additionally, chronoamperometry (CA tests were conducted to study the long-term performance of the catalyst for catalyzing the methanol oxidation reaction (MOR. The binding energies of the reactants and products are compared to determine the kinetics and potential surface energy for methanol oxidation. The FESEM analysis results indicate that well-dispersed nanoscale (2–5 nm PtRu particles are formed on the MWCNTs. Finally, PtRuFeNi/MWCNT improves the reaction kinetics of anode catalysts for DMFCs and obtains a mass current of 31 A g−1 catalyst.

  2. Autonomous Voltage Oscillations in a Direct Methanol Fuel Cell

    Nogueira, Jéssica A.; Peña Arias, Ivonne K.; Hanke-Rauschenbach, Richard; Vidakovic-Koch, Tanja; Varela, Hamilton; Sundmacher, Kai

    2016-01-01

    Proton exchange membrane fuel cells fed with H_2/CO mixtures at the anode have a considerably lower performance than fuel cells fed with pure hydrogen. However, when operated in an autonomous oscillatory regime, the overall voltage loss decreases due to a self-cleaning mechanism. Another molecule, also widely used as feed in the fuel cell and susceptible to kinetic instabilities, is methanol. To the best of our knowledge, there are no reports on autonomous voltage oscillations in the direct methanol fuel cell (DMFC). The purpose of this work was to explore if such instabilities also occur in the DMFC system. Initially, half-cell experiments with a gas diffusion electrode were performed. Then, a DMFC was operated under current control and studied by means of electrochemical impedance spectroscopy. The half-cell measurements revealed that the induction period for oscillations depends on the mass transfer conditions, where on stagnant electrode the induction time was shorter than in the case of forced convection. The DMFC showed also autonomous voltage oscillations above a certain threshold current. The results obtained by electrochemical impedance spectroscopy give evidence of a negative differential resistance in the fuel cell, hitherto not described in the literature, which can be related to the appearance of oscillations during galvanostatic methanol electro-oxidation. These results open the possibility to evaluate the performance of low-temperature fuel cells fed with carbon-containing fuels under oscillatory operating conditions.

  3. Novel anode catalyst for direct methanol fuel cells.

    Basri, S; Kamarudin, S K; Daud, W R W; Yaakob, Z; Kadhum, A A H

    2014-01-01

    PtRu catalyst is a promising anodic catalyst for direct methanol fuel cells (DMFCs) but the slow reaction kinetics reduce the performance of DMFCs. Therefore, this study attempts to improve the performance of PtRu catalysts by adding nickel (Ni) and iron (Fe). Multiwalled carbon nanotubes (MWCNTs) are used to increase the active area of the catalyst and to improve the catalyst performance. Electrochemical analysis techniques, such as energy dispersive X-ray spectrometry (EDX), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS), are used to characterize the kinetic parameters of the hybrid catalyst. Cyclic voltammetry (CV) is used to investigate the effects of adding Fe and Ni to the catalyst on the reaction kinetics. Additionally, chronoamperometry (CA) tests were conducted to study the long-term performance of the catalyst for catalyzing the methanol oxidation reaction (MOR). The binding energies of the reactants and products are compared to determine the kinetics and potential surface energy for methanol oxidation. The FESEM analysis results indicate that well-dispersed nanoscale (2-5 nm) PtRu particles are formed on the MWCNTs. Finally, PtRuFeNi/MWCNT improves the reaction kinetics of anode catalysts for DMFCs and obtains a mass current of 31 A g(-1) catalyst.

  4. Passive direct methanol fuel cells for portable electronic devices

    Achmad, F.; Kamarudin, S.K.; Daud, W.R.W.; Majlan, E.H.

    2011-01-01

    Due to the increasing demand for electricity, clean, renewable energy resources must be developed. Thus, the objective of the present study was to develop a passive direct methanol fuel cell (DMFC) for portable electronic devices. The power output of six dual DMFCs connected in series with an active area of 4 cm 2 was approximately 600 mW, and the power density of the DMFCs was 25 mW cm -2 . The DMFCs were evaluated as a power source for mobile phone chargers and media players. The results indicated that the open circuit voltage of the DMFC was between 6.0 V and 6.5 V, and the voltage under operating conditions was 4.0 V. The fuel cell was tested on a variety of cell phone chargers, media players and PDAs. The cost of energy consumption by the proposed DMFC was estimated to be USD 20 W -1 , and the cost of methanol is USD 4 kW h. Alternatively, the local conventional electricity tariff is USD 2 kW h. However, for the large-scale production of electronic devices, the cost of methanol will be significantly lower. Moreover, the electricity tariff is expected to increase due to the constraints of fossil fuel resources and pollution. As a result, DMFCs will become competitive with conventional power sources.

  5. A microfluidic-structured flow field for passive direct methanol fuel cells operating with highly concentrated fuels

    Wu, Q X; Zhao, T S; Chen, R; Yang, W W

    2010-01-01

    Conventional direct methanol fuel cells (DMFCs) have to operate with excessively diluted methanol solutions to limit methanol crossover and its detrimental consequences. Operation with such diluted methanol solutions not only results in a significant penalty in the specific energy of the power pack, limiting the runtime of this type of fuel cell, but also lowers the cell performance and operating stability. In this paper, a microfluidic-structured anode flow field for passive DMFCs with neither liquid pumps nor gas compressors/blowers is developed. This flow field consists of plural micro flow passages. Taking advantage of the liquid methanol and gas CO 2 two-phase counter flow, the unique fluidic structure enables the formation of a liquid–gas meniscus in each flow passage. The evaporation from the small meniscus in each flow passage can lead to an extremely large interfacial mass-transfer resistance, creating a bottleneck of methanol delivery to the anode CL. The fuel cell tests show that the innovative flow field allows passive DMFCs to achieve good cell performance with a methanol concentration as high as 18.0 M, increasing the specific energy of the DMFC system by about five times compared with conventional designs.

  6. Characteristics of a direct methanol fuel cell system with the time shared fuel supplying approach

    Na, Youngseung; Kwon, Jungmin; Kim, Hyun; Cho, Hyejung; Song, Inseob

    2013-01-01

    DMFC (direct methanol fuel cell) systems usually employ two pumps for supplying the methanol solution. The conventional system configuration, however, may bring about free flow from the methanol reservoir and malfunctions in the self-priming of the pumps. When instruments such as check valves and pressure regulators are applied, they result in excessive weight and control system malfunctions. In this paper, a light and robust DMFC system is proposed. By using the time sharing approach to supply fuel with a 3-way valve, free flow does not occur because only one inlet is opened at one time which means that both the circulation flow from gas liquid separator and the fuel flow from the methanol cartridge are not allowed to be opened at same time. As a result, back flow and self-priming problems do not occur. This makes the system stable and robust due to the removal of both the check valves and the fluctuation from unstable back pressure. Stabilized system doesn't need excessive battery buffering and recycling water any more, which are responsible for the heavy system. The proposed system performs the same level of power and efficiency with the conventional system. Adaptability is also carried out in various environmental temperature conditions. - Highlights: ►A light and robust DMFC system is proposed. ► The circulation pump is able to self-prime by itself after long term storage. ► The time sharing approach to supply fuel enables to control the methanol concentration precisely. ► The methanol concentration is controlled without free flow and the back flow from the fuel feeding pump. ► The excessive buffer of the batteries and the recycling water level are reduced

  7. (Liquid + liquid) equilibrium of (dibutyl ether + methanol + water) at different temperatures

    Arce, Alberto; Rodriguez, Hector; Rodriguez, Oscar; Soto, Ana

    2005-01-01

    (Liquid + liquid) equilibrium data for the ternary system (dibutyl ether + methanol + water) were experimentally determined at T = (298.15, 308.15, and 318.15) K. The experimental results were correlated by means of the NRTL and UNIQUAC equations, the best results being achieved with the UNIQUAC equation, both for the individual correlations at each temperature and for the overall correlation considering all the three experimental data sets. The experimental tie-lines were also compared to the values predicted by the UNIFAC method

  8. Operation characteristic analysis of a direct methanol fuel cell system using the methanol sensor-less control method

    Chen, C.Y.; Chang, C.L. [Institute of Nuclear Energy Research (INER), Longtan Township, Taoyuan County (China); Sung, C.C. [National Taiwan University (China)

    2012-10-15

    The application of methanol sensor-less control in a direct methanol fuel cell (DMFC) system eliminates most of the problems encountered when using a methanol sensor and is one of the major solutions currently used in commercial DMFCs. This study focuses on analyzing the effect of the operating characteristics of a DMFC system on its performance under the methanol sensor-less control as developed by Institute of Nuclear Energy Research (INER). Notably, the influence of the dispersion of the methanol injected on the behavior of the system is investigated systematically. In addition, the mechanism of the methanol sensor-less control is investigated by varying factors such as the timing of the injection of methanol, the cathode flow rate, and the anode inlet temperature. These results not only provide insight into the mechanism of methanol sensor-less control but can also aid in the improvement and application of DMFC systems in portable and low-power transportation. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Improved Anode for a Direct Methanol Fuel Cell

    Valdez, Thomas; Narayanan, Sekharipuram

    2005-01-01

    A modified chemical composition has been devised to improve the performance of the anode of a direct methanol fuel cell. The main feature of the modified composition is the incorporation of hydrous ruthenium oxide into the anode structure. This modification can reduce the internal electrical resistance of the cell and increase the degree of utilization of the anode catalyst. As a result, a higher anode current density can be sustained with a smaller amount of anode catalyst. These improvements can translate into a smaller fuel-cell system and higher efficiency of conversion. Some background information is helpful for understanding the benefit afforded by the addition of hydrous ruthenium oxide. The anode of a direct methanol fuel cell sustains the electro-oxidation of methanol to carbon dioxide in the reaction CH3OH + H2O--->CO2 + 6H(+) + 6e(-). An electrocatalyst is needed to enable this reaction to occur. The catalyst that offers the highest activity is an alloy of approximately equal numbers of atoms of the noble metals platinum and ruthenium. The anode is made of a composite material that includes high-surface-area Pt/Ru alloy particles and a proton-conducting ionomeric material. This composite is usually deposited onto a polymer-electrolyte (proton-conducting) membrane and onto an anode gas-diffusion/current-collector sheet that is subsequently bonded to the proton-conducting membrane by hot pressing. Heretofore, the areal density of noble-metal catalyst typically needed for high performance has been about 8 mg/cm2. However, not all of the catalyst has been utilized in the catalyzed electro-oxidation reaction. Increasing the degree of utilization of the catalyst would make it possible to improve the performance of the cell for a given catalyst loading and/or reduce the catalyst loading (thereby reducing the cost of the cell). The use of carbon and possibly other electronic conductors in the catalyst layer has been proposed for increasing the utilization of the

  10. Vapor-Liquid Equilibrium of Methane with Water and Methanol. Measurements and Modeling

    Frost, Michael Grynnerup; Karakatsani, Eirini; von Solms, Nicolas

    2014-01-01

    that rely on phase equilibrium data for optimization. The objective of this work is to provide experimental data for hydrocarbon systems with polar chemicals such as alcohols, glycols, and water. New vapor-liquid equilibrium data are reported for methane + water, methane + methanol, and methane + methanol...

  11. Micro-electro-mechanical systems (MEMS)-based micro-scale direct methanol fuel cell development

    Yao, S.-C.; Tang Xudong; Hsieh, C.-C.; Alyousef, Yousef; Vladimer, Michael; Fedder, Gary K.; Amon, Cristina H.

    2006-01-01

    This paper describes a high-power density, silicon-based micro-scale direct methanol fuel cell (DMFC), under development at Carnegie Mellon. Major issues in the DMFC design include the water management and energy-efficient micro fluidic sub-systems. The air flow and the methanol circulation are both at a natural draft, while a passive liquid-gas separator removes CO 2 from the methanol chamber. An effective approach for maximizing the DMFC energy density, pumping the excess water back to the anode, is illustrated. The proposed DMFC contains several unique features: a silicon wafer with arrays of etched holes selectively coated with a non-wetting agent for collecting water at the cathode; a silicon membrane micro pump for pumping the collected water back to the anode; and a passive liquid-gas separator for CO 2 removal. All of these silicon-based components are fabricated using micro-electro-mechanical systems (MEMS)-based processes on the same silicon wafer, so that interconnections are eliminated, and integration efforts as well as post-fabrication costs are both minimized. The resulting fuel cell has an overall size of one cubic inch, produces a net output of 10 mW, and has an energy density three to five times higher than that of current lithium-ion batteries

  12. Novel crosslinked membranes based on sulfonated poly(ether ether ketone) for direct methanol fuel cells.

    Zhu, Yuanqin; Zieren, Shelley; Manthiram, Arumugam

    2011-07-14

    Novel covalently crosslinked membranes based on sulfonated poly(ether ether ketone) and carboxylated polysulfone exhibit much lower methanol crossover and better performance in direct methanol fuel cells at 65 °C in 1 and 2 M methanol solutions compared to Nafion 115 membranes.

  13. Modeling of the Transport Phenomena in Passive Direct Methanol Fuel Cells Using a Two-Phase Anisotropic Model

    Zheng Miao

    2014-04-01

    Full Text Available The transport phenomena in a passive direct methanol fuel cell (DMFC were numerically simulated by the proposed two-dimensional two-phase nonisothermal mass transport model. The anisotropic transport characteristic and deformation of the gas diffusion layer (GDL were considered in this model. The natural convection boundary conditions were adopted for the transport of methanol, oxygen, and heat at the GDL outer surface. The effect of methanol concentration in the reservoir on cell performance was examined. The distribution of multiphysical fields in the membrane electrode assembly (MEA, especially in the catalyst layers (CLs, was obtained and analyzed. The results indicated that transport resistance for the methanol mainly existed in the MEA while that for oxygen and heat was primarily due to natural convection at the GDL outer surface. Because of the relatively high methanol concentration, the local reaction rate in CLs was mainly determined by the overpotential. Methanol concentration between 3 M and 4 M was recommended for passive liquid feed DMFC in order to achieve a balance between the cell performance and the methanol crossover.

  14. Performance evaluation of direct methanol fuel cells for portable applications

    Rashidi, R.; Dincer, I.; Naterer, G.F. [Faculty of Engineering and Applied Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, Ontario (Canada); Berg, P. [Faculty of Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, Ontario (Canada)

    2009-02-15

    This study examines the feasibility of powering a range of portable devices with a direct methanol fuel cell (DMFC). The analysis includes a comparison between a Li-ion battery and DMFC to supply the power for a laptop, camcorder and a cell phone. A parametric study of the systems for an operational period of 4 years is performed. Under the assumptions made for both the Li-ion battery and DMFC system, the battery cost is lower than the DMFC during the first year of operation. However, by the end of 4 years of operational time, the DMFC system would cost less. The weight and cost comparisons show that the fuel cell system occupies less space than the battery to store a higher amount of energy. The weight of both systems is almost identical. Finally, the CO{sub 2} emissions can be decreased by a higher exergetic efficiency of the DMFC, which leads to improved sustainability. (author)

  15. Development of an electrode for direct methanol fuel cell

    Ramzia, A. M. S.; Iqbal, J.

    2006-01-01

    This paper presents the efficient use of platinum catalyst ruthenium with in the anode of a Direct Methanol Fuel Cell (DMFC). This is achieved by depositing platinum and ruthenium nano-particles on the pre-refluxed multi-walled carbon nano-tubes (MWCNT): MWCNTs were synthesized using the Chemical Vapor Deposition (CVD) with floating catalyst technique. The synthesized carbon nano tubes (CNT) were refluxed in 12M nitric acid to produce anchoring sites on the surface of the CNT. The platinum and ruthenium nano-particles were in a ratio of (3.1). These particles are deposited on the surface of the CNT at 60 wt % by reduction in ethylene glycol. Transmission micrograph (TEM) and scanning electron micrograph (SEM) images show the success of the deposition method. (author)

  16. Thin Film Catalyst Layers for Direct Methanol Fuel Cells

    Witham, C. K.; Chun, W.; Ruiz, R.; Valdez, T. I.; Narayanan, S. R.

    2000-01-01

    One of the primary obstacles to the widespread use of the direct methanol fuel cell (DMFC) is the high cost of the catalyst. Therefore, reducing the catalyst loading well below the current level of 8-12 mg/cm 2 would be important to commercialization. The current methods for preparation of catalyst layers consisting of catalyst, ionomer and sometimes a hydrophobic additive are applied by either painting, spraying, decal transfer or screen printing processes. Sputter deposition is a coating technique widely used in manufacturing and therefore particularly attractive. In this study we have begun to explore sputtering as a method for catalyst deposition. Present experiments focus on Pt-Ru catalyst layers for the anode.

  17. Recovery Act: Advanced Direct Methanol Fuel Cell for Mobile Computing

    Fletcher, James H. [University of North Florida; Cox, Philip [University of North Florida; Harrington, William J [University of North Florida; Campbell, Joseph L [University of North Florida

    2013-09-03

    ABSTRACT Project Title: Recovery Act: Advanced Direct Methanol Fuel Cell for Mobile Computing PROJECT OBJECTIVE The objective of the project was to advance portable fuel cell system technology towards the commercial targets of power density, energy density and lifetime. These targets were laid out in the DOE’s R&D roadmap to develop an advanced direct methanol fuel cell power supply that meets commercial entry requirements. Such a power supply will enable mobile computers to operate non-stop, unplugged from the wall power outlet, by using the high energy density of methanol fuel contained in a replaceable fuel cartridge. Specifically this project focused on balance-of-plant component integration and miniaturization, as well as extensive component, subassembly and integrated system durability and validation testing. This design has resulted in a pre-production power supply design and a prototype that meet the rigorous demands of consumer electronic applications. PROJECT TASKS The proposed work plan was designed to meet the project objectives, which corresponded directly with the objectives outlined in the Funding Opportunity Announcement: To engineer the fuel cell balance-of-plant and packaging to meet the needs of consumer electronic systems, specifically at power levels required for mobile computing. UNF used existing balance-of-plant component technologies developed under its current US Army CERDEC project, as well as a previous DOE project completed by PolyFuel, to further refine them to both miniaturize and integrate their functionality to increase the system power density and energy density. Benefits of UNF’s novel passive water recycling MEA (membrane electrode assembly) and the simplified system architecture it enabled formed the foundation of the design approach. The package design was hardened to address orientation independence, shock, vibration, and environmental requirements. Fuel cartridge and fuel subsystems were improved to ensure effective fuel

  18. Improved Cathode Structure for a Direct Methanol Fuel Cell

    Valdez, Thomas; Narayanan, Sekharipuram

    2005-01-01

    An improved cathode structure on a membrane/electrode assembly has been developed for a direct methanol fuel cell, in a continuing effort to realize practical power systems containing such fuel cells. This cathode structure is intended particularly to afford better cell performance at a low airflow rate. A membrane/electrode assembly of the type for which the improved cathode structure was developed (see Figure 1) is fabricated in a process that includes brush painting and spray coating of catalyst layers onto a polymer-electrolyte membrane and onto gas-diffusion backings that also act as current collectors. The aforementioned layers are then dried and hot-pressed together. When completed, the membrane/electrode assembly contains (1) an anode containing a fine metal black of Pt/Ru alloy, (2) a membrane made of Nafion 117 or equivalent (a perfluorosulfonic acid-based hydrophilic, proton-conducting ion-exchange polymer), (3) a cathode structure (in the present case, the improved cathode structure described below), and (4) the electrically conductive gas-diffusion backing layers, which are made of Toray 060(TradeMark)(or equivalent) carbon paper containing between 5 and 6 weight percent of poly(tetrafluoroethylene). The need for an improved cathode structure arises for the following reasons: In the design and operation of a fuel-cell power system, the airflow rate is a critical parameter that determines the overall efficiency, cell voltage, and power density. It is desirable to operate at a low airflow rate in order to obtain thermal and water balance and to minimize the size and mass of the system. The performances of membrane/electrode assemblies of prior design are limited at low airflow rates. Methanol crossover increases the required airflow rate. Hence, one way to reduce the required airflow rate is to reduce the effect of methanol crossover. Improvement of the cathode structure - in particular, addition of hydrophobic particles to the cathode - has been

  19. Direct observation of deformation of nafion surfaces induced by methanol treatment by using atomic force microscopy

    Umemura, Kazuo; Kuroda, Reiko; Gao Yanfeng; Nagai, Masayuki; Maeda, Yuta

    2008-01-01

    We successfully characterized the effect of methanol treatment on the nanoscopic structures of a nafion film, which is widely used in direct methanol fuel cells (DMFCs). Atomic force microscopy (AFM) was used to repetitively image a particular region of a nafion sample before and after methanol solutions were dropped onto the nafion film and dried in air. When the surface was treated with 20% methanol for 5 min, many nanopores appeared on the surface. The number of nanopores increased when the sample was treated twice or thrice. By repetitive AFM imaging of a particular region of the same sample, we found that the shapes of the nanopores were deformed by the repeated methanol treatment, although the size of the nanopores had not significantly changed. The creation of the nanopores was affected by the concentration of methanol. Our results directly visualized the effects of methanol treatment on the surface structures of a nafion film at nanoscale levels for the first time

  20. Matlab Source Code for Species Transport through Nafion Membranes in Direct Ethanol, Direct Methanol, and Direct Glucose Fuel Cells

    JH, Summerfield; MW, Manley

    2016-01-01

    A simple simulation of chemical species movement is presented. The species traverse a Nafion membrane in a fuel cell. Three cells are examined: direct methanol, direct ethanol, and direct glucose. The species are tracked using excess proton concentration, electric field strength, and voltage. The Matlab computer code is provided.

  1. Three-dimensional two-phase mass transport model for direct methanol fuel cells

    Yang, W.W.; Zhao, T.S.; Xu, C.

    2007-01-01

    A three-dimensional (3D) steady-state model for liquid feed direct methanol fuel cells (DMFC) is presented in this paper. This 3D mass transport model is formed by integrating five sub-models, including a modified drift-flux model for the anode flow field, a two-phase mass transport model for the porous anode, a single-phase model for the polymer electrolyte membrane, a two-phase mass transport model for the porous cathode, and a homogeneous mist-flow model for the cathode flow field. The two-phase mass transport models take account the effect of non-equilibrium evaporation/ condensation at the gas-liquid interface. A 3D computer code is then developed based on the integrated model. After being validated against the experimental data reported in the literature, the code was used to investigate numerically transport behaviors at the DMFC anode and their effects on cell performance

  2. Bifunctional anode catalysts for direct methanol fuel cells

    Rossmeisl, Jan; Ferrin, Peter; Tritsaris, Georgios

    2012-01-01

    Using the binding energy of OH* and CO* on close-packed surfaces as reactivity descriptors, we screen bulk and surface alloy catalysts for methanol electro-oxidation activity. Using these two descriptors, we illustrate that a good methanol electro-oxidation catalyst must have three key properties......: (1) the ability to activate methanol, (2) the ability to activate water, and (3) the ability to react off surface intermediates (such as CO* and OH*). Based on this analysis, an alloy catalyst made up of Cu and Pt should have a synergistic effect facilitating the activity towards methanol electro-oxidation....... Adding Cu to a Pt(111) surface increases the methanol oxidation current by more than a factor of three, supporting our theoretical predictions for improved electrocatalysts....

  3. Long range order and hydrogen bonding in liquid methanol: A Monte Carlo simulation

    Shilov, I.Y.; Rode, B.M. [Department of Theoretical Chemistry, Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 52a, A-6020 Innsbruck (Austria); Durov, V.A. [Department of Physical Chemistry, Faculty of Chemistry, Lomonosov Moscow State University, Moscow (Russian Federation)

    1999-02-01

    A Monte Carlo simulation of liquid methanol was performed in NVT ensemble at 298 K using a cubic simulation box containing 500 molecules. Long-range correlations in the liquid are discussed on the basis of site-site radial distribution functions. Hydrogen bonding and topological structure of the methanol aggregates were evaluated in detail, namely the number of linked molecules, formation of branches and cyclic structures. The necessity of larger simulation boxes for a full structural description and thermodynamic characterization of hydrogen-bonded liquids is clearly established by the results. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  4. Temperature effects on the structure of liquid D-methanol through ...

    Here, the liquid consists of deuterated methanol and neutron data was collected on the high- diffractometer at Dhruva, BARC. The corrected data at elevated temperatures (BP (boiling point) and double the BP) show that there is a large change in the H-bonded structure of this liquid. The pre-peak or hump, known to be ...

  5. Nano-Engineered Catalysts for Direct Methanol Fuel Cells

    Myung, Nosang; Narayanan, Sekharipuram; Wiberg, Dean

    2008-01-01

    Nano-engineered catalysts, and a method of fabricating them, have been developed in a continuing effort to improve the performances of direct methanol fuel cells as candidate power sources to supplant primary and secondary batteries in a variety of portable electronic products. In order to realize the potential for high energy densities (as much as 1.5 W h/g) of direct methanol fuel cells, it will be necessary to optimize the chemical compositions and geometric configurations of catalyst layers and electrode structures. High performance can be achieved when catalyst particles and electrode structures have the necessary small feature sizes (typically of the order of nanometers), large surface areas, optimal metal compositions, high porosity, and hydrophobicity. The present method involves electrodeposition of one or more catalytic metal(s) or a catalytic-metal/polytetrafluoroethylene nanocomposite on an alumina nanotemplate. The alumina nanotemplate is then dissolved, leaving the desired metal or metal/polytetrafluoroethylene-composite catalyst layer. Unlike some prior methods of making fine metal catalysts, this method does not involve processing at elevated temperature; all processing can be done at room temperature. In addition, this method involves fewer steps and is more amenable to scaling up for mass production. Alumina nanotemplates are porous alumina membranes that have been fabricated, variously, by anodizing either pure aluminum or aluminum that has been deposited on silicon by electronbeam evaporation. The diameters of the pores (7 to 300 nm), areal densities of pores (as much as 7 x 10(exp 10)sq cm), and lengths of pores (up to about 100 nm) can be tailored by selection of fabrication conditions. In a given case, the catalytic metal, catalytic metal alloy, or catalytic metal/ polytetrafluoroethylene composite is electrodeposited in the pores of the alumina nanotemplate. The dimensions of the pores, together with the electrodeposition conditions

  6. Measurements and modeling of quaternary (liquid + liquid) equilibria for mixtures of (methanol or ethanol + water + toluene + n-dodecane)

    Mohammad Doulabi, F.S.; Mohsen-Nia, M.; Modarress, H.

    2006-01-01

    The extraction of aromatic compound toluene from alkane, dodecane, by mixed solvents (water + methanol) (water + ethanol) and (methanol + ethanol) have been studied by (liquid + liquid) equilibrium (LLE) measurements at three temperatures (298.15, 303.15, and 313.15) K and ambient pressure. The compositions of liquid phases at equilibrium were determined by gas liquid chromatography. The experimental tie-line data for three quaternary mixtures of {(water + methanol) + toluene + dodecane}, {(water + ethanol) + toluene + dodecane}, and {(methanol + ethanol) + toluene + dodecane} are presented. The experimental quaternary LLE data have been satisfactorily correlated by using the UNIQUAC and NRTL activity coefficient models. The parameters of the models have been evaluated and presented. The tie-line data of the studied quaternary mixtures also were correlated using the Hand method. The partition coefficients and the selectivity factor of solvent are calculated and compared for the three mixed solvents. The comparisons indicate that the selectivity factor for mixed solvent (methanol + ethanol) is higher than the other two mixed solvents at the three studied temperatures. However, considering the temperature variations of partition coefficients of toluene in two liquid phases at equilibrium, an optimum temperature may be obtained for an efficient extraction of toluene from dodecane by the mixed solvents

  7. Long Term Performance Study of a Direct Methanol Fuel Cell Fed with Alcohol Blends

    Eleuterio Mora

    2013-01-01

    Full Text Available The use of alcohol blends in direct alcohol fuel cells may be a more environmentally friendly and less toxic alternative to the use of methanol alone in direct methanol fuel cells. This paper assesses the behaviour of a direct methanol fuel cell fed with aqueous methanol, aqueous ethanol and aqueous methanol/ethanol blends in a long term experimental study followed by modelling of polarization curves. Fuel cell performance is seen to decrease as the ethanol content rises, and subsequent operation with aqueous methanol only partly reverts this loss of performance. It seems that the difference in the oxidation rate of these alcohols may not be the only factor affecting fuel cell performance.

  8. Methanol electro-oxidation and direct methanol fuel cell using Pt/Rh and Pt/Ru/Rh alloy catalysts

    Choi, Jong-Ho; Park, Kyung-Won; Park, In-Su; Nam, Woo-Hyun; Sung, Yung-Eun

    2004-01-01

    Pt-based binary or ternary catalysts containing Rh for use as anodes in direct methanol fuel cells (DMFC) were synthesized by borohydride reduction method combined with freeze-drying. The resulting catalysts had a specific surface area of approximately 65-75 m 2 /g. X-ray diffraction (XRD) patterns indicated that the catalysts were well alloyed and the average size of alloy catalysts was confirmed by transmission electron microscopy (TEM). The Pt/Rh (2:1) and Pt/Ru/Rh (5:4:1) alloy catalysts showed better catalytic activities for methanol electro-oxidation than Pt or Pt/Ru (1:1), respectively

  9. Manufacturing technologies for direct methanol fuel cells (DMFCs)

    Gluesen, Andreas; Mueller, Martin; Kimiaie, Nicola; Konradi, Irene; Mergel, Juergen; Stolten, Detlef [Forschungszentrum Juelich (Germany). Inst. of Energy Research - IEF-3: Fuel Cells

    2010-07-01

    Fuel cell research is focussing on increasing power density and lifetime and reducing costs of the whole fuel cell system. In order to reach these aims, it is necessary to develop appropriately designed components outgoing from high quality materials, a suitable manufacturing process and a well balanced system. To make use of the advantages that can be obtained by developing production technology, we are mainly improving the coating and assembling techniques for polymer electrolyte fuel cells, especially Direct Methanol Fuel Cells (DMFCs). Coating is used for making fuel cell electrodes as well as highly conductive contacts. Assembling is used to join larger components like membrane electrode assemblies (MEAs) and bipolar units consisting of flow fields and the separator plate, as well as entire stacks. On the one hand a reproducible manufacturing process is required to study fine differences in fuel cell performance affected by new materials or new designs. On the other hand a change in each parameter of the manufacturing process itself can change product properties and therefore affect fuel cell performance. As a result, gas diffusion electrodes (GDEs) are now produced automatically in square-meter batches, the hot-pressing of MEAs is a fully automated process and by pre-assembling the number of parts that have to be assembled in a stack was reduced by a factor of 10. These achievements make DMFC manufacturing more reproducible and less error-prone. All these and further developments of manufacturing technology are necessary to make DMFCs ready for the market. (orig.)

  10. Nafion®/H-ZSM-5 composite membranes with superior performance for direct methanol fuel cells

    Yildirim, M.H.; Curos, Anna Roca; Motuzas, Julius; Motuzas, J.; Julbe, Anne; Stamatialis, Dimitrios; Wessling, Matthias

    2009-01-01

    Solution cast composite direct methanol fuel cell membranes (DEZ) based on DE2020 Nafion® dispersion and in-house prepared H-ZSM-5 zeolites with different Si/Al ratios were prepared and thoroughly characterized for direct methanol fuel cell (DMFC) applications. All composite membranes have indeed

  11. Electrochemical characterization of Pt-Ru-Pd catalysts for methanol oxidation reaction in direct methanol fuel cells.

    Choi, M; Han, C; Kim, I T; An, J C; Lee, J J; Lee, H K; Shim, J

    2011-01-01

    PtRuPd nanoparticles on carbon black were prepared and characterized as electrocatalysts for methanol oxidation reaction in direct methanol fuel cells. Nano-sized Pd (2-4 nm) particles were deposited on Pt/C and PtRu/C (commercial products) by a simple chemical reduction process. The structural and physical information of the PtRuPd/C were confirmed by TEM and XRD, and their electrocatalytic activities were measured by cyclic voltammetry and linear sweep voltammetry. The catalysts containing Pd showed higher electrocatalytic activity for methanol oxidation reaction than the other catalysts. This might be attributed to an increase in the electrochemical surface area of Pt, which is caused by the addition of Pd; this results in increased catalyst utilization.

  12. Low methanol-permeable polyaniline/Nafion composite membrane for direct methanol fuel cells

    Wang, C. H.; Chen, C. C.; Hsu, H. C.; Du, H. Y.; Chen, C. P.; Hwang, J. Y.; Chen, L. C.; Shih, H. C.; Stejskal, Jaroslav; Chen, K. H.

    2009-01-01

    Roč. 190, č. 2 (2009), s. 279-284 ISSN 0378-7753 R&D Projects: GA AV ČR IAA4050313 Institutional research plan: CEZ:AV0Z40500505 Keywords : DMFC * methanol crossover * polyaniline Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.792, year: 2009

  13. First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation

    Riisager, Anders; Jørgensen, Betina; Wasserscheid, Peter

    2006-01-01

    A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)(2)I-2]-[BMIM]I -SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation.......A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)(2)I-2]-[BMIM]I -SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation....

  14. New polymeric electrolyte membranes based on proton donor proton acceptor properties for direct methanol fuel cells

    Manea, G.C.; Mulder, M.H.V.

    2002-01-01

    In order to reduce the high methanol permeability of membranes in a direct methanol fuel cell application new and better materials are still required. In this paper membranes made from polybenzimidazole/sulfonated polysulfone are given and compared with homopolymer membranes made from sulfonated

  15. Characterization of polymer blends PES/SPSf and PES/SPEEK for direct methanol fuel cells

    Manea, G.C.; Mulder, M.H.V.

    2002-01-01

    Existing polymer electrolyte membranes (PEMs) applied for hydrogen fuel cells are frequently not suitable for direct methanol fuel cells due to the high methanol permeability. Therefore, new materials are required and in order to avoid laborious fuel cell experiments with a so-called

  16. Enhancing the methanol tolerance of platinum nanoparticles for the cathode reaction of direct methanol fuel cells through a geometric design.

    Feng, Yan; Ye, Feng; Liu, Hui; Yang, Jun

    2015-11-18

    Mastery over the structure of nanoparticles might be an effective way to enhance their performance for a given application. Herein we demonstrate the design of cage-bell nanostructures to enhance the methanol tolerance of platinum (Pt) nanoparticles while remaining their catalytic activity for oxygen reduction reaction. This strategy starts with the synthesis of core-shell-shell nanoparticles with Pt and silver (Ag) residing respectively in the core and inner shell regions, which are then agitated with saturated sodium chloride (NaCl) solution to eliminate the Ag component from the inner shell region, leading to the formation of bimetallic nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a metal shell with nano-channels, which exhibit superior methanol-tolerant property in catalyzing oxygen reduction reaction due to the different diffusion behaviour of methanol and oxygen in the porous metal shell of cage-bell structured nanoparticles. In particular, the use of remarkably inexpensive chemical agent (NaCl) to promote the formation of cage-bell structured particles containing a wide spectrum of metal shells highlights its engineering merit to produce highly selective electrocatalysts on a large scale for the cathode reaction of direct methanol fuel cells.

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

    Sheng, Tian; Lin, Xiao; Chen, Zhao-Yang; Hu, P; Sun, Shi-Gang; Chu, You-Qun; Ma, Chun-An; Lin, Wen-Feng

    2015-10-14

    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.

  18. Investigation of Novel Electrolytes for Use in Lithium-Ion Batteries and Direct Methanol Fuel Cells

    Pilar, Kartik

    Energy storage and conversion plays a critical role in the efficient use of available energy and is crucial for the utilization of renewable energy sources. To achieve maximum efficiency of renewable energy sources, improvements to energy storage materials must be developed. In this work, novel electrolytes for secondary batteries and fuel cells have been studied using nuclear magnetic resonance and high pressure x-ray scattering techniques to form a better understanding of dynamic and structural properties of these materials. Ionic liquids have been studied due to their potential as a safer alternative to organic solvent-based electrolytes in lithium-ion batteries and composite sulfonated polyetheretherketone (sPEEK) membranes have been investigated for their potential use as a proton exchange membrane electrolyte in direct methanol fuel cells. The characterization of these novel electrolytes is a step towards the development of the next generation of improved energy storage and energy conversion devices.

  19. First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation.

    Riisager, Anders; Jørgensen, Betina; Wasserscheid, Peter; Fehrmann, Rasmus

    2006-03-07

    A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)2I2]-[BMIM]I-SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation.

  20. (Vapour + liquid) equilibria for (2,2-dimethoxypropane + methanol) and (2,2-dimethoxypropane + acetone)

    Jiang Hui; Li Haoran; Wang Congmin; Tan Taijun; Han Shijun

    2003-01-01

    The isothermal and isobaric (vapour + liquid) equilibria for (2,2-dimethoxypropane + methanol) and (2,2-dimethoxypropane + acetone) measured with an inclined ebulliometer are presented. The experimental results are analysed using the UNIQUAC equation with the temperature-dependent binary parameters with satisfactory results. Isobaric (vapour + liquid) equilibria data for these systems at p=99.99 kPa are compared with the literature data. Experimental vapour pressure of 2,2-dimethoxypropane are also included

  1. A novel method of methanol concentration control through feedback of the amplitudes of output voltage fluctuations for direct methanol fuel cells

    An, Myung-Gi; Mehmood, Asad; Hwang, Jinyeon; Ha, Heung Yong

    2016-01-01

    This study proposes a novel method for controlling the methanol concentration without using methanol sensors for DMFC (direct methanol fuel cell) systems that have a recycling methanol-feed loop. This method utilizes the amplitudes of output voltage fluctuations of DMFC as a feedback parameter to control the methanol concentration. The relationship between the methanol concentrations and the amplitudes of output voltage fluctuations is correlated under various operating conditions and, based on the experimental correlations, an algorithm to control the methanol concentration with no sensor is established. Feasibility tests of the algorithm have been conducted under various operating conditions including varying ambient temperature with a 200 W-class DMFC system. It is demonstrated that the sensor-less controller is able to control the methanol-feed concentration precisely and to run the DMFC systems more energy-efficiently as compared with other control systems. - Highlights: • A new sensor-less algorithm is proposed to control the methanol concentration without using a sensor. • The algorithm utilizes the voltage fluctuations of DMFC as a feedback parameter to control the methanol feed concentration. • A 200 W DMFC system is operated to evaluate the validity of the sensor-less algorithm. • The algorithm successfully controls the methanol feed concentration within a small error bound.

  2. Survey report for fiscal 1998. Achievement report on research and development of direct methanol fuel cell; 1998 nendo direct methanol nenryo denchi no kenkyu kaihatsu seika hokokusho

    NONE

    1999-12-01

    Research and development has been performed on a direct methanol fuel cell (DMFC) to generate electric power through direct chemical reaction of methanol not being given modification as a fuel cell to be used for automotive engines. This paper summarizes the achievements in fiscal 1998. In the research of the membranes to conduct ions for the DMFC, an ion conduction membrane which introduces POSS group as the methanol eliminating functional group was prepared to achieve enhancement in tensile strength, heat resistance, and ion conductivity. In the power generation characteristics of the DMFC, verification was given on power generation performance with as high main power density as 0.1 W/cm{sup 2} by using the available electrolytic membranes and electrode catalysts. The characteristics showed effectiveness of the DMFC as the electric power supply source. In addition, fundamental findings were obtained on factors affecting the power generation characteristics of the DMFC as a result of generating power under different conditions. Research and development was given also on the water-methanol-ion exchange polymeric membrane, ion exchange membranes provided with lipophilic and water repellent electrolyte, solid polymeric membranes having high proton conductivity and low methanol permeability, and a new micro-porous filling type polymeric membrane. (NEDO)

  3. A high selectivity quaternized polysulfone membrane for alkaline direct methanol fuel cells

    Abuin, GC

    2015-04-01

    Full Text Available polysulfone membrane for alkaline direct methanol fuel cells Graciela C. Abuina, Esteban A. Franceschinib, Patrick Nonjolac, Mkhulu K. Mathec, Mmalewane Modibedic, Horacio R. Cortib,* aCentro de Procesos Superficiales, Instituto Nacional de Tecnología...

  4. Direct synthesis of dimethyl carbonate from CO2 and methanol over ...

    The direct synthesis of dimethyl carbonate (DMC) from carbon dioxide (CO2) and methanol is ... Zirconia and ceria-based catalysts were most effective ... construction of a validation plant for dialkyl carbonates .... (mmol of MeOH consumed/2).

  5. A small mono-polar direct methanol fuel cell stack with passive operation

    Chan, Y. H.; Zhao, T. S.; Chen, R.; Xu, C.

    A passive direct methanol fuel cell (DMFC) stack that consists of six unit cells was designed, fabricated, and tested. The stack was tested with different methanol concentrations under ambient conditions. It was found that the stack performance increased when the methanol concentration inside the fuel tank was increased from 2.0 to 6.0 M. The improved performance is primarily due to the increased cell temperature as a result of the exothermic reaction between the permeated methanol and oxygen on the cathode. Moreover, the increased cell temperature enhanced the water evaporation rate on the air-breathing cathode, which significantly reduced water flooding on the cathode and further improved the stack performance. This passive DMFC stack, providing 350 mW at 1.8 V, was successfully applied to power a seagull display kit. The seagull display kit can continuously run for about 4 h on a single charge of 25 cm 3 4.0-M methanol solution.

  6. Optimisation of polypyrrole/Nafion composite membranes for direct methanol fuel cells

    Zhu Jun; Sattler, Rita R.; Garsuch, Arnd; Yepez, Omar; Pickup, Peter G.

    2006-01-01

    Acidic and neutral Nafion[reg] 115 perfluorosulphonate membranes have been modified by in situ polymerization of pyrrole using Fe(III) and H 2 O 2 as oxidizing agents, in order to decrease methanol crossover in direct methanol fuel cells. Improved selectivities for proton over methanol transport and improved fuel cell performances were only obtained with membranes that were modified while in the acid form. Use of Fe(III) as the oxidizing agent can produce a large decrease in methanol crossover, but causes polypyrrole deposition on the surface of the membrane. This increases the resistance of the membrane, and leads to poor fuel cell performances due to poor bonding with the electrodes. Surface polypyrrole deposition can be minimized, and surface polypyrrole can be removed, by using H 2 O 2 . The use of Nafion in its tetrabutylammonium form leads to very low methanol permeabilities, and appears to offer potential for manipulating the location of polypyrrole within the Nafion structure

  7. Characteristics of PVdF copolymer/Nafion blend membrane for direct methanol fuel cell (DMFC)

    Cho, Ki-Yun; Eom, Ji-Yong; Jung, Ho-Young; Choi, Nam-Soon; Lee, Yong Min; Park, Jung-Ki; Choi, Jong-Ho; Park, Kyung-Won; Sung, Yung-Eun

    2004-01-01

    For direct methanol fuel cell, blends of vinylidene fluoride-hexafluoropropylene copolymer (P(VdF-co-HFP)) and Nafion were prepared the different equivalent weight of Nafion. The investigations of the blend morphology were performed by means of permeability test, uptake measurement, differential-scanning calorimetry (DSC), and scanning electron microscopy. In the blend membranes, many pores were created as the content of Nafion in blend increased. Then, the methanol uptake was sharply increased. But the methanol permeability was not sharply increased because the methanol permeation through blend membranes is diffusion-controlled process. The methanol permeability of N10 (low equivalent weight) series was similar to that of N11 series (high equivalent weight). The proton conductivity of N10 series was around one and a half times higher than that of N11 series. The cell performance of the blend was much enhanced when the equivalent weight of Nafion was 1000

  8. Water transport in the cathode channels of direct methanol fuel cells; Wasseraustrag aus den Kathodenkanaelen von Direkt-Methanol-Brennstoffzellen

    Schroeder, Alexander

    2011-10-26

    Mass transport phenomena are vital for the operating performance of direct methanol fuel cells. In particular, the discharge of liquid water from the cathode channels is crucial for the supply of oxygen to the cathode and thus for operational stability. Droplets of water in the pores of the the diffusion layer and the cathode channels may lower the power output and induce locally negative current densities as they considerably limit the oxygen supply. This work investigates the water discharge from the cathode channels using neutron radiography, synchrotron radiography and locally resolved current density measurements and it identifies ways of improving the operational stability. Neutron radiography is a measuring technique suitable for detecting the water distribution in fuels cells under operating conditions. Synchrotron radiography is a method complementary to neutron radiography, allowing a more detailed analysis of smaller areas. Special test cells adapted to both measuring methods are developed. Their electrode areas are radiographed either frontally or laterally. To enable locally resolved current density measurements, a printed circuit board with a segmented contact area is integrated into each of the test cells. The measuring technique used is based on compensated sensor resistors, which ensure a reactionless measurement. In addition, the temperature distribution and the pressure drop on the cathod side are recorded. In order to correlated the water distribution, the current density distribution and the pressure drop, neutron radiography and synchrotron radiography are both combined with locally resolved current density measurements. Furthermore, current density measurements are performed under constant laboratory conditions to study the variation of paramenters. A measurement with a stack is also performed. The experiments reveal fundamental interdependencies between different factors and the discharge of water. At a given air ratio, the geometry and the

  9. Emerging methanol-tolerant AlN nanowire oxygen reduction electrocatalyst for alkaline direct methanol fuel cell.

    Lei, M; Wang, J; Li, J R; Wang, Y G; Tang, H L; Wang, W J

    2014-08-11

    Replacing precious and nondurable Pt catalysts with cheap materials is a key issue for commercialization of fuel cells. In the case of oxygen reduction reaction (ORR) catalysts for direct methanol fuel cell (DMFC), the methanol tolerance is also an important concern. Here, we develop AlN nanowires with diameters of about 100-150 nm and the length up to 1 mm through crystal growth method. We find it is electrochemically stable in methanol-contained alkaline electrolyte. This novel material exhibits pronounced electrocatalytic activity with exchange current density of about 6.52 × 10(-8) A/cm(2). The single cell assembled with AlN nanowire cathodic electrode achieves a power density of 18.9 mW cm(-2). After being maintained at 100 mA cm(-2) for 48 h, the AlN nanowire-based single cell keeps 92.1% of the initial performance, which is in comparison with 54.5% for that assembled with Pt/C cathode. This discovery reveals a new type of metal nitride ORR catalyst that can be cheaply produced from crystal growth method.

  10. Coupling of subcritical methanol with acidic ionic liquids for the acidity reduction of naphthenic acids

    Zafar Faisal

    2017-09-01

    Full Text Available The presence of naphthenic acids (NAs in crude oil is the major cause of corrosion in the refineries and its processing equipment. The goal of this study is to reduce the total acid number (TAN of NAs by treating them with subcritical methanol in the presence of acidic ionic liquid (AIL catalysts. Experiments were carried out in an autoclave batch reactor and the effect of different reaction parameters was investigated. It was observed that TAN reduction was positively dependent on the temperature and concentration of the AIL whereas excess of methanol has a negative effect. Approximately 90% TAN reduction was achieved under the optimized reaction conditions using [BMIM]HSO4 as catalyst. It was also perceived from the experimental results that the AILs with longer alkyl chain exhibited higher catalytic activity. The activity and stability of AIL showed that they can be promising catalyst to esterify NAs under subcritical methanol.

  11. Development and characterisation of a portable direct methanol fuel cell stack

    Oedegaard, A.

    2005-11-21

    This thesis deals with the development and characterisation of a portable direct methanol fuel cell stack. In addition, calculations of the transport of methanol and water in the membrane are compared with experimentally determined values. It also includes investigations of the behaviour of single-cells and some of its components, as the anode gas diffusion layer and the anode flow-field. For the addition of methanol to the anode feed loop, a passive concept based on a permeable tube was developed and verified by both experiments and simulations. (orig.)

  12. A simple preparation of very high methanol tolerant cathode electrocatalyst for direct methanol fuel cell based on polymer-coated carbon nanotube/platinum.

    Yang, Zehui; Nakashima, Naotoshi

    2015-07-20

    The development of a durable and methanol tolerant electrocatalyst with a high oxygen reduction reaction activity is highly important for the cathode side of direct methanol fuel cells. Here, we describe a simple and novel methodology to fabricate a practically applicable electrocatalyst with a high methanol tolerance based on poly[2,2'-(2,6-pyridine)-5,5'-bibenzimidazole]-wrapped multi-walled carbon nanotubes, on which Pt nanoparticles have been deposited, then coated with poly(vinylphosphonic acid) (PVPA). The polymer coated electrocatalyst showed an ~3.3 times higher oxygen reduction reaction activity compared to that of the commercial CB/Pt and methanol tolerance in the presence of methanol to the electrolyte due to a 50% decreased methanol adsorption on the Pt after coating with the PVPA. Meanwhile, the peroxide generation of the PVPA coated electrocatalyst was as low as 0.8% with 2 M methanol added to the electrolyte, which was much lower than those of the non-PVPA-coated electrocatalyst (7.5%) and conventional CB/Pt (20.5%). Such a high methanol tolerance is very important for the design of a direct methanol fuel cell cathode electrocatalyst with a high performance.

  13. Performance of direct methanol fuel cell with a palladium–silica nanofibre/Nafion composite membrane

    Thiam, H.S.; Daud, W.R.W.; Kamarudin, S.K.; Mohamad, A.B.; Kadhum, A.A.H.; Loh, K.S.; Majlan, E.H.

    2013-01-01

    Highlights: • This study introduces Pd–SiO 2 Carbon Nano Fibre as an additive to Nafion membrane. • It investigates the effects of membrane annealing temperature and casting solvent. • Results show that Pd–SiO 2 fibre/Nafion performs lower methanol permeability. • This could effectively reduces methanol crossover in direct methanol fuel cell. - Abstract: Palladium–silica nanofibres (Pd–SiO 2 fibre) were adopted as an additive to Nafion recast membranes in order to reduce methanol crossover and improve the cell performance. The performance of a membrane electrode assembly (MEA) with fabricated composite membrane was evaluated through a passive air-breathing single cell direct methanol fuel cell (DMFC). The limiting crossover current density was measured to determine the methanol permeation in the DMFC. The effects of membrane annealing temperature and casting solvent of composite membrane on the cell performance were investigated and are discussed here. Compared to recast Nafion with the same thickness (150 μm), the Pd–SiO 2 fibre/Nafion composite membrane exhibited higher performance and lower methanol permeability. A maximum power density of 10.4 mW cm −2 was obtained with a 2 M methanol feed, outperforming the much thicker commercial Nafion 117 with a power density of 7.95 mW cm −2 under the same operating conditions. The experimental results showed that the Pd–SiO 2 fibre as inorganic fillers for Nafion could effectively reduce methanol crossover and improve the membrane performance in DMFC applications

  14. Core-hole-induced dynamical effects in the x-ray emission spectrum of liquid methanol.

    Ljungberg, M P; Zhovtobriukh, I; Takahashi, O; Pettersson, L G M

    2017-04-07

    We compute the x-ray emission spectrum of liquid methanol, with the dynamical effects that result from the creation of the core hole included in a semiclassical way. Our method closely reproduces a fully quantum mechanical description of the dynamical effects for relevant one-dimensional models of the hydrogen-bonded methanol molecules. For the liquid, we find excellent agreement with the experimental spectrum, including the large isotope effect in the first split peak. The dynamical effects depend sensitively on the initial structure in terms of the local hydrogen-bonding (H-bonding) character: non-donor molecules contribute mainly to the high-energy peak while molecules with a strong donating H-bond contribute to the peak at lower energy. The spectrum thus reflects the initial structure mediated by the dynamical effects that are, however, seen to be crucial in order to reproduce the intensity distribution of the recently measured spectrum.

  15. High-Performance Direct Methanol Fuel Cells with Precious-Metal-Free Cathode.

    Li, Qing; Wang, Tanyuan; Havas, Dana; Zhang, Hanguang; Xu, Ping; Han, Jiantao; Cho, Jaephil; Wu, Gang

    2016-11-01

    Direct methanol fuel cells (DMFCs) hold great promise for applications ranging from portable power for electronics to transportation. However, apart from the high costs, current Pt-based cathodes in DMFCs suffer significantly from performance loss due to severe methanol crossover from anode to cathode. The migrated methanol in cathodes tends to contaminate Pt active sites through yielding a mixed potential region resulting from oxygen reduction reaction and methanol oxidation reaction. Therefore, highly methanol-tolerant cathodes must be developed before DMFC technologies become viable. The newly developed reduced graphene oxide (rGO)-based Fe-N-C cathode exhibits high methanol tolerance and exceeds the performance of current Pt cathodes, as evidenced by both rotating disk electrode and DMFC tests. While the morphology of 2D rGO is largely preserved, the resulting Fe-N-rGO catalyst provides a more unique porous structure. DMFC tests with various methanol concentrations are systematically studied using the best performing Fe-N-rGO catalyst. At feed concentrations greater than 2.0 m, the obtained DMFC performance from the Fe-N-rGO cathode is found to start exceeding that of a Pt/C cathode. This work will open a new avenue to use nonprecious metal cathode for advanced DMFC technologies with increased performance and at significantly reduced cost.

  16. Effect of alkanolammonium formates ionic liquids on vapour liquid equilibria of binary systems containing water, methanol, and ethanol

    Li Xuemei; Shen Chong; Li Chunxi

    2012-01-01

    Highlights ► Vapour pressures for six ternary systems containing an IL were measured. ► Components studied were water, ethanol, methanol, and alkanolammonium formates. ► The isobaric VLE were predicted using the fitted binary NRTL parameters. ► The ILs studied can generate a promising salt effect on VLE of azeotrope. ► [HMEA][HCOO] might be used as a potential entrainer in extractive distillation. - Abstract: Vapour pressures were measured using a quasi-static ebulliometer for the pseudo-binary mixtures of (water + ethanol), (water + methanol), and (methanol + ethanol) containing an alkanolammonium-based ionic liquid (IL), namely, mono-ethanolammonium formate ([HMEA][HCOO]) and di-ethanolammonium formate ([HDEA][HCOO]), respectively, with fixed IL mass fraction of 0.30 and over the temperature ranges of (292.12 to 371.13) K. The vapour pressures of the IL-containing ternary systems were favourably correlated using the NRTL model with an overall average absolute relative deviation (AARD) of 0.0082. Further, the salt effects of [HMEA][HCOO] and [HDEA][HCOO] on isobaric vapour liquid equilibria (VLE) of azeotrope and close boiling mixture, especially for the mixtures of (water + ethanol) and (methanol + ethanol), were investigated and compared with other ILs in terms of the x′–y phase diagrams predicted with the binary NRTL parameters. It is demonstrated that the relative volatilities of ethanol to water and ethanol to methanol are enhanced, and [HMEA][HCOO] might be used as a promising entrainer for the efficient separation of ethanol aqueous solution by special rectification.

  17. Influencing parameters of water and methanol transport in a big direct methanol fuel cell; Einflussgroessen auf den Wasser- und Methanoltransport einer groesseren Direkt-Methanol Brennstoffzelle

    Schonert, Morten

    2008-07-01

    The author investigated the influencing parameters of water and methanol transport in a big direct methanol fuel cell (Pel > 1 kW) with the intention of making the direct methanol fuel cell system water-autonomous. As water is consumed during the electrochemical reaction on the anode while more water is produced on the cathode, the difference must be removed via the air. Any further water produced on the cathode must be condensed and recirculated to the anode. With increasing ambient temperature, the air volume flow must be reduced because otherwise more water would be removed than is acceptable. Low air volume flow on the cathode causes unstable cell voltage, which is also assumed to be caused by excess water production. For this reason, an attempt was made to prevent excess water production on the cathode by a system engineering approach. It was found that at the low air volume flow required for water autonomy, water permeation through the membrane-electrode aggregate (MEA) depends on the uptake capacity and on the time of residue of air over the cathode and less on the cathode material. Water permeation stops when the concentration gradient is balanced. Apart from the water permeation, there is also water transport through the Nafion {sup registered} membrane, i.e. so-called electroosmotic drag (ESD). This is an active transport mechanism that can also work against a concentration gradient. It could be shown that the EOD can be reduced by using water-impermeable materials for the gas diffusion layer on the anode. This will reduce the water volume that reaches the membrane, i.e. the water on the cathode. On the other hand, there was no measurable effect of the cathode design on water or methanol transport. The electrochemical performance of the membrane-electrode units under investigation was robust in case of many influencing parameters, e.g. dispersion, the conditions of MEA fabrication by hot pressing, themembrane thickness and the rate of methanol permeation

  18. Mixtures of methanol and 2-propanol as a potential fuel for direct alcohol fuel cells

    S. LJ. GOJKOVIC

    2007-12-01

    Full Text Available The electrochemical oxidation of methanol, 2-propanol, and their mixtures was investigated on a Pt/C thin film electrode in acid solution. It was confirmed that the oxidation of 2-propanol commences at less positive potentials than that of methanol and exhibits significantly higher oxidation current densities at low potentials. When both methanol and 2-propanol were present in the solution, the onset of the oxidation current was the same as for the oxidation of pure 2-propanol. Although both alcohols inhibit the oxidation reaction of each other to a certain extent, steady-state polarization measurements showed that their mixture provides higher current densities than single alcohols over the entire potential region from the hydrogen region to oxide formation on the Pt surface. This implies that the addition of 2-propanol into the fuel may extend the operational range of direct methanol fuel cells.

  19. Selective electrocatalysts toward a prototype of the membraneless direct methanol fuel cell.

    Feng, Yan; Yang, Jinhua; Liu, Hui; Ye, Feng; Yang, Jun

    2014-01-22

    Mastery over the structure of nanomaterials enables control of their properties to enhance their performance for a given application. Herein we demonstrate the design and fabrication of Pt-based nanomaterials with enhanced catalytic activity and superior selectivity toward the reactions in direct methanol fuel cells (DMFCs) upon the deep understanding of the mechanisms of these electrochemical reactions. In particular, the ternary Au@Ag2S-Pt nanocomposites display superior methanol oxidation reaction (MOR) selectivity due to the electronic coupling effect among different domains of the nanocomposites, while the cage-bell structured Pt-Ru nanoparticles exhibit excellent methanol tolerance for oxygen reduction reaction (ORR) at the cathode because of the differential diffusion of methanol and oxygen in the porous Ru shell of the cage-bell nanoparticles. The good catalytic selectivity of these Pt-based nanomaterials via structural construction enables a DMFC to be built without a proton exchange membrane between the fuel electrode and the oxygen electrode.

  20. Supported Ionic Liquid Phase (SILP) Catalysis for the Production of Acetic acid by Methanol Carbonylation

    Hanning, Christopher William

    at the beginning with the construction of a suitable test reactor, then followed by the synthesis and testing of all the catalysts reported. A variety of nitrogen based ionic liquids were initially tested, giving good results and stability in the system. Later a number of phosphonium based salts were tested (these......The work presented here is focused on the development of a new reaction process. It applies Supported Ionic Liquid Phase (SILP) catalysis to a specific reaction. By reacting methanol and carbon monoxide over a rhodium catalyst, acetic acid can be formed. This reaction is important on a large scale...... were no longer classified as ionic liquids due to melting points above 100◦C). The phosphonium salts showed even better activity in the system compared to the ionic liquids. Overall the work has shown that this process for the manufacture of acetic acid is viable industrially. This is backed up...

  1. Investigation of nano Pt and Pt-based alloys electrocatalysts for direct methanol fuel cells and their properties

    Chunguang Suo

    2014-03-01

    Full Text Available The electrocatalysts used in micro direct methanol fuel cell (μDMFC, such as Pt/C and Pt alloy/C, prepared by liquid-phase NaBH4 reduction method have been investigated. XC-72 (Cobalt corp. Company, U.S.A is chosen as the activated carrier for the electrocatalysts to keep the catalysts powder in the range of several nanometers. The XRD, SEM, EDX analyses indicated that the catalysts had small particle size in several nanometers, in excellent dispersed phase and the molar ratio of the precious metals was found to be optimal. The performances of the DMFCs using cathodic catalyst with Pt percentage of 30wt% and different anodic catalysts (Pt-Ru, Pt-Ru-Mo were tested. The polarization curves and power density curves of the cells were measured to determine the optimal alloy composition and condition for the electrocatalysts. The results showed that the micro direct methanol fuel cell with 30wt% Pt/C as the cathodic catalyst and n(Pt:n(Ru:n(Mo = 3:2:2 PtRuMo/C as the anodic catalyst at room temperature using 2.0mol/L methanol solution has the best performances.

  2. Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOTH) Process

    None

    1998-12-21

    The Liquid Phase Methanol (LPMEOW) Demonstration Project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership) to produce methanol from coal-derived synthesis gas (syngas). Air Products and Chemicals, Inc. (Air Products) and Eastman Chemical Company (Eastman) formed the Partnership to execute the Demonstration Project. The LPMEOI-P Process Demonstration Unit was built at a site located at the Eastman coal-to-chemicals complex in Kingsport. During this quarter, initial planning and procurement work continued on the seven project sites which have been accepted for participation in the off-site, product-use test program. Approximately 12,000 gallons of fuel-grade methanol (98+ wt% methanol, 4 wt% water) produced during operation on carbon monoxide (CO)-rich syngas at the LPMEOW Demonstration Unit was loaded into trailers and shipped off-site for Mure product-use testing. At one of the projects, three buses have been tested on chemical-grade methanol and on fhel-grade methanol from the LPMEOW Demonstration Project. During the reporting period, planning for a proof-of-concept test run of the Liquid Phase Dimethyl Ether (LPDME~ Process at the Alternative Fuels Development Unit (AFDU) in LaPorte, TX continued. The commercial catalyst manufacturer (Calsicat) has prepared the first batch of dehydration catalyst in large-scale equipment. Air Products will test a sample of this material in the laboratory autoclave. Catalyst activity, as defined by the ratio of the rate constant at any point in time to the rate constant for freshly reduced catalyst (as determined in the laborato~ autoclave), was monitored for the initial extended operation at the lower initial reactor operating temperature of 235oC. At this condition, the decrease in catalyst activity with time from the period 20 December 1997 through 27 January 1998 occurred at a rate of 1.0% per

  3. Effect of operating conditions on energy efficiency for a small passive direct methanol fuel cell

    Chu Deryn; Jiang Rongzhong

    2006-01-01

    Energy conversion efficiency was studied in a direct methanol fuel cell (DMFC) with an air-breathing cathode using Nafion 117 as electrolyte membrane. The effect of operating conditions, such as methanol concentration, discharge voltage and temperature, on Faradic and energy conversion efficiencies was analyzed under constant voltage discharge with quantitative amount of fuel. Both of Faradic and energy conversion efficiencies decrease significantly with increasing methanol concentration and environmental temperature. The Faradic conversion efficiency can be as high as 94.8%, and the energy conversion efficiency can be as high as 23.9% if the environmental temperature is low enough (10 deg. C) under constant voltage discharge at 0.6 V with 3 M methanol for a DMFC bi-cell. Although higher temperature and higher methanol concentration can achieve higher discharge power, it will result in considerable losses of Faradic and energy conversion efficiencies for using Nafion electrolyte membrane. Development of alternative highly conductive membranes with significantly lower methanol crossover is necessary to avoid loss of Faradic conversion efficiency with temperature and with fuel concentration

  4. Low-Pt-Content Anode Catalyst for Direct Methanol Fuel Cells

    Narayanan, Sekharipuram; Whitacre, Jay

    2008-01-01

    Combinatorial experiments have led to the discovery that a nanophase alloy of Pt, Ru, Ni, and Zr is effective as an anode catalyst material for direct methanol fuel cells. This discovery has practical significance in that the electronic current densities achievable by use of this alloy are comparable or larger than those obtained by use of prior Pt/Ru catalyst alloys containing greater amounts of Pt. Heretofore, the high cost of Pt has impeded the commercialization of direct methanol fuel cells. By making it possible to obtain a given level of performance at reduced Pt content (and, hence, lower cost), the discovery may lead to reduction of the economic impediment to commercialization.

  5. Fabrication and Characterization of Chitosan Nanoparticle-Incorporated Quaternized Poly(Vinyl Alcohol) Composite Membranes as Solid Electrolytes for Direct Methanol Alkaline Fuel Cells

    Li, Pin-Chieh; Liao, Guan–Ming; Kumar, S. Rajesh; Shih, Chao-Ming; Yang, Chun-Chen; Wang, Da-Ming; Lue, Shingjiang Jessie

    2016-01-01

    Highlights: • Preparation of chitosan nanoparticles from bulk to enhance the degree of deacetylation. • The incorporation of chitosan nanoparticles into a QPVA matrix to form a nanocomposite membrane. • The nanocomposite constructed into thin-film membranes using the solution casting method. • To improve permeability, glutaraldehyde was cross-linked with the nanocomposite membranes. • A direct methanol alkaline fuel cell was studied at different temperatures. - Abstract: In this study, we designed a method for the preparation of chitosan nanoparticles incorporated into a quaternized poly(vinyl alcohol) (QPVA) matrix for direct methanol alkaline fuel cells (DMAFCs). The structural and morphological properties of the prepared nanocomposites were studied using X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscope (TEM) and dynamic laser-light scattering (DLS). The crystallinity of the nanocomposite solid electrolytes containing 0 and 10% chitosan nanoparticles were investigated using differential scanning calorimetry (DSC). The electrochemical measurement of resulting nanocomposite membranes were analyzed according to the following parameters: methanol permeability, liquid uptakes, ionic conductivity and cell performances. The composite membranes with 10% chitosan nanoparticles in a QPVA matrix (CQPVA) show suppressed methanol permeability and higher ionic conductivity than pristine QPVA. In addition, the glutaraldehyde cross-linked nanocomposite film exhibited improvement on the methanol barrier property at 80 °C. The peak power density of the DMAFCs reached 67 mW cm −2 when fed into 1 M of methanol in 6 M of KOH.

  6. Design and Control of High Temperature PEM Fuel Cell Systems using Methanol Reformers with Air or Liquid Heat Integration

    Andreasen, Søren Juhl; Kær, Søren Knudsen; Sahlin, Simon Lennart

    2013-01-01

    The present work describes the ongoing development of high temperature PEM fuel cell systems fuelled by steam reformed methanol. Various fuel cell system solutions exist, they mainly differ depending on the desired fuel used. High temperature PEM (HTPEM) fuel cells offer the possibility of using...... methanol is converted to a hydrogen rich gas with CO2 trace amounts of CO, the increased operating temperatures allow the fuel cell to tolerate much higher CO concentrations than Nafion-based membranes. The increased tolerance to CO also enables the use of reformer systems with less hydrogen cleaning steps...... liquid fuels such as methanol, due to the increased robustness of operating at higher temperatures (160-180oC). Using liquid fuels such as methanol removes the high volume demands of compressed hydrogen storages, simplifies refueling, and enables the use of existing fuel distribution systems. The liquid...

  7. Nuclear magnetic resonance spectroscopic investigation of anode exhaust of direct methanol fuel cells without isotope enrichment

    Byun, Young Seok; Hwang, Reo Yun; Han, Ochee

    2016-01-01

    Fuel cells are devices that electrochemically convert the chemical energy of fuels such as natural gas, gasoline, and methanol, into electricity. Fuel cells more efficiently use energy than internal combustion engines and do not produce undesirable pollutants, such as NO_x ,SO_x and particulates. Fuel cells can be distinguished from one another by their electrolytes. Among the various direct alcohol fuel cells, direct methanol fuel cells (DMFCs) have been developed most. However, DMFCs have several practical problems such as methanol crossove r from an anode to a cathode and slow methanol oxidation reaction rates. Therefore, understanding the electrochemical reaction mechanisms of DMFCs may provide clues to solve these problems, and various analytical methods have been employed to examine these mechanisms. We demonstrated that "1H and "1"3C NMR spectroscopy can be used for analyzing anode exhausts of DMFCs operated with methanol without any isotope enrichment. However, the low sensitivity of NMR spectroscopy hindered our efforts to detect minor reaction intermediates. Therefore, sensitivity enhancement techniques such as dynamic nuclear polarization (DNP) NMR methods and/or presaturation methods to increase the dynamic range of the proton spectra by pre-saturating large water signals, are expected to be useful to detect low-concentration species

  8. Nuclear magnetic resonance spectroscopic investigation of anode exhaust of direct methanol fuel cells without isotope enrichment

    Byun, Young Seok; Hwang, Reo Yun; Han, Ochee [Western Seoul Center, Korea Basic Science Institute, Seoul (Korea, Republic of)

    2016-12-15

    Fuel cells are devices that electrochemically convert the chemical energy of fuels such as natural gas, gasoline, and methanol, into electricity. Fuel cells more efficiently use energy than internal combustion engines and do not produce undesirable pollutants, such as NO{sub x} ,SO{sub x} and particulates. Fuel cells can be distinguished from one another by their electrolytes. Among the various direct alcohol fuel cells, direct methanol fuel cells (DMFCs) have been developed most. However, DMFCs have several practical problems such as methanol crossove r from an anode to a cathode and slow methanol oxidation reaction rates. Therefore, understanding the electrochemical reaction mechanisms of DMFCs may provide clues to solve these problems, and various analytical methods have been employed to examine these mechanisms. We demonstrated that {sup 1}H and {sup 13}C NMR spectroscopy can be used for analyzing anode exhausts of DMFCs operated with methanol without any isotope enrichment. However, the low sensitivity of NMR spectroscopy hindered our efforts to detect minor reaction intermediates. Therefore, sensitivity enhancement techniques such as dynamic nuclear polarization (DNP) NMR methods and/or presaturation methods to increase the dynamic range of the proton spectra by pre-saturating large water signals, are expected to be useful to detect low-concentration species.

  9. Experimental Validation of Methanol Crossover in a Three-dimensional, Two-Fluid Model of a Direct Methanol Fuel Cell

    Olesen, Anders Christian; Berning, Torsten; Kær, Søren Knudsen

    2012-01-01

    A fully coupled three-dimensional, steady-state, two-fluid, multi-component and non-isothermal DMFC model has been developed in the commercial CFD package CFX 13 (ANSYS inc.). It accounts for the presence of micro porous layers, non-equilibrium phase change, and methanol and water uptake...... in the ionomer phase of the catalytic layer, and detailed membrane transport of methanol and water. In order to verify the models ability to predict methanol crossover, simulation results are compared with experimental measurements under different current densities along with air and methanol stoichiometries....... Methanol crossover is indirectly measured based on the combined anode and cathode exhaust CO2 mole fraction and by accounting for the CO2 production at the anode as a function of current density. This approach is simple and assumes that all crossed over methanol is oxidized. Moreover, it takes CO2...

  10. Reduction of methanol crossover by thin cracked metal barriers at the interface between membrane and electrode in direct methanol fuel cells

    Kim, Sungjun; Jang, Segeun; Kim, Sang Moon; Ahn, Chi-Yeong; Hwang, Wonchan; Cho, Yong-Hun; Sung, Yung-Eun; Choi, Mansoo

    2017-09-01

    This work reports the successful reduction in methanol crossover by creating a thin cracked metal barrier at the interface between a Nafion® membrane and an electrode in direct methanol fuel cells (DMFCs). The cracks are generated by simple mechanical stretching of a metal deposited Nafion® membrane as a result of the elastic mismatch between the two attached surfaces. The cracked metal barriers with varying strains (∼0.5 and ∼1.0) are investigated and successfully incorporated into the DMFC. Remarkably, the membrane electrode assembly with the thin metal crack exhibits comparable ohmic resistance as well as reduction of methanol crossover, which enhanced the device performance.

  11. Liquid methane gelled with methanol and water reduces rate of nitrogen absorption

    Vanderwall, E. M.

    1972-01-01

    Dilution of gelant vapor with inert carrier gas accomplishes gelation. Mixture is injected through heated tube and orifice into liquid methane for immediate condensation within bulk of liquid. Direct dispersion of particles in liquid avoids condensation on walls of vessel and eliminates additional mixing.

  12. Sensor-less control of the methanol concentration of direct methanol fuel cells at varying ambient temperatures

    An, Myung-Gi; Mehmood, Asad; Ha, Heung Yong

    2014-01-01

    Highlights: • A new algorithm is proposed for the sensor-less control of methanol concentration. • Two different strategies are used depending on the ambient temperatures. • Energy efficiency of the DMFC system has been improved by using the new algorithm. - Abstract: A new version of an algorithm is used to control the methanol concentration in the feed of DMFC systems without using methanol sensors under varying ambient temperatures. The methanol concentration is controlled indirectly by controlling the temperature of the DMFC stack, which correlates well with the methanol concentration. Depending on the ambient temperature relative to a preset reference temperature, two different strategies are used to control the stack temperature: either reducing the cooling rate of the methanol solution passing through an anode-side heat exchanger; or, lowering the pumping rate of the pure methanol to the depleted feed solution. The feasibility of the algorithm is evaluated using a DMFC system that consists of a 200 W stack and the balance of plant (BOP). The DMFC system includes a sensor-less methanol controller that is operated using a LabView system as the central processing unit. The algorithm is experimentally confirmed to precisely control the methanol concentration and the stack temperature at target values under an environment of varying ambient temperatures

  13. Liquid densities and excess molar volumes for (ionic liquids + methanol + water) ternary system at atmospheric pressure and at various temperatures

    Deenadayalu, Nirmala [Department of Chemistry, Durban University of Technology, Steve Biko Campus, P.O. Box 1334, Durban, KwaZulu-Natal 4001 (South Africa)], E-mail: NirmalaD@dut.ac.za; Kumar, Satish; Bhujrajh, Pravena [Department of Chemistry, Durban University of Technology, Steve Biko Campus, P.O. Box 1334, Durban, KwaZulu-Natal 4001 (South Africa)

    2007-09-15

    Excess molar volumes, V{sub m}{sup E} have been evaluated from density measurements over the entire composition range for ternary liquid system of ionic liquid (1-ethyl-3-methyl-imidazolium diethylenglycol monomethylether sulphate {l_brace}[EMIM][CH{sub 3}(OCH{sub 2}CH{sub 2}){sub 2}OSO{sub 3}]) (1) + methanol (2) + water (3){r_brace} at T = (298.15, 303.15, and 313.15) K. A vibrating tube densimeter was used for these measurements at atmospheric pressure. The V{sub m}{sup E} values were found to be negative at T = (298.15 and 303.15) K. For {l_brace}[EMIM][CH{sub 3}(OCH{sub 2}CH{sub 2}){sub 2}OSO{sub 3}] (1) + methanol (2) + water (3){r_brace} at T = 313.15 K the V{sub m}{sup E} values become positive at higher mole fraction of ionic liquid and at a corresponding decrease in mole fraction of water. All the experimental data were fitted with the Redlich-Kister equation. The results have also been analysed in term of graph theoretical approach.

  14. Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOH(TM)) Process

    None

    1996-12-31

    The Liquid Phase Methanol (LPMEOH(TM)) Demonstration Project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership). The LPMEOIWM Process Demonstration Unit is being built at a site located at the Eastman Chemical Company (Eastman) complex in Kingsport. During this quarter, the Cooperative Agreement was modified (Mod AO11) on 8 October 1996, authorizing the transition born Budget Period No. 2 (Design and Construction) to the . final Budget Period (Commissioning, Start-up, and Operation), A draft Topical Report on Process Economics Studies concludes that methanol coproduction with integrated gasification combined cycle (IGCC) electric power utilizing the LPMEOW process technology, will be competitive in serving local market needs. Planning for a proof-of- concept test run of the liquid phase dimethyl ether (DME) process at the LaPorte Alternative Fuels Development Unit (AFDU) was recommended; and a deeision to proceed is pending. Construction (Task 2.2) is 97'Mo complete, asof31 December 1996. Completion of pipe pressure testing has taken longer than expected. This will delay completion of construction by about three weeks. Commissioning activities (Task 2.3) commenced in mid-October of 1996, and the demonstration unit is scheduled to be mechanically complete on 24 January 1997.

  15. Measurement of (vapor + liquid) equilibrium for the systems {methanol + dimethyl carbonate} and {methanol + dimethyl carbonate + tetramethylammonium bicarbonate} at p = (34.43, 67.74) kPa

    Yang Changsheng; Zeng Hao; Yin Xia; Ma Shengyong; Sun Feizhong; Li Yafei; Li Jiao

    2012-01-01

    Highlights: ► VLE data for the binary system and the ternary system were measured. ► Methanol, dimethyl carbonate, and tetramethylammonium bicarbonate were studied. ► Isobaric experimental data were measured at p = (34.43, 67.74) kPa. ► VLE data of binary system were correlated with the Wilson, NRTL, and UNIQUAC models. ► The salt effect of TMAB on the VLE of {methanol + DMC} system was investigated. - Abstract: Isobaric (vapor + liquid) equilibrium (VLE) data for the binary system (methanol + dimethyl carbonate) and the ternary system (methanol + dimethyl carbonate + tetramethylammonium bicarbonate) have been measured at p = (34.43, 67.74) kPa using a modified Rose–Williams still. The experimental data for the binary system were well correlated by Wilson, NRTL, and UNIQUAC activity-coefficient models at the two reduced pressures. All the experimental results of the binary system passed the thermodynamic consistency test by the area test of Redlich–Kister and the point test of Van Ness et al. The experimental results of ternary system show that the salt tetramethylammonium bicarbonate has a salting-in effect on methanol. And this effect enhances when the salt concentration increases.

  16. Micro-patterned Nafion membranes for direct methanol fuel cell applications

    Yildirim, M.H.; te Braake, J.; Aran, H.C.; Stamatialis, Dimitrios; Wessling, Matthias

    2010-01-01

    In this work, we report the direct methanol fuel cell (DMFC) performance of micro-patterned (μp) Nafion® 117 (N117) membranes prepared by hot embossing and compare them with that of normal N117 and heat and pressure treated (hp) N117 non-patterned (smooth) membranes. Our results suggest that the

  17. Challenges in Design of an Orientation free Micro Direct Methanol Fuel Cell (µDMFC)

    Omidvarnia, Farzaneh; Hansen, Hans Nørgaard; Hales, Jan Harry

    2014-01-01

    the challenges in design and manufacturing of a micro direct methanol fuel cell (μDMFC) as the power generator in hearing aid devices is investigated. Among the different challenges in design for μDMFC, the CO2 bubble management and orientation independency of the cell are addressed by proposing a spring loaded...

  18. Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cells Stacks

    Valdez, T. I.; Firdosy, S.; Koel, B. E.; Narayanan, S. R.

    2005-01-01

    This viewgraph presentation gives a detailed review of the Direct Methanol Based Fuel Cell (DMFC) stack and investigates the Ruthenium that was found at the exit of the stack. The topics include: 1) Motivation; 2) Pathways for Cell Degradation; 3) Cell Duration Testing; 4) Duration Testing, MEA Analysis; and 5) Stack Degradation Analysis.

  19. In situ synthesis of nanocomposite membranes: comprehensive improvement strategy for direct methanol fuel cells.

    Rao, Siyuan; Xiu, Ruijie; Si, Jiangju; Lu, Shanfu; Yang, Meng; Xiang, Yan

    2014-03-01

    In situ synthesis is a powerful approach to control nanoparticle formation and consequently confers extraordinary properties upon composite membranes relative to conventional doping methods. Herein, uniform nanoparticles of cesium hydrogen salts of phosphotungstic acid (CsPW) are controllably synthesized in situ in Nafion to form CsPW–Nafion nanocomposite membranes with both improved proton conductivity and methanol-crossover suppression. A 101.3% increase of maximum power density has been achieved relative to pristine Nafion in a direct methanol fuel cell (DMFC), indicating a potential pathway for large-scale fabrication of DMFC alternative membranes.

  20. A quasi-direct methanol fuel cell system based on blend polymer membrane electrolytes

    Li, Qingfeng; Hjuler, Hans Aage; Hasiotis, C.

    2002-01-01

    , compared to less than 100 ppm CO for the Nafion-based technology at 80degrees C. The high CO tolerance makes it possible to use the reformed hydrogen directly from a simple methanol reformer without further CO removal. That both the fuel cell and the methanol reformer operate at temperatures around 200......On the basis of blend polymer electrolytes of polybenzimidazole and sulfonated polysulfone, a polymer electrolyte membrane fuel cell was developed with an operational temperature up to 200degrees C. Due to the high operational temperature, the fuel cell can tolerate 1.0-3.0 vol % CO in the fuel...

  1. Design of an optimal micro direct methanol fuel cell for portable applications

    Ahmad, M.M.; Kamarudin, S.K.; Daud, W.R.W

    2010-01-01

    The main constraint for the commercialization of micro Direct Methanol Fuel cell (μDMFC) for small power generation is the performance of the fuel cell. In this study, a high-power μDMFC with a power output of 14.10 mW on an active area of 4 cm 2 and catalyst loading of 0.5 mg cm -2 cathode was successfully developed. The optimal parameters for methanol concentration and catalyst loading were determined. Besides that, testing of performance, long term and open circuit voltage (OCV) was also performed. (author)

  2. Effects of dissolved iron and chromium on the performance of direct methanol fuel cell

    Chen, Weimin; Xin, Qin; Sun, Gongquan; Yang, Shaohua; Zhou, Zhenhua; Mao, Qing; Sun, Pichang

    2007-01-01

    Effects of Fe 3+ and Cr 3+ ions on the performance of direct methanol fuel cell were investigated. The results show that the cell performance decreased remarkably when the concentration of Fe 3+ or Cr 3+ exceeded 1 x 10 -4 mol L -1 . Fe 3+ displayed a strong negative effect on the catalytic oxidation of methanol, while Cr 3+ affected the cell performance primarily by exchanging with protons of the membrane/ionomer and resulted in ionic conductivity losses. Complete recovery of the cell performance was not obtained after flushing the cell with deionized water

  3. Mould Design and Material selection for Film Insert Moulding of Direct Methanol Fuel Cell Packaging

    Wöhner, Timo; Senkbeil, S.; Olesen, T. L.

    2015-01-01

    This paper presents the mould design for an injection moulding (IM) process for the production of a methanol container for the use in small, passive Direct Methanol Fuel Cell (DMFC) systems, which are intended to be used in behind-the-ear hearing aid systems. One of the crucial properties...... for the production of containers with different venting area and location of the venting holes and the use of different membrane thicknesses by using the same mould. Mould design and material selection are presented....

  4. Final environmental assessment for the Liquid Phase Methanol (LPMEOH trademark) Project

    1995-06-01

    The proposed project is to demonstrate on a commercial scale the production of methanol from coal-derived synthesis gas using the LPMEOH trademark process. The methanol produced during this demonstration will be used as a chemical feedstock (on-site) and/or as an alternative fuel in stationary and transportation applications (off-site). In addition, the production of dimethyl ether (DME) as a mixed co-product with methanol may be demonstrated for a six month period under the proposed project pending the results of laboratory/pilot-scale research on scale-up. The DME would be used as fuel in on-site boilers. The proposed LPMEOH facility would occupy approximately 0.6 acres of the 3,890-acre Eastman Chemical facility in Kingsport, TN. The effects of the proposed project include changes in air emissions, wastewater discharge, cooling water discharge, liquid waste quantities, transportation activities, socioeconomic effects, and quantity of solids for disposal. No substantive negative impacts or environmental concerns were identified

  5. On the actual cathode mixed potential in direct methanol fuel cells

    Zago, M.; Bisello, A.; Baricci, A.; Rabissi, C.; Brightman, E.; Hinds, G.; Casalegno, A.

    2016-09-01

    Methanol crossover is one of the most critical issues hindering commercialization of direct methanol fuel cells since it leads to waste of fuel and significantly affects cathode potential, forming a so-called mixed potential. Unfortunately, due to the sluggish anode kinetics, it is not possible to obtain a reliable estimation of cathode potential by simply measuring the cell voltage. In this work we address this limitation, quantifying the mixed potential by means of innovative open circuit voltage (OCV) tests with a methanol-hydrogen mixture fed to the anode. Over a wide range of operating conditions, the resulting cathode overpotential is between 250 and 430 mV and is strongly influenced by methanol crossover. We show using combined experimental and modelling analysis of cathode impedance that the methanol oxidation at the cathode mainly follows an electrochemical pathway. Finally, reference electrode measurements at both cathode inlet and outlet provide a local measurement of cathode potential, confirming the reliability of the innovative OCV tests and permitting the evaluation of cathode potential up to typical operating current. At 0.25 A cm-2 the operating cathode potential is around 0.85 V and the Ohmic drop through the catalyst layer is almost 50 mV, which is comparable to that in the membrane.

  6. Modeling of the anode side of a direct methanol fuel cell with analytical solutions

    Mosquera, Martin A.; Lizcano-Valbuena, William H.

    2009-01-01

    In this work, analytical solutions were derived (for any methanol oxidation reaction order) for the profiles of methanol concentration and proton current density, by assuming diffusion mass transport mechanism, Tafel kinetics, and fast proton transport in the anodic catalyst layer of a direct methanol fuel cell. An expression for the Thiele modulus that allows to express the anodic overpotential as a function of the cell current and kinetic and mass transfer parameters was obtained. For high cell current densities, it was found that the Thiele modulus (φ 2 ) varies quadratically with cell current density; yielding a simple correlation between anodic overpotential and cell current density. Analytical solutions were derived for the profiles of both local methanol concentration in the catalyst layer and local anodic current density in the catalyst layer. Under the assumptions of the model presented here, in general, the local methanol concentration in the catalyst layer cannot be expressed as an explicit function of the position in the layer. In spite of this, the equations presented here for the anodic overpotential allow the derivation of new semi-empirical equations

  7. Carbon-Supported Pd and PdFe Alloy Catalysts for Direct Methanol Fuel Cell Cathodes

    Luis M. Rivera Gavidia

    2017-05-01

    Full Text Available Direct methanol fuel cells (DMFCs are electrochemical devices that efficiently produce electricity and are characterized by a large flexibility for portable applications and high energy density. Methanol crossover is one of the main obstacles for DMFC commercialization, forcing the search for highly electro-active and methanol tolerant cathodes. In the present work, carbon-supported Pd and PdFe catalysts were synthesized using a sodium borohydride reduction method and physico-chemically characterized using transmission electron microscopy (TEM and X-ray techniques such as photoelectron spectroscopy (XPS, diffraction (XRD and energy dispersive spectroscopy (EDX. The catalysts were investigated as DMFC cathodes operating at different methanol concentrations (up to 10 M and temperatures (60 °C and 90 °C. The cell based on PdFe/C cathode presented the best performance, achieving a maximum power density of 37.5 mW·cm−2 at 90 °C with 10 M methanol, higher than supported Pd and Pt commercial catalysts, demonstrating that Fe addition yields structural changes to Pd crystal lattice that reduce the crossover effects in DMFC operation.

  8. Three-dimensional anode engineering for the direct methanol fuel cell

    Bauer, A.; Oloman, C. W.; Gyenge, E. L.

    Catalyzed graphite felt three-dimensional anodes were investigated in direct methanol fuel cells (DMFCs) operated with sulfuric acid supporting electrolyte. With a conventional serpentine channel flow field the preferred anode thickness was 100 μm, while a novel flow-by anode showed the best performance with a thickness of 200-300 μm. The effects of altering the methanol concentration, anolyte flow rate and operating temperature on the fuel cell superficial power density were studied by full (2 3 + 1) factorial experiments on a cell with anode area of 5 cm 2 and excess oxidant O 2 at 200 kPa(abs). For operation in the flow-by mode with 2 M methanol at 2 cm 3 min -1 and 353 K the peak power density was 2380 W m -2 with a PtRuMo anode catalyst, while a PtRu catalyst yielded 2240 W m -2 under the same conditions.

  9. Direct synthesis of few-layer graphene supported platinum nanocatalyst for methanol oxidation

    Tan, Hong; Ma, Xiaohui; Sheng, Leimei; An, Kang; Yu, Liming; Zhao, Hongbin; Xu, Jiaqiang; Ren, Wei; Zhao, Xinluo

    2014-11-01

    High-crystalline few-layer graphene supported Pt nanoparticles have been synthesized by arc discharge evaporation of carbon electrodes containing Pt element. A high-temperature treatment under hydrogen atmosphere has been carried out to obtain a new type of Pt/graphene catalyst for methanol oxidation in direct methanol fuel cell. The morphology and structure characterizations of as-grown few-layer graphene supported Pt nanoparticles and Pt/graphene catalysts have been studied by Raman spectroscopy, scanning electron microscopy with energy-dispersive spectroscopy, and high-resolution transmission electron microscopy. Cyclic voltammograms and chronoamperometric curves show that our present Pt/graphene catalysts have larger current density for methanol oxidation, higher tolerance to carbon monoxide poisoning, and better stability during the operating procedure, compared to commercial Pt/C catalysts.

  10. Ruthenium–Platinum Catalysts and Direct Methanol Fuel Cells (DMFC: A Review of Theoretical and Experimental Breakthroughs

    Ana S. Moura

    2017-02-01

    Full Text Available The increasing miniaturization of devices creates the need for adequate power sources and direct methanol fuel cells (DMFC are a strong option in the various possibilities under current development. DMFC catalysts are mostly based on platinum, for its outperformance in three key areas (activity, selectivity and stability within methanol oxidation framework. However, platinum poisoning with products of methanol oxidation led to the use of alloys. Ruthenium–platinum alloys are preferred catalysts active phases for methanol oxidation from an industrial point of view and, indeed, ruthenium itself is a viable catalyst for this reaction. In addition, the route of methanol decomposition is crucial in the goal of producing H2 from water reaction with methanol. However, the reaction pathway remains elusive and new approaches, namely in computational methods, have been ensued to determine it. This article reviews the various recent theoretical approaches for determining the pathway of methanol decomposition, and systematizes their validation with experimental data, within methodological context.

  11. Vapor-liquid equilibria of a minute amount of furfural in water-methanol-ethanol system; Mizu-methanol-ethanol keichu no biryo no furfural no kieki heiko

    Ikari, A.; Hatate, Y.; Uemura, Y. [Kagoshima University, Kagoshima (Japan). Faculty of Engineering

    1997-01-10

    Vapor-liquid equilibria of a water-methanol-ethanol system containing a minute amount of furfural were measured at atmospheric pressure by use of an Othmer-type still. The experimental results are represented by four triangular diagrams against the liquid compositions of the major components (water, methanol and ethanol), in which three diagrams show the vapor composition of the major components, respectively, and one diagram shows the equilibrium ratio of the trace component (furfural). The curved surface of the equilibrium ratio of the trace component exhibits a gentle downward slope in most areas, but shows a half-saddle face in the neighborhood of the water-ethanol side. 4 refs., 10 figs., 3 tabs.

  12. Separation of thorium and uranium by liquid-liquid extraction from mixed aqueous nitric acidic-methanolic solutions

    Schmid, E.R.; Kenndler, E.

    1976-01-01

    A method is described for the separation of Th and U from each other and from other elements, usually occuring in minerals, by liquid-liquid extraction with Aliquat Nitrate (tricaprylmethyl ammoniumnitrate, 6 vol%) in benzene from a mixed solution of 2.5 M HNO 3 and methanol (1:1 volume ratio). Permissible upper concentration ratios of interfering elements, such as Li, Na, K, Mg, Ca, Al, Cu, Co(II), Fe(III), Mn(II), Ti(IV), La(III), U(VI), Cl - , ClO 4 - , SO 4 2- , PO 4 3- , have been determined. Following the separation, Th has been determined by spectrophotometry using Thorin, and U by fluorometry. Results for yield under varying conditions, together with elemental concentrations in the ppm range for U and Th in minerals, are given. (B.T.)

  13. Methanol-Tolerant Platinum-Palladium Catalyst Supported on Nitrogen-Doped Carbon Nanofiber for High Concentration Direct Methanol Fuel Cells.

    Kim, Jiyoung; Jang, Jin-Sung; Peck, Dong-Hyun; Lee, Byungrok; Yoon, Seong-Ho; Jung, Doo-Hwan

    2016-08-15

    Pt-Pd catalyst supported on nitrogen-doped carbon nanofiber (N-CNF) was prepared and evaluated as a cathode electrode of the direct methanol fuel cell (DMFC). The N-CNF, which was directly synthesized by the catalytic chemical vapor deposition from acetonitrile at 640 °C, was verified as having a change of electrochemical surface properties such as oxygen reduction reaction (ORR) activities and the electrochemical double layer compared with common carbon black (CB). To attain the competitive oxygen reduction reaction activity with methanol tolerance, the Pt and Pd metals were supported on the CB or the N-CNF. The physical and electrochemical characteristics of the N-CNF-supported Pt-Pd catalyst were examined and compared with catalyst supported on the CB. In addition, DMFC single cells using these catalysts as the cathode electrode were applied to obtain I-V polarization curves and constant current operating performances with high-concentration methanol as the fuel. Pt-Pd catalysts had obvious ORR activity even in the presence of methanol. The higher power density was obtained at all the methanol concentrations when it applied to the membrane electrode assembly (MEA) of the DMFC. When the N-CNF is used as the catalyst support material, a better performance with high-concentration methanol is expected.

  14. Methanol-Tolerant Platinum-Palladium Catalyst Supported on Nitrogen-Doped Carbon Nanofiber for High Concentration Direct Methanol Fuel Cells

    Jiyoung Kim

    2016-08-01

    Full Text Available Pt-Pd catalyst supported on nitrogen-doped carbon nanofiber (N-CNF was prepared and evaluated as a cathode electrode of the direct methanol fuel cell (DMFC. The N-CNF, which was directly synthesized by the catalytic chemical vapor deposition from acetonitrile at 640 °C, was verified as having a change of electrochemical surface properties such as oxygen reduction reaction (ORR activities and the electrochemical double layer compared with common carbon black (CB. To attain the competitive oxygen reduction reaction activity with methanol tolerance, the Pt and Pd metals were supported on the CB or the N-CNF. The physical and electrochemical characteristics of the N-CNF–supported Pt-Pd catalyst were examined and compared with catalyst supported on the CB. In addition, DMFC single cells using these catalysts as the cathode electrode were applied to obtain I-V polarization curves and constant current operating performances with high-concentration methanol as the fuel. Pt-Pd catalysts had obvious ORR activity even in the presence of methanol. The higher power density was obtained at all the methanol concentrations when it applied to the membrane electrode assembly (MEA of the DMFC. When the N-CNF is used as the catalyst support material, a better performance with high-concentration methanol is expected.

  15. Atomic motions in solid and liquid methanol by neutron inelastic scattering

    Figueiredo Neto, A.M.; Vinhas, L.A.

    1979-01-01

    The frequency spectra of methanol in three phases liquid, crystal I and crystal II were determined by incoherent inelastic neutron scattering. The measurements were performed using a Beryllium Filter Time-of-Flight Spectrometer. Neutron inelastic scattering spectra and frequency spectra allowed assignments of five peaks, corresponding to frequencies: 420 cm -1 attributed to vibrational modes of crystalline lattice, 240 and 160 cm -1 associated to stretching of hydrogen bonds, 82 and 50 cm -1 interpreted as vibrational and torsional modes of CH 3 OH units in dimers, trimers, tetramers and pentames. The results suggest crystal I phase as an intermediate phase between liquid and crystal II, concerning the structural and dynamical properties of molecules and their correlation. The plastic character of crystal I is discussed. (Author) [pt

  16. Characterization of an anionic-exchange membranes for direct methanol alkaline fuel cells

    Abuin, Graciela C. [Centro de Procesos Superficiales, Instituto Nacional de Tecnologia Industrial (INTI), Av. Gral. Paz 5445, B1650KNA, San Martin, Buenos Aires (Argentina); Nonjola, Patrick; Mathe, Mkhulu K. [Council for Scientific and Industrial Research (CSIR), Material Science and Manufacturing, PO Box 395, Brumeria, Pretoria 0001 (South Africa); Franceschini, Esteban A.; Izraelevitch, Federico H.; Corti, Horacio R. [Departamento de Fisica de la Materia Condensada, Comision Nacional de Energia Atomica (CNEA), Av. Gral. Paz 1499, B1650KNA, San Martin, Buenos Aires (Argentina)

    2010-06-15

    Ammonium quaternized polymers such as poly (arylene ether sulfones) are being developed and studied as candidates of ionomeric materials for application in alkaline fuel cells, due to their low cost and promising electrochemical properties. In this work, a quaternary ammonium polymer was synthesized by chloromethylation of a commercial polysulfone followed by amination process. Quaternized polysulfone membrane properties such us water and water-methanol uptake, electrical conductivity and Young's modulus were evaluated and compared to Nafion 117, commonly employed in direct methanol fuel cells. The anionic polysulfone membrane sorbs more water than Nafion all over the whole range of water activities, but it uptakes much less methanol as compared to Nafion. The specific conductivity of the fully hydrated polysulfone membrane equilibrated with KOH solutions at ambient temperature increases with the KOH concentration, reaching a maximum of 0.083 S cm{sup -1} for 2 M KOH, slightly less conductive than Nafion 117. The elastic modulus of the polysulfone membranes inmersed in water is similar to that reported for Nafion membranes under the same conditions. We concluded that quaternized polysulfone membrane are good candidates as electrolytes in alkaline direct methanol fuel cells. (author)

  17. Proton conducting hydrocarbon membranes: Performance evaluation for room temperature direct methanol fuel cells

    Krivobokov, Ivan M.; Gribov, Evgeniy N.; Okunev, Alexey G.

    2011-01-01

    The methanol permeability, proton conductivity, water uptake and power densities of direct methanol fuel cells (DMFCs) at room temperature are reported for sulfonated hydrocarbon (sHC) and perfluorinated (PFSA) membranes from Fumatech, and compared to Nafion membranes. The sHC membranes exhibit lower proton conductivity (25-40 mS cm -1 vs. ∼95-40 mS cm -1 for Nafion) as well as lower methanol permeability (1.8-3.9 x 10 -7 cm 2 s -1 vs. 2.4-3.4 x 10 -6 cm 2 s -1 for Nafion). Water uptake was similar for all membranes (18-25 wt%), except for the PFSA membrane (14 wt%). Methanol uptake varied from 67 wt% for Nafion to 17 wt% for PFSA. The power density of Nafion in DMFCs at room temperature decreases with membrane thickness from 26 mW cm -2 for Nafion 117 to 12.5 mW cm -2 for Nafion 112. The maximum power density of the Fumatech membranes ranges from 4 to 13 mW cm -1 . Conventional transport parameters such as membrane selectivity fail to predict membrane performance in DMFCs. Reliable and easily interpretable results are obtained when the power density is plotted as a function of the transport factor (TF), which is the product of proton concentration in the swollen membrane and the methanol flux. At low TF values, cell performance is limited by low proton conductivity, whereas at high TF values it decreases due to methanol crossover. The highest maximum power density corresponds to intermediate values of TF.

  18. Insight into the influence of liquid paraffin for methanol synthesis on Cu(110) surface using continuum and atomistic models

    Jiao, Wei-Hong [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Liu, Shi-Zhong [Department of Chemistry, Stony Brook University, Stony Brook, NY 11794 (United States); Zuo, Zhi-Jun, E-mail: zuozhijun@tyut.edu.cn [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Ren, Rui-Peng; Gao, Zhi-Hua [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Huang, Wei, E-mail: huangwei@tyut.edu.cn [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China)

    2016-11-30

    Highlights: • The influence of liquid paraffin is studied using continuum and atomistic models. • Liquid paraffin does not alter the reaction pathways of CO hydrogenation and WGS. • Liquid paraffin alters the reaction pathways of CO{sub 2} hydrogenation. - Abstract: Methanol synthesis from CO/CO{sub 2} hydrogenation and water-gas shift (WGS) reaction on Cu(110) in liquid paraffin and vacuum have been systematically researched with density functional theory calculation (DFT). For methanol synthesis from CO hydrogenation, the reaction pathways in liquid paraffin and vacuum are CO + H → HCO → H{sub 2}CO → H{sub 3}CO → H{sub 3}COH; in the case of WGS, the reaction pathways in liquid paraffin and vacuum are CO + 2H{sub 2}O → CO + 2OH + 2H → CO + H{sub 2}O + O + H{sub 2} → CO{sub 2} + H{sub 2}O + H{sub 2}; the reaction pathways of methanol synthesis from CO{sub 2} hydrogenation in liquid paraffin and vacuum are CO{sub 2} + H → HCOO → H{sub 2}COO → H{sub 2}CO → H{sub 3}CO → H{sub 3}COH and CO{sub 2} + H → HCOO → HCOOH → H{sub 2}COOH → H{sub 3}CO → H{sub 3}COH, respectively. The result shows that liquid paraffin does not affect the reaction mechanisms of methanol synthesis from CO and WGS, but it changes the reaction mechanisms of methanol synthesis from CO{sub 2} hydrogenation. Hirshfeld charge and the d-band centers indicate that the catalytic activity of Cu(110) in liquid paraffin is smaller than that in vacuum. Our results also show that it is necessary to consider both continuum and atomistic models in the slurry bed.

  19. Metamorphosis of the mixed phase PtRu anode catalyst for direct methanol fuel cells after exposure of methanol: In situ and ex situ characterizations

    Chakraborty, Debasish [Center for Individual Nanoparticle Functionality (CINF), Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark); Aerosol Laboratory, Nano.DTU, Department of Chemical Engineering, Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark); Chorkendorff, Ib [Center for Individual Nanoparticle Functionality (CINF), Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark); Department of Physics, Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark); Johannessen, Tue [Aerosol Laboratory, Nano.DTU, Department of Chemical Engineering, Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark)

    2007-11-08

    The change in the mixed phase heavily oxidized PtRu anode with the exposure of methanol in a direct methanol fuel cell (DMFC) has been investigated by electrochemical impedance spectroscopy (EIS) and X-ray diffraction (XRD). The investigation had two major objectives: (i) to explore the original state of the active catalyst and (ii) to understand if alloying of Pt and Ru is a requirement for higher methanol oxidation activity. It was found that the methanol oxidation activity gradually improved for {proportional_to}2 h of exposure. The impedance spectra were taken at different times within this time of improvement of activity. The impedance spectra were deconvoluted in different contributions like membrane resistance (R{sub m}), charge transfer resistance (R{sub Ct}), adsorption resistance (R{sub ad}), and oxidation resistance (R{sub ox}). The improvement of the activity was explained in terms of the effect of the pretreatment on different contributions. XRD was done on the virgin and methanol exposed sample as a possible mean to identify the difference. It was postulated that the reduction of the as prepared PtRu after exposure was responsible for the activity improvement. Also, it was shown that bulk alloy formation is not a necessary condition for higher methanol activity of PtRu catalysts. (author)

  20. Mixed phase Pt-Ru catalyst for direct methanol fuel cell anode by flame aerosol synthesis

    Chakraborty, Debasish; Bischoff, H.; Chorkendorff, Ib

    2005-01-01

    A spray-flame aerosol catalyzation technique was studied for producing Pt-Ru anode electrodes for the direct methanol fuel cell. Catalysts were produced as aerosol nanoparticles in a spray-flame reactor and deposited directly as a thin layer on the gas diffusion layer. The as-prepared catalyst wa......Ru1/Vulcan carbon. The kinetics of methanol oxidation on the mixed phase catalyst was also explored by electrochemical impedance spectroscopy. (c) 2005 The Electrochemical Society.......A spray-flame aerosol catalyzation technique was studied for producing Pt-Ru anode electrodes for the direct methanol fuel cell. Catalysts were produced as aerosol nanoparticles in a spray-flame reactor and deposited directly as a thin layer on the gas diffusion layer. The as-prepared catalyst...... was found to be a mixture of nanocrystalline, mostly unalloyed Pt and an amorphous phase mostly of Ru and to a lesser extent of Pt oxides on top of the crystalline phase. The flame-produced Pt1Ru1 demonstrated similar onset potential but similar to 60% higher activity compared to commercially available Pt1...

  1. Recast Nafion{sup R}-based membranes for direct methanol fuel cells

    Dimitrova, Penka; Friedrich, Kaspar A.; Stimming, Ulrich; Vogt, Brunhilde [Department of Physics, Technische Universitaet Muenchen, D-80333 Munich (Germany)

    2001-07-01

    Commercially available Nafion{sup R} membranes at present do not meet the requirements for direct methanol fuel cell (DMFC) applications, amongst others factors because of their high methanol permeability. With the aim of improving this undesirable characteristic, a modification procedure has been applied to recast Nafion-based membranes. Membranes, containing different additives, are assessed with regard to their conductivity and methanol permeation rate. The preparation of the samples involves the introduction of a small amount of a high boiling point solvent to the as-received Nafion solution and then shaping the membranes by a recasting procedure (drying at room temperature and heating up to 150{sup o}C). An enhancement of the conductivity of the thermally treated membranes in comparison to the commercial Nafion 117 is found. The thickness-normalised methanol permeation rate of the samples, containing inorganic additives (Aerosil and molybdophosphoric acid) decreases compared to the pure recast and as-received Nafion membranes. The observed results are discussed in terms of the membrane structure and preparation. (author)

  2. Novel fluoropolymer anion exchange membranes for alkaline direct methanol fuel cells.

    Zhang, Yanmei; Fang, Jun; Wu, Yongbin; Xu, Hankun; Chi, Xianjun; Li, Wei; Yang, Yixu; Yan, Ge; Zhuang, Yongze

    2012-09-01

    A series of novel fluoropolymer anion exchange membranes based on the copolymer of vinylbenzyl chloride, butyl methacrylate, and hexafluorobutyl methacrylate has been prepared. Fourier transform infrared (FT-IR) spectroscopy and elemental analysis techniques are used to study the chemical structure and chemical composition of the membranes. The water uptake, ion-exchange capacity (IEC), conductivity, methanol permeability, and chemical stability of the membranes are also determined. The membranes exhibit high anionic conductivity in deionized water at 65 °C ranging from 3.86×10(-2) S cm(-1) to 4.36×10(-2) S cm(-1). The methanol permeability coefficients of the membranes are in the range of 4.21-5.80×10(-8) cm(2) s(-1) at 65 °C. The novel membranes also show good chemical and thermal stability. An open-circuit voltage of 0.7 V and a maximum power density of 53.2 mW cm(-2) of alkaline direct methanol fuel cell (ADMFC) with the membrane C, 1 M methanol, 1 M NaOH, and humidified oxygen are achieved at 65 °C. Therefore, these membranes have great potential for applications in fuel cell systems. Copyright © 2012 Elsevier Inc. All rights reserved.

  3. A three-dimensional non-isothermal model for a membraneless direct methanol redox fuel cell

    Wei, Lin; Yuan, Xianxia; Jiang, Fangming

    2018-05-01

    In the membraneless direct methanol redox fuel cell (DMRFC), three-dimensional electrodes contribute to the reduction of methanol crossover and the open separator design lowers the system cost and extends its service life. In order to better understand the mechanisms of this configuration and further optimize its performance, the development of a three-dimensional numerical model is reported in this work. The governing equations of the multi-physics field are solved based on computational fluid dynamics methodology, and the influence of the CO2 gas is taken into consideration through the effective diffusivities. The numerical results are in good agreement with experimental data, and the deviation observed for cases of large current density may be related to the single-phase assumption made. The three-dimensional electrode is found to be effective in controlling methanol crossover in its multi-layer structure, while it also increases the flow resistance for the discharging products. It is found that the current density distribution is affected by both the electronic conductivity and the concentration of reactants, and the temperature rise can be primarily attributed to the current density distribution. The sensitivity and reliability of the model are analyzed through the investigation of the effects of cell parameters, including porosity values of gas diffusion layers and catalyst layers, methanol concentration and CO2 volume fraction, on the polarization characteristics.

  4. Mathematical Modeling of Transport Phenomena in Polymer Electrolyte and Direct Methanol Fuel Cells

    Birgersson, Erik

    2004-02-01

    This thesis deals with modeling of two types of fuel cells: the polymer electrolyte fuel cell (PEFC) and the direct methanol fuel cell (DMFC), for which we address four major issues: a) mass transport limitations; b) water management (PEFC); c) gas management (DMFC); d) thermal management. Four models have been derived and studied for the PEFC, focusing on the cathode. The first exploits the slenderness of the cathode for a two-dimensional geometry, leading to a reduced model, where several non dimensional parameters capture the behavior of the cathode. The model was extended to three dimensions, where four different flow distributors were studied for the cathode. A quantitative comparison shows that the interdigitated channels can sustain the highest current densities. These two models, comprising isothermal gas phase flow, limit the studies to (a). Returning to a two-dimensional geometry of the PEFC, the liquid phase was introduced via a separate flow model approach for the cathode. In addition to conservation of mass, momentum and species, the model was extended to consider simultaneous charge and heat transfer for the whole cell. Different thermal, flow fields, and hydrodynamic conditions were studied, addressing (a), (b) and (d). A scale analysis allowed for predictions of the cell performance prior to any computations. Good agreement between experiments with a segmented cell and the model was obtained. A liquid-phase model, comprising conservation of mass, momentum and species, was derived and analyzed for the anode of the DMFC. The impact of hydrodynamic, electrochemical and geometrical features on the fuel cell performance were studied, mainly focusing on (a). The slenderness of the anode allows the use of a narrow-gap approximation, leading to a reduced model, with benefits such as reduced computational cost and understanding of the physical trends prior to any numerical computations. Adding the gas-phase via a multiphase mixture approach, the gas

  5. A transient multi-scale model for direct methanol fuel cells

    Jahnke, T.; Zago, M.; Casalegno, A.; Bessler, W.G.; Latz, A.

    2017-01-01

    The DMFC is a promising option for backup power systems and for the power supply of portable devices. However, from the modeling point of view liquid-feed DMFC are challenging systems due to the complex electrochemistry, the inherent two-phase transport and the effect of methanol crossover. In this paper we present a physical 1D cell model to describe the relevant processes for DMFC performance ranging from electrochemistry on the surface of the catalyst up to transport on the cell level. A two-phase flow model is implemented describing the transport in gas diffusion layer and catalyst layer at the anode side. Electrochemistry is described by elementary steps for the reactions occurring at anode and cathode, including adsorbed intermediate species on the platinum and ruthenium surfaces. Furthermore, a detailed membrane model including methanol crossover is employed. The model is validated using polarization curves, methanol crossover measurements and impedance spectra. It permits to analyze both steady-state and transient behavior with a high level of predictive capabilities. Steady-state simulations are used to investigate the open circuit voltage as well as the overpotentials of anode, cathode and electrolyte. Finally, the transient behavior after current interruption is studied in detail.

  6. High-performance alkaline direct methanol fuel cell using a nitrogen-postdoped anode.

    Joghee, Prabhuram; Pylypenko, Svitlana; Wood, Kevin; Bender, Guido; O'Hayre, Ryan

    2014-07-01

    A commercial PtRu/C catalyst postdoped with nitrogen demonstrates a significantly higher performance (~10-20% improvement) in the anode of an alkaline direct methanol fuel cell than an unmodified commercial PtRu/C catalyst control. The enhanced performance shown herein is attributed at least partially to the increased electrochemical surface area of the PtRu/C after postdoping with nitrogen. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Enrichment and detection of microorganisms involved in direct and indirect methanogenesis from methanol in an anaerobic thermophilic bioreactor

    Roest, de K.; Altinbas, M.; Paulo, P.L.; Heilig, H.G.H.J.; Akkermans, A.D.L.; Smidt, H.; Vos, de W.M.; Stams, A.J.M.

    2005-01-01

    To gain insight into the microorganisms involved in direct and indirect methane formation from methanol in a laboratory-scale thermophilic (55°C) methanogenic bioreactor, reactor sludge was disrupted and serial dilutions were incubated in specific growth media containing methanol and possible

  8. Breaking through the glass ceiling: The correlation between the self-diffusivity in and krypton permeation through deeply supercooled liquid nanoscale methanol films

    Smith, R. Scott; Matthiesen, Jesper; Kay, Bruce D.

    2010-03-01

    Molecular beam techniques, temperature-programmed desorption (TPD), and reflection absorption infrared spectroscopy (RAIRS) are used to explore the relationship between krypton permeation through and the self-diffusivity of supercooled liquid methanol at temperatures (100-115 K) near the glass transition temperature, Tg (103 K). Layered films, consisting of CH3OH and CD3OH, are deposited on top of a monolayer of Kr on a graphene covered Pt(111) substrate at 25 K. Concurrent Kr TPD and RAIRS spectra are acquired during the heating of the composite film to temperatures above Tg. The CO vibrational stretch is sensitive to the local molecular environment and is used to determine the supercooled liquid diffusivity from the intermixing of the isotopic layers. We find that the Kr permeation and the diffusivity of the supercooled liquid are directly and quantitatively correlated. These results validate the rare-gas permeation technique as a tool for probing the diffusivity of supercooled liquids.

  9. Mutual diffusion of binary liquid mixtures containing methanol, ethanol, acetone, benzene, cyclohexane, toluene, and carbon tetrachloride

    Guevara-Carrion, Gabriela; Janzen, Tatjana; Muñoz-Muñoz, Y. Mauricio; Vrabec, Jadran, E-mail: jadran.vrabec@uni-paderborn.de [Thermodynamics and Energy Technology, University of Paderborn, 33098 Paderborn (Germany)

    2016-03-28

    Mutual diffusion coefficients of all 20 binary liquid mixtures that can be formed out of methanol, ethanol, acetone, benzene, cyclohexane, toluene, and carbon tetrachloride without a miscibility gap are studied at ambient conditions of temperature and pressure in the entire composition range. The considered mixtures show a varying mixing behavior from almost ideal to strongly non-ideal. Predictive molecular dynamics simulations employing the Green-Kubo formalism are carried out. Radial distribution functions are analyzed to gain an understanding of the liquid structure influencing the diffusion processes. It is shown that cluster formation in mixtures containing one alcoholic component has a significant impact on the diffusion process. The estimation of the thermodynamic factor from experimental vapor-liquid equilibrium data is investigated, considering three excess Gibbs energy models, i.e., Wilson, NRTL, and UNIQUAC. It is found that the Wilson model yields the thermodynamic factor that best suits the simulation results for the prediction of the Fick diffusion coefficient. Four semi-empirical methods for the prediction of the self-diffusion coefficients and nine predictive equations for the Fick diffusion coefficient are assessed and it is found that methods based on local composition models are more reliable. Finally, the shear viscosity and thermal conductivity are predicted and in most cases favorably compared with experimental literature values.

  10. Thermophysical properties of binary mixtures of {ionic liquid 2-hydroxy ethylammonium acetate + (water, methanol, or ethanol)}

    Alvarez, Victor H.; Mattedi, Silvana; Martin-Pastor, Manuel; Aznar, Martin; Iglesias, Miguel

    2011-01-01

    Research highlights: → This paper reports the density and speed of sound data of binary mixtures {2-hydroxy ethylammonium acetate + (water, or methanol, or ethanol)} measured between the temperatures (298.15 and 313.15) K at atmospheric pressure. → The aggregation, dynamic behavior, and hydrogen-bond network were studied using thermo-acoustic, X-ray, and NMR techniques. → The Peng-Robinson equation of state, coupled with the Wong-Sandler mixing rule using the COSMO-SAC model predicted the density of the solutions with relative mean deviations below than 3.0%. - Abstract: In this work, density and speed of sound data of binary mixtures of an ionic liquid consisting of {2-hydroxy ethylammonium acetate (2-HEAA) + (water, methanol, or ethanol)} have been measured throughout the entire concentration range, from the temperature of (288.15 to 323.15) K at atmospheric pressure. The excess molar volumes, variations of the isentropic compressibility, the apparent molar volume, isentropic apparent molar compressibility, and thermal expansion coefficient were calculated from the experimental data. The excess molar volumes were negative throughout the whole composition range. Compressibility data in combination with low angle X-ray scattering and NMR measurements proved that the presence of micelles formed due to ion pair interaction above a critical concentration of the ionic liquid in the mixtures. The Peng-Robinson equation of state coupled with the Wong-Sandler mixing rule and COSMO-SAC model was used to predict densities and the calculated deviations were lower than 3%, for binary mixtures in all composition range.

  11. Development of cesium phosphotungstate salt and chitosan composite membrane for direct methanol fuel cells.

    Xiao, Yanxin; Xiang, Yan; Xiu, Ruijie; Lu, Shanfu

    2013-10-15

    A novel composite membrane has been developed by doping cesium phosphotungstate salt (CsxH3-xPW12O40 (0≤x≤3), Csx-PTA) into chitosan (CTS/Csx-PTA) for application in direct methanol fuel cells (DMFCs). Uniform distribution of Csx-PTA nanoparticles has been achieved in the chitosan matrix. The proton conductivity of the composite membrane is significantly affected by the Csx-PTA content in the composite membrane as well as the Cs substitution in PTA. The highest proton conductivity for the CTS/Csx-PTA membranes was obtained with x=2 and Cs2-PTA content of 5 wt%. The value is 6×10(-3) S cm(-1) and 1.75×10(-2) S cm(-1) at 298 K and 353 K, respectively. The methanol permeability of CTS/Cs2-PTA membrane is about 5.6×10(-7), 90% lower than that of Nafion-212 membrane. The highest selectivity factor (φ) was obtained on CTS/Cs2-PTA-5 wt% composite membrane, 1.1×10(4)/Scm(-3)s. The present study indicates the promising potential of CTS/Csx-PTA composite membrane as alternative proton exchange membranes in direct methanol fuel cells. Copyright © 2013 Elsevier Ltd. All rights reserved.

  12. Proton exchange membrane materials for the advancement of direct methanol fuel-cell technology

    Cornelius, Christopher J [Albuquerque, NM

    2006-04-04

    A new class of hybrid organic-inorganic materials, and methods of synthesis, that can be used as a proton exchange membrane in a direct methanol fuel cell. In contrast with Nafion.RTM. PEM materials, which have random sulfonation, the new class of materials have ordered sulfonation achieved through self-assembly of alternating polyimide segments of different molecular weights comprising, for example, highly sulfonated hydrophilic PDA-DASA polyimide segment alternating with an unsulfonated hydrophobic 6FDA-DAS polyimide segment. An inorganic phase, e.g., 0.5 5 wt % TEOS, can be incorporated in the sulfonated polyimide copolymer to further improve its properties. The new materials exhibit reduced swelling when exposed to water, increased thermal stability, and decreased O.sub.2 and H.sub.2 gas permeability, while retaining proton conductivities similar to Nafion.RTM.. These improved properties may allow direct methanol fuel cells to operate at higher temperatures and with higher efficiencies due to reduced methanol crossover.

  13. Biodiesel synthesis by direct transesterification of microalga Botryococcus braunii with continuous methanol reflux.

    Hidalgo, Pamela; Ciudad, Gustavo; Schober, Sigurd; Mittelbach, Martin; Navia, Rodrigo

    2015-04-01

    Direct transesterification of Botryococcus braunii with continuous acyl acceptor reflux was evaluated. This method combines in one step lipid extraction and esterification/transesterification. Fatty acid methyl esters (FAME) synthesis by direct conversion of microalgal biomass was carried out using sulfuric acid as catalyst and methanol as acyl acceptor. In this system, once lipids are extracted, they are contacted with the catalyst and methanol reaching 82%wt of FAME yield. To optimize the reaction conditions, a factorial design using surface response methodology was applied. The effects of catalyst concentration and co-solvent concentration were studied. Hexane was used as co-solvent for increasing lipid extraction performance. The incorporation of hexane in the reaction provoked an increase in FAME yield from 82% (pure methanol) to 95% when a 47%v/v of hexane was incorporated in the reaction. However, the selectivity towards non-saponifiable lipids such as sterols was increased, negatively affecting biodiesel quality. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOH) Process

    None

    1998-12-21

    The Liquid Phase Methanol (LPMEOW) Demonstration Project at Kingsport Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership) to produce methanol from coal-derived synthesis gas (syngas). Air Products and Chemicals, Inc. (Air Products) and Eastman Chemical Company (Eastman) formed the Partnership to execute the Demonstration Project. The LPMEOW Process Demonstration Unit was built at a site located at the Eastman complex in Kingsport. During this quarter, initial planning and procurement work began on the seven project sites which have been accepted for participation in the off-site, methanol product-use test plan. Two of the projects have begun pre-testing of equipment and three other projects have commenced with equipment procurement, Methanol produced from carbon monoxide (CO)- rich syngas at the Alternative Fuels Development Unit (AFDU) in LaPorte, TX has been shipped to four of the project sites in anticipation of the start of testing during the first quarter of calendar year 1998. Catalyst activity, as defined by the ratio of the rate constant at any point in time to the rate constant for a freshly reduced catalyst (as determined in the laboratory autoclave), continued to decline more rapidly than expected. In response to concentrations of arsenic and sulfbr detected on catalyst samples from the LPMEOW Reactor, Eastman replaced both the arsine- and sulfiwremoval material in the Eastman guard bed which treats the primary syngas feed stream (&danced Gas) prior to its introduction into both the Eastman fixed-bed methanol plant and the LPMEOWM Demonstration Unit. After restarting the demonstration unit, the catalyst deactivation rate remained essentially unchanged. Parallel testing in the laboratory using arsine-doped, and subsequently arsine- and SuIfi-doped syngas, ako ftiIed to prove that arsine was responsible for the higher-than-expected rate of

  15. Development of a Crosslinked Pore-filling Membrane with an Extremely Low Swelling Ratio and Methanol Crossover for Direct Methanol Fuel Cells

    Li, Yunxi; Hoorfar, Mina; Shen, Kuizhi; Fang, Jiyong; Yue, Xigui; Jiang, Zhenhua

    2017-01-01

    A poly (ether sulphone)-based pore-filling membrane was successfully fabricated and tested against a conventional Nafion-based membrane in direct methanol fuel cells. An amino-containing polymer with a low degree of sulphonation (DS) was synthesized and used as the supporting substrate. The porous substrate was prepared by introducing the porogenic agent (tetrafluoroborate) into the membrane casting solution. The effects of the content of the porogenic agent on the pore morphologies were evaluated using field emission scanning electron microscopy. Then, an epoxy resin was introduced into the porous electrolyte for the first time to minimize the swelling and methanol crossover that resulted from the high degree of sulphonation. In essence, solidification of the amino groups in the substrate results in 3D crosslinking of epoxy resins, which greatly suppresses the swelling and methanol crossover of the composite membranes with enhanced mechanical properties and enhances the thermal and oxidation stability compared to Nafion 117. The resulting composite membrane also shows high proton conductivity that is only slightly lower than that of Nafion 117. However, the selectivity between the proton conductivity and methanol permeability is higher for the composite membranes than that of Nafion 117. The composite membrane also shows a better performance in single cell tests with 10 M methanol.

  16. A CNT (carbon nanotube) paper as cathode gas diffusion electrode for water management of passive μ-DMFC (micro-direct methanol fuel cell) with highly concentrated methanol

    Deng, Huichao; Zhang, Yufeng; Zheng, Xue; Li, Yang; Zhang, Xuelin; Liu, Xiaowei

    2015-01-01

    A novel MEA (membrane electrode assembly) structure of passive μ-DMFC (micro-direct methanol fuel cell) controls water management and decreases methanol crossover. The CNT (carbon nanotube) paper replacing CP (carbon paper) as GDL (gas diffusion paper) enhances water back diffusion which passively prevents flooding in the cathode and promotes low methanol crossover. Moreover, the unique structure of CNT paper can also enhance efficiency of oxygen mass transport and catalyst utilization. The passive μ-DMFC with CNT-MEA exhibits significantly higher performance than passive μ-DMFC with CP-MEA and can operate in high methanol concentration, showing the peak power density of 23.2 mW cm −2 . The energy efficiency and fuel utilization efficiency are obviously improved from 11.54% to 22.7% and 36.61%–49.34%, respectively, and the water transport coefficient is 0.47 which is lower than previously reported passive μ-DMFC with CP. - Highlights: • This novel GDL (gas diffusion layer) solves water management and methanol crossover. • This GDL creates a hydraulic pressure in the cathode increasing water back diffusion. • This GDL improves the electrical conductivity and activity of catalyst

  17. Numerical simulation of direct methanol fuel cells using lattice Boltzmann method

    Delavar, Mojtaba Aghajani; Farhadi, Mousa; Sedighi, Kurosh [Faculty of Mechanical Engineering, Babol University of Technology, Babol, P.O. Box 484 (Iran)

    2010-09-15

    In this study Lattice Boltzmann Method (LBM) as an alternative of conventional computational fluid dynamics method is used to simulate Direct Methanol Fuel Cell (DMFC). A two dimensional lattice Boltzmann model with 9 velocities, D2Q9, is used to solve the problem. The computational domain includes all seven parts of DMFC: anode channel, catalyst and diffusion layers, membrane and cathode channel, catalyst and diffusion layers. The model has been used to predict the flow pattern and concentration fields of different species in both clear and porous channels to investigate cell performance. The results have been compared well with results in literature for flow in porous and clear channels and cell polarization curves of the DMFC at different flow speeds and feed methanol concentrations. (author)

  18. Controlled disulfonated poly(arylene ether sulfone) multiblock copolymers for direct methanol fuel cells.

    Li, Qing; Chen, Yu; Rowlett, Jarrett R; McGrath, James E; Mack, Nathan H; Kim, Yu Seung

    2014-04-23

    Structure-property-performance relationships of disulfonated poly(arylene ether sulfone) multiblock copolymer membranes were investigated for their use in direct methanol fuel cell (DMFC) applications. Multiple series of reactive polysulfone, polyketone, and polynitrile hydrophobic block segments having different block lengths and molecular composition were synthesized and reacted with a disulfonated poly(arylene ether sulfone) hydrophilic block segment by a coupling reaction. Large-scale morphological order of the multiblock copolymers evolved with the increase of block size that gave notable influence on mechanical toughness, water uptake, and proton/methanol transport. Chemical structural changes of the hydrophobic blocks through polar group, fluorination, and bisphenol type allowed further control of the specific properties. DMFC performance was analyzed to elicit the impact of structural variations of the multiblock copolymers. Finally, DMFC performances of selected multiblock copolymers were compared against that of the industrial standard Nafion in the DMFC system.

  19. Development of an air-breathing direct methanol fuel cell with the cathode shutter current collectors

    Zhang, Yufeng; Liu, Xiaowei [Key Laboratory of Micro-Systems and Micro-Structures Manufacturing, Ministry of Education, Harbin 150001 (China); MEMS Center, Harbin Institute of Technology, Harbin 150001 (China); Zhang, Peng; Zhang, Bo; Li, Jianmin; Deng, Huichao [MEMS Center, Harbin Institute of Technology, Harbin 150001 (China)

    2010-06-15

    An air-breathing direct methanol fuel cell with a novel cathode shutter current collector is fabricated to develop the power sources for consumer electronic devices. Compared with the conventional circular cathode current collector, the shutter one improves the oxygen consumption and mass transport. The anode and cathode current collectors are made of stainless steel using thermal stamping die process. Moreover, an encapsulation method using the tailor-made clamps is designed to assemble the current collectors and MEA for distributing the stress of the edges and inside uniformly. It is observed that the maximum power density of the air-breathing DMFC operating with 1 M methanol solution achieves 19.7 mW/cm{sup 2} at room temperature. Based on the individual DMFCs, the air-breathing stack consisting of 36 DMFC units is achieved and applied to power a notebook computer. (author)

  20. A direct methanol fuel cell system to power a humanoid robot

    Joh, Han-Ik; Ha, Tae Jung; Hwang, Sang Youp; Kim, Jong-Ho; Chae, Seung-Hoon; Cho, Jae Hyung; Prabhuram, Joghee; Kim, Soo-Kil; Lim, Tae-Hoon; Cho, Baek-Kyu; Oh, Jun-Ho; Moon, Sang Heup; Ha, Heung Yong

    In this study, a direct methanol fuel cell (DMFC) system, which is the first of its kind, has been developed to power a humanoid robot. The DMFC system consists of a stack, a balance of plant (BOP), a power management unit (PMU), and a back-up battery. The stack has 42 unit cells and is able to produce about 400 W at 19.3 V. The robot is 125 cm tall, weighs 56 kg, and consumes 210 W during normal operation. The robot is integrated with the DMFC system that powers the robot in a stable manner for more than 2 h. The power consumption by the robot during various motions is studied, and load sharing between the fuel cell and the back-up battery is also observed. The loss of methanol feed due to crossover and evaporation amounts to 32.0% and the efficiency of the DMFC system in terms of net electric power is 22.0%.

  1. Increasing Fuel Efficiency of Direct Methanol Fuel Cell Systems with Feedforward Control of the Operating Concentration

    Youngseung Na

    2015-09-01

    Full Text Available Most of the R&D on fuel cells for portable applications concentrates on increasing efficiencies and energy densities to compete with other energy storage devices, especially batteries. To improve the efficiency of direct methanol fuel cell (DMFC systems, several modifications to system layouts and operating strategies are considered in this paper, rather than modifications to the fuel cell itself. Two modified DMFC systems are presented, one with an additional inline mixer and a further modification of it with a separate tank to recover condensed water. The set point for methanol concentration control in the solution is determined by fuel efficiency and varies with the current and other process variables. Feedforward concentration control enables variable concentration for dynamic loads. Simulation results were validated experimentally with fuel cell systems.

  2. The performance analysis of direct methanol fuel cells with different hydrophobic anode channels

    Yeh, Hung-Chun; Yang, Ruey-Jen; Luo, Win-Jet; Jiang, Jia-You; Kuan, Yean-Der; Lin, Xin-Quan

    In order to enhance the performance of the direct methanol fuel cell (DMFC), the product of CO 2 bubble has to be efficiently removed from the anode channel during the electrochemical reaction. In this study, the materials of Polymethyl Methacrylate (PMMA) with hydrophilic property and polydimethylsiloxane (PDMS) with hydrophobic property are used to form the anode cannel. The channel is fabricated through a microelectromechanical system (MEMS) manufacture process of the DMFCs. In addition, some particles with high hydrophobic properties are added into the PDMS materials in order to further reduce the hydro-resistance in the anode channel. The performance of the DMFCs is investigated under the influence of operation conditions, including operation temperature, flow rate, and methanol concentration. It is found that the performance of the DMFC, which is made of PDMS with high hydrophobic particles, can be greatly enhanced and the hydrophobic property of the particles can be unaffected by different operation conditions.

  3. Low contaminant formic acid fuel for direct liquid fuel cell

    Masel, Richard I [Champaign, IL; Zhu, Yimin [Urbana, IL; Kahn, Zakia [Palatine, IL; Man, Malcolm [Vancouver, CA

    2009-11-17

    A low contaminant formic acid fuel is especially suited toward use in a direct organic liquid fuel cell. A fuel of the invention provides high power output that is maintained for a substantial time and the fuel is substantially non-flammable. Specific contaminants and contaminant levels have been identified as being deleterious to the performance of a formic acid fuel in a fuel cell, and embodiments of the invention provide low contaminant fuels that have improved performance compared to known commercial bulk grade and commercial purified grade formic acid fuels. Preferred embodiment fuels (and fuel cells containing such fuels) including low levels of a combination of key contaminants, including acetic acid, methyl formate, and methanol.

  4. Experimental Validation of Methanol Crossover in a Three-dimensional, Two-Fluid Model of a Direct Methanol Fuel Cell

    Olesen, Anders Christian; Berning, Torsten; Kær, Søren Knudsen

    2012-01-01

    A fully coupled three-dimensional, steady-state, two-fluid, multi-component and non-isothermal DMFC model has been developed in the commercial CFD package CFX 13 (ANSYS inc.). It accounts for the presence of micro porous layers, non-equilibrium phase change, and methanol and water uptake in the i...

  5. Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOH(TM)) Process

    None

    1997-06-30

    The Liquid Phase Methanol (LPMEOHTM) Demonstration Project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership). Air Products and Chemicals, Inc. (Air Products) and Eastman Chemical Company (Eastman) formed the Partnership to execute the Demonstration Project. The LPMEOIYM Process Demonstration Unit was built at a site located at the Eastman complex in Kingsport. During this quarter, comments from the DOE on the Topical Report "Economic Analysis - LPMEOHTM Process as an Add-on to IGCC for Coproduction" were received. A recommendation to continue with design verification testing for the coproduction of dimethyl ether (DIME) and methanol was made. DME design verification testing studies show the liquid phase DME (LPDME) process will have a significant economic advantage for the coproduction of DME for local markets. An LPDME catalyst system with reasonable long-term activity and stability is being developed. A recommendation document summarizing catalyst targets, experimental results, and the corresponding economics for a commercially successful LPDME catalyst was issued on 30 June 1997. The off-site, product-use test plan was updated in June of 1997. During this quarter, Acurex Environmental Corporation and Air Products screened proposals for this task by the likelihood of the projects to proceed and the timing for the initial methanol requirement. Eight sites from the list have met these criteria. The formal submission of the eight projects for review and concurrence by the DOE will be made during the next reporting period. The site paving and final painting were completed in May of 1997. Start-up activities were completed during the reporting period, and the initial methanol production from the demonstration unit occurred on 02 April 1997. The first extended stable operation at the nameplate capacity of 80,000 gallons per day (260 tons

  6. Thermodynamic models to predict gas-liquid solubilities in the methanol synthesis, the methanol-higher alcohol synthesis, and the Fischer-Tropsch synthesis via gas-slurry processes

    Breman, B.B; Beenackers, A.A C M

    1996-01-01

    Various thermodynamic models were tested concerning their applicability to predict gas-liquid solubilities, relevant for synthesis gas conversion to methanol, higher alcohols, and hydrocarbons via gas-slurry processes. Without any parameter optimization the group contribution equation of state

  7. Two-phase, mass-transport model for direct methanol fuel cells with effect of non-equilibrium evaporation and condensation

    Yang, W. W.; Zhao, T. S.

    A two-phase, mass-transport model for liquid-feed direct methanol fuel cells (DMFCs) is developed by taking into account the effect of non-equilibrium evaporation and condensation of methanol and water. The comparison between the present model and other models indicates that the present model yields more reasonable predictions of cell performance. Particularly, it is shown that the models that invoke a thermodynamic-equilibrium assumption between phases will overestimate mass-transport rates of methanol and water, thereby resulting in an inaccurate prediction of cell performance. The parametric study using the present model reveals that the gas coverage at the flow channel-diffusion-layer interface is directly related to the gas-void fraction inside the anode porous region; increasing the gas-void fraction will increase the mass-transfer resistance of methanol and thus lower cell performance. The effects of the geometric dimensions of the cell structure, such as channel width and rib width, on cell performance are also investigated with the model developed in this work.

  8. Three-dimensional anode engineering for the direct methanol fuel cell

    Bauer, A.; Oloman, C.W.; Gyenge, E.L. [Department of Chemical and Biological Engineering, The University of British Columbia, 2360 East Mall, Vancouver, BC (Canada)

    2009-09-05

    Catalyzed graphite felt three-dimensional anodes were investigated in direct methanol fuel cells (DMFCs) operated with sulfuric acid supporting electrolyte. With a conventional serpentine channel flow field the preferred anode thickness was 100 {mu}m, while a novel flow-by anode showed the best performance with a thickness of 200-300 {mu}m. The effects of altering the methanol concentration, anolyte flow rate and operating temperature on the fuel cell superficial power density were studied by full (2{sup 3} + 1) factorial experiments on a cell with anode area of 5 cm{sup 2} and excess oxidant O{sub 2} at 200 kPa(abs). For operation in the flow-by mode with 2 M methanol at 2 cm{sup 3} min{sup -1} and 353 K the peak power density was 2380 W m{sup -2} with a PtRuMo anode catalyst, while a PtRu catalyst yielded 2240 W m{sup -2} under the same conditions. (author)

  9. Radiation-grafted membranes based on polyethylene for direct methanol fuel cells

    Sherazi, Tauqir A. [Department of Chemistry, Government College University, Lahore 54000 (Pakistan); Institute for Chemical Process and Environmental Technology, National Research Council Canada, 1200 Montreal Road, Ottawa, ON K1A 0R6 (Canada); Guiver, Michael D.; Kingston, David; Xue, Xinzhong [Institute for Chemical Process and Environmental Technology, National Research Council Canada, 1200 Montreal Road, Ottawa, ON K1A 0R6 (Canada); Ahmad, Shujaat [PIEAS/PINSTECH, P O Nilore, Islamabad 45650 (Pakistan); Kashmiri, M. Akram [Department of Chemistry, Government College University, Lahore 54000 (Pakistan); Board of Intermediate and Secondary Education, Lahore 54000 (Pakistan)

    2010-01-01

    Styrene was grafted onto ultrahigh molecular weight polyethylene powder (UHMWPE) by gamma irradiation using a {sup 60}Co source. Compression moulded films of selected pre-irradiated styrene-grafted ultrahigh molecular weight polyethylene (UHMWPE-g-PS) were post-sulfonated to the sulfonic acid derivative (UHMWPE-g-PSSA) for use as proton exchange membranes (PEMs). The sulfonation was confirmed by X-ray photoelectron spectroscopy (XPS). The melting and flow properties of UHMWPE and UHMWPE-g-PS are conducive to forming homogeneous pore-free membranes. Both the ion conductivity and methanol permeability coefficient increased with degree of grafting, but the grafted membranes showed comparable or higher ion conductivity and lower methanol permeability than Nafion {sup registered} 117 membrane. One UHMWPE-g-PS membrane was fabricated into a membrane-electrode assembly (MEA) and tested as a single cell direct methanol fuel cell (DMFC). Low membrane cost and acceptable fuel cell performance indicate that UHMWPE-g-PSSA membranes could offer an alternative approach to perfluorosulfonic acid-type membranes for DMFC. (author)

  10. Tuning of size and shape of Au–Pt nanocatalysts for direct methanol fuel cells

    Hunyadi Murph, Simona E.; Murphy, Catherine J.; Colon-Mercado, Hector R.; Torres, Ricardo D.; Heroux, Katie J.; Fox, Elise B.; Thompson, Lucas B.; Haasch, Richard T.

    2011-01-01

    In this article, we report the precise control of the size, shape, and surface morphology of Au–Pt nanocatalysts (cubes, blocks, octahedrons, and dogbones) synthesized via a seed-mediated approach. Gold “seeds” of different aspect ratios (1–4.2), grown by a silver-assisted approach, were used as templates for high-yield production of novel Au–Pt nanocatalysts at a low temperature (40 °C). Characterization by electron microscopy (SEM, TEM, HRTEM), energy dispersive X-ray analysis, UV–Vis spectroscopy, zeta-potential (surface charge), atomic force microscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma mass spectrometry were used to better understand their physico-chemical properties, preferred reactivities and underlying nanoparticle growth mechanism. A rotating disk electrode was employed to evaluate the Au–Pt nanocatalysts electrochemical performance in the oxygen reduction reaction (ORR) and the methanol oxidation reaction of direct methanol fuel cells. The results indicate the Au–Pt dogbones are partially and in some cases completely unaffected by methanol poisoning during the evaluation of the ORR. The ORR performance of the octahedron particles in the absence of MeOH is superior to that of the Au–Pt dogbones and Pt-black; however, its performance is affected by the presence of MeOH.

  11. Model-based analysis of water management in alkaline direct methanol fuel cells

    Weinzierl, C.; Krewer, U.

    2014-12-01

    Mathematical modelling is used to analyse water management in Alkaline Direct Methanol Fuel Cells (ADMFCs) with an anion exchange membrane as electrolyte. Cathodic water supply is identified as one of the main challenges and investigated at different operation conditions. Two extreme case scenarios are modelled to study the feasible conditions for sufficient water supply. Scenario 1 reveals that water supply by cathodic inlet is insufficient and, thus, water transport through membrane is essential for ADMFC operation. The second scenario is used to analyse requirements on water transport through the membrane for different operation conditions. These requirements are influenced by current density, evaporation rate, methanol cross-over and electro-osmotic drag of water. Simulations indicate that water supply is mainly challenging for high current densities and demands on high water diffusion are intensified by water drag. Thus, current density might be limited by water transport through membrane. The presented results help to identify important effects and processes in ADMFCs with a polymer electrolyte membrane and to understand these processes. Furthermore, the requirements identified by modelling show the importance of considering water transport through membrane besides conductivity and methanol cross-over especially for designing new membrane materials.

  12. TUNING OF SIZE AND SHAPE OF AU-PT NANOCATALYST FOR DIRECT METHANOL FUEL CELLS

    Murph, S.

    2011-04-20

    In this paper, we report the precise control of the size, shape and surface morphology of Au-Pt nanocatalysts (cubes, blocks, octahedrons and dogbones) synthesized via a seed-mediated approach. Gold 'seeds' of different aspect ratios (1 to 4.2), grown by a silver-assisted approach, were used as templates for high-yield production of novel Au-Pt nanocatalysts at a low temperature (40 C). Characterization by electron microscopy (SEM, TEM, HRTEM), energy dispersive X-ray analysis (EDX), UV-Vis spectroscopy, zeta-potential (surface charge), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS) were used to better understand their physico-chemical properties, preferred reactivities and underlying nanoparticle growth mechanism. A rotating disk electrode was used to evaluate the Au-Pt nanocatalysts electrochemical performance in the oxygen reduction reaction (ORR) and the methanol oxidation reaction (MOR) of direct methanol fuel cells. The results indicate the Au-Pt dogbones are partially and in some cases completely unaffected by methanol poisoning during the evaluation of the ORR. The ORR performance of the octahedron particles in the absence of MeOH is superior to that of the Au-Pt dogbones and Pt-black, however its performance is affected by the presence of MeOH.

  13. Co-catalytic effect of Ni in the methanol electro-oxidation on Pt-Ru/C catalyst for direct methanol fuel cell

    Wang, Z.B.; Yin, G.P.; Zhang, J.; Sun, Y.C.; Shi, P.F.

    2006-01-01

    This research is aimed to improve the utilization and activity of anodic catalysts, thus to lower the contents of noble metals loading in anodes for methanol electro-oxidation. The direct methanol fuel cell anodic catalysts, Pt-Ru-Ni/C and Pt-Ru/C, were prepared by chemical reduction method. Their performances were tested by using a glassy carbon working electrode through cyclic voltammetric curves, chronoamperometric curves and half-cell measurement in a solution of 0.5 mol/L CH 3 OH and 0.5 mol/L H 2 SO 4 . The composition of the Pt-Ru-Ni and Pt-Ru surface particles were determined by EDAX analysis. The particle size and lattice parameter of the catalysts were determined by means of X-ray diffraction (XRD). XRD analysis showed that both of the catalysts exhibited face-centered cubic structures and had smaller lattice parameters than Pt-alone catalyst. Their sizes are small, about 4.5 nm. No significant differences in the methanol electro-oxidation on both electrodes were found by using cyclic voltammetry, especially regarding the onset potential for methanol electro-oxidation. The electrochemically active-specific areas of the Pt-Ru-Ni/C and Pt-Ru/C catalysts are almost the same. But, the catalytic activity of the Pt-Ru-Ni/C catalyst is higher for methanol electro-oxidation than that of the Pt-Ru/C catalyst. Its tolerance performance to CO formed as one of the intermediates of methanol electro-oxidation is better than that of the Pt-Ru/C catalyst

  14. Experimental study on methanol recovery through flashing vaporation in continuous production of biodiesel via supercritical methanol

    Wang Cunwen; Chen Wen; Wang Weiguo; Wu Yuanxin; Chi Ruan; Tang Zhengjiao

    2011-01-01

    To improve the oil conversion, high methanol/oil molar ratio is required in the continuous production of biodiesel via supercritical methanol transesterification in tubular reactor. And thus the subsequent excess methanol recovery needs high energy consumption. Based on the feature of high temperature and high pressure in supercritical methanol transesterification, excess methanol recovery in reaction system by flashing vaporation is conducted and the effect of reaction temperature, reaction pressure and flashing pressure on methanol recovery and methanol concentration in gas phase is discussed in detail in this article. Results show that at the reaction pressure of 9-15 MPa and the reaction temperature of 240-300 o C, flashing pressure has significant influence on methanol recovery and methanol content in gas phase, which can be effectively improved by reducing flashing pressure. At the same time, reaction temperature and reaction pressure also have an important effect on methanol recovery and methanol content in gas phase. At volume flow of biodiesel and methanol 1:2, tubular reactor pressure 15 MPa, tubular reactor temperature 300 o C and the flashing pressure 0.4 MPa, methanol recovery is more than 85% and methanol concentration of gas phase (mass fraction) is close to 99% after adiabatic braising; therefore, the condensate liquid of gas phase can be injected directly into methanol feedstock tank to be recycled. Research abstracts: Biodiesel is an important alternative energy, and supercritical methanol transesterification is a new and green technology to prepare biodiesel with some obvious advantages. But it also exists some problems: high reaction temperature, high reaction pressure and large molar ratio of methanol/oil will cause large energy consumption which restricts supercritical methanol for the industrial application of biodiesel. So a set of tubular reactor-coupled flashing apparatus is established for continuous preparing biodiesel in supercritical

  15. Modeling of a 5-cell direct methanol fuel cell using adaptive-network-based fuzzy inference systems

    Wang, Rongrong; Qi, Liang; Xie, Xiaofeng; Ding, Qingqing; Li, Chunwen; Ma, ChenChi M.

    The methanol concentrations, temperature and current were considered as inputs, the cell voltage was taken as output, and the performance of a direct methanol fuel cell (DMFC) was modeled by adaptive-network-based fuzzy inference systems (ANFIS). The artificial neural network (ANN) and polynomial-based models were selected to be compared with the ANFIS in respect of quality and accuracy. Based on the ANFIS model obtained, the characteristics of the DMFC were studied. The results show that temperature and methanol concentration greatly affect the performance of the DMFC. Within a restricted current range, the methanol concentration does not greatly affect the stack voltage. In order to obtain higher fuel utilization efficiency, the methanol concentrations and temperatures should be adjusted according to the load on the system.

  16. Modeling of a 5-cell direct methanol fuel cell using adaptive-network-based fuzzy inference systems

    Wang, Rongrong; Li, Chunwen [Department of Automation, Tsinghua University, Beijing 100084 (China); Qi, Liang; Xie, Xiaofeng [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Ding, Qingqing [Department of Electrical Engineering, Tsinghua University, Beijing 100084 (China); Ma, ChenChi M. [National Tsing Hua University, Hsinchu 300 (China)

    2008-12-01

    The methanol concentrations, temperature and current were considered as inputs, the cell voltage was taken as output, and the performance of a direct methanol fuel cell (DMFC) was modeled by adaptive-network-based fuzzy inference systems (ANFIS). The artificial neural network (ANN) and polynomial-based models were selected to be compared with the ANFIS in respect of quality and accuracy. Based on the ANFIS model obtained, the characteristics of the DMFC were studied. The results show that temperature and methanol concentration greatly affect the performance of the DMFC. Within a restricted current range, the methanol concentration does not greatly affect the stack voltage. In order to obtain higher fuel utilization efficiency, the methanol concentrations and temperatures should be adjusted according to the load on the system. (author)

  17. Effect of fumigation methanol and ethanol on the gaseous and particulate emissions of a direct-injection diesel engine

    Zhang, Z. H.; Tsang, K. S.; Cheung, C. S.; Chan, T. L.; Yao, C. D.

    2011-02-01

    Experiments were conducted on a four-cylinder direct-injection diesel engine with methanol or ethanol injected into the air intake of each cylinder, to compare their effect on the engine performance, gaseous emissions and particulate emissions of the engine under five engine loads at the maximum torque speed of 1800 rev/min. The methanol or ethanol was injected to top up 10% and 20% of the engine loads under different engine operating conditions. The experimental results show that both fumigation methanol and fumigation ethanol decrease the brake thermal efficiency (BTE) at low engine load but improves it at high engine load; however the fumigation methanol has higher influence on the BTE. Compared with Euro V diesel fuel, fumigation methanol or ethanol could lead to reduction of both NOx and particulate mass and number emissions of the diesel engine, with fumigation methanol being more effective than fumigation ethanol in particulate reduction. The NOx and particulate reduction is more effective with increasing level of fumigation. However, in general, fumigation fuels increase the HC, CO and NO 2 emissions, with fumigation methanol leading to higher increase of these pollutants. Compared with ethanol, the fumigation methanol has stronger influence on the in-cylinder gas temperature, the air/fuel ratio, the combustion processes and hence the emissions of the engine.

  18. Performance of direct alcohol fuel cells fed with mixed methanol/ethanol solutions

    Wongyao, N. [The Joint Graduate School of Energy and Environment, King Mongkut' s University of Technology Thonburi, 126 Pracha-Uthit Rd., Bang Mod, Thung Khru, Bangkok 10140 (Thailand); Therdthianwong, A., E-mail: apichai.the@kmutt.ac.t [Fuel Cell and Hydrogen Research and Engineering Center, Clean Energy System Group, PDTI, King Mongkut' s University of Technology Thonburi, 126 Pracha-Uthit Rd., Bang Mod, Thung Khru, Bangkok 10140 (Thailand); Therdthianwong, S. [Department of Chemical Engineering, Faculty of Engineering, King Mongkut' s University of Technology Thonburi, 126 Pracha-Uthit Rd., Bang Mod, Thung Khru, Bangkok 10140 (Thailand)

    2011-07-15

    Research highlights: {yields} We examined the performance of direct alcohol fuel cells fed with mixed alcohol. {yields} PtRu-PtSn/C and PtRu/C as catalysts for mixed alcohol electrooxidation reaction. {yields} Misplace adsorption of ethanol on PtRu/C caused the cell performance drop. {yields} PtRu/C showed higher performance than PtRu-PtSn/C for mixed alcohol fuel. -- Abstract: In combining the advantages of both methanol and ethanol, direct alcohol fuel cells fed with mixed alcohol solutions (1 M methanol and 1 M ethanol in varying volume ratios) were tested for performance. Employing a PtRu-PtSn/C catalyst as anode, cell performance was found to diminish rapidly even at 2.5% by volume ethanol mixture. Further increase of ethanol exceeded 10%, the cell performance gradually decreased and finally approached that of direct ethanol fuel cells. The causes of the decrease in the cell performance were the slow electro-oxidation of ethanol and the misplaced adsorption of ethanol on PtRu/C. By comparing the PtRu-PtSn/C cell with the PtRu/C cell operated with mixed alcohol solutions, the cell using PtRu/C as an anode catalyst provided higher power density since more PtRu/C surface was available for methanol oxidation reaction and less ohmic resistance of PtRu/C than that of PtRu-PtSn/C. In order to reach optimization of DAFC performance fed with mixed alcohol, the electrocatalyst used for the anode must selectively adsorb an alcohol, especially ethanol.

  19. Performance of direct alcohol fuel cells fed with mixed methanol/ethanol solutions

    Wongyao, N.; Therdthianwong, A.; Therdthianwong, S.

    2011-01-01

    Research highlights: → We examined the performance of direct alcohol fuel cells fed with mixed alcohol. → PtRu-PtSn/C and PtRu/C as catalysts for mixed alcohol electrooxidation reaction. → Misplace adsorption of ethanol on PtRu/C caused the cell performance drop. → PtRu/C showed higher performance than PtRu-PtSn/C for mixed alcohol fuel. -- Abstract: In combining the advantages of both methanol and ethanol, direct alcohol fuel cells fed with mixed alcohol solutions (1 M methanol and 1 M ethanol in varying volume ratios) were tested for performance. Employing a PtRu-PtSn/C catalyst as anode, cell performance was found to diminish rapidly even at 2.5% by volume ethanol mixture. Further increase of ethanol exceeded 10%, the cell performance gradually decreased and finally approached that of direct ethanol fuel cells. The causes of the decrease in the cell performance were the slow electro-oxidation of ethanol and the misplaced adsorption of ethanol on PtRu/C. By comparing the PtRu-PtSn/C cell with the PtRu/C cell operated with mixed alcohol solutions, the cell using PtRu/C as an anode catalyst provided higher power density since more PtRu/C surface was available for methanol oxidation reaction and less ohmic resistance of PtRu/C than that of PtRu-PtSn/C. In order to reach optimization of DAFC performance fed with mixed alcohol, the electrocatalyst used for the anode must selectively adsorb an alcohol, especially ethanol.

  20. Graphene-derived Fe/Co-N-C catalyst in direct methanol fuel cells: Effects of the methanol concentration and ionomer content on cell performance

    Park, Jong Cheol; Choi, Chang Hyuck

    2017-08-01

    Non-precious metal catalysts (typically Fe(Co)-N-C catalysts) have been widely investigated for use as cost-effective cathode materials in low temperature fuel cells. Despite the high oxygen reduction activity and methanol-tolerance of graphene-based Fe(Co)-N-C catalysts in an acidic medium, their use in direct methanol fuel cells (DMFCs) has not yet been successfully implemented, and only a few studies have investigated this topic. Herein, we synthesized a nano-sized graphene-derived Fe/Co-N-C catalyst by physical ball-milling and a subsequent chemical modification of the graphene oxide. Twelve membrane-electrode-assemblies are fabricated with various cathode compositions to determine the effects of the methanol concentration, ionomer (i.e. Nafion) content, and catalyst loading on the DMFC performance. The results show that a graphene-based catalyst is capable of tolerating a highly-concentrated methanol feed up to 10.0 M. The optimized electrode composition has an ionomer content and catalyst loading of 66.7 wt% and 5.0 mg cm-2, respectively. The highest maximum power density is ca. 32 mW cm-2 with a relatively low PtRu content (2 mgPtRu cm-2). This study overcomes the drawbacks of conventional graphene-based electrodes using a nano-sized graphene-based catalyst and further shows the feasibility of their potential applications in DMFC systems.

  1. High Performance and Cost-Effective Direct Methanol Fuel Cells: Fe-N-C Methanol-Tolerant Oxygen Reduction Reaction Catalysts.

    Sebastián, David; Serov, Alexey; Artyushkova, Kateryna; Gordon, Jonathan; Atanassov, Plamen; Aricò, Antonino S; Baglio, Vincenzo

    2016-08-09

    Direct methanol fuel cells (DMFCs) offer great advantages for the supply of power with high efficiency and large energy density. The search for a cost-effective, active, stable and methanol-tolerant catalyst for the oxygen reduction reaction (ORR) is still a great challenge. In this work, platinum group metal-free (PGM-free) catalysts based on Fe-N-C are investigated in acidic medium. Post-treatment of the catalyst improves the ORR activity compared with previously published PGM-free formulations and shows an excellent tolerance to the presence of methanol. The feasibility for application in DMFC under a wide range of operating conditions is demonstrated, with a maximum power density of approximately 50 mW cm(-2) and a negligible methanol crossover effect on the performance. A review of the most recent PGM-free cathode formulations for DMFC indicates that this formulation leads to the highest performance at a low membrane-electrode assembly (MEA) cost. Moreover, a 100 h durability test in DMFC shows suitable applicability, with a similar performance-time behavior compared to common MEAs based on Pt cathodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Characterization of Polyethylene-Graft-Sulfonated Polyarylsulfone Proton Exchange Membranes for Direct Methanol Fuel Cell Applications.

    Kim, Hyung Kyu; Zhang, Gang; Nam, Changwoo; Chung, T C Mike

    2015-12-04

    This paper examines polymer film morphology and several important properties of polyethylene-graft-sulfonated polyarylene ether sulfone (PE-g-s-PAES) proton exchange membranes (PEMs) for direct methanol fuel cell applications. Due to the extreme surface energy differences between a semi-crystalline and hydrophobic PE backbone and several amorphous and hydrophilic s-PAES side chains, the PE-g-s-PAES membrane self-assembles into a unique morphology, with many proton conductive s-PAES channels embedded in the stable and tough PE matrix and a thin hydrophobic PE layer spontaneously formed on the membrane surfaces. In the bulk, these membranes show good mechanical properties (tensile strength >30 MPa, Young's modulus >1400 MPa) and low water swelling (λ 3 mmol/g in the s-PAES domains. On the surface, the thin hydrophobic and semi-crystalline PE layer shows some unusual barrier (protective) properties. In addition to exhibiting higher through-plane conductivity (up to 160 mS/cm) than in-plane conductivity, the PE surface layer minimizes methanol cross-over from anode to cathode with reduced fuel loss, and stops the HO• and HO₂• radicals, originally formed at the anode, entering into PEM matrix. Evidently, the thin PE surface layer provides a highly desirable protecting layer for PEMs to reduce fuel loss and increase chemical stability. Overall, the newly developed PE-g-s-PAES membranes offer a desirable set of PEM properties, including conductivity, selectivity, mechanical strength, stability, and cost-effectiveness for direct methanol fuel cell applications.

  3. Characterization of Polyethylene-Graft-Sulfonated Polyarylsulfone Proton Exchange Membranes for Direct Methanol Fuel Cell Applications

    Hyung Kyu Kim

    2015-12-01

    Full Text Available This paper examines polymer film morphology and several important properties of polyethylene-graft-sulfonated polyarylene ether sulfone (PE-g-s-PAES proton exchange membranes (PEMs for direct methanol fuel cell applications. Due to the extreme surface energy differences between a semi-crystalline and hydrophobic PE backbone and several amorphous and hydrophilic s-PAES side chains, the PE-g-s-PAES membrane self-assembles into a unique morphology, with many proton conductive s-PAES channels embedded in the stable and tough PE matrix and a thin hydrophobic PE layer spontaneously formed on the membrane surfaces. In the bulk, these membranes show good mechanical properties (tensile strength >30 MPa, Young’s modulus >1400 MPa and low water swelling (λ < 15 even with high IEC >3 mmol/g in the s-PAES domains. On the surface, the thin hydrophobic and semi-crystalline PE layer shows some unusual barrier (protective properties. In addition to exhibiting higher through-plane conductivity (up to 160 mS/cm than in-plane conductivity, the PE surface layer minimizes methanol cross-over from anode to cathode with reduced fuel loss, and stops the HO• and HO2• radicals, originally formed at the anode, entering into PEM matrix. Evidently, the thin PE surface layer provides a highly desirable protecting layer for PEMs to reduce fuel loss and increase chemical stability. Overall, the newly developed PE-g-s-PAES membranes offer a desirable set of PEM properties, including conductivity, selectivity, mechanical strength, stability, and cost-effectiveness for direct methanol fuel cell applications.

  4. A Four-Site Molecular Model for Simulations of Liquid Methanol and Water-Methanol Mixtures: MeOH-4P.

    Martínez-Jiménez, Manuel; Saint-Martin, Humberto

    2018-04-17

    In this work, we present a new four-site potential for methanol, MeOH-4P, fitted to reproduce the dielectric constant ε, the surface tension γ s , and the liquid density ρ of the pure liquid at T = 298.15 K and p = 1 bar. The partial charges on each site were taken from the OPLS/2016 model with the only difference of putting the negative charge on the fourth site ( M) instead of on the O atom, as done in four-site water models. The original Lennard-Jones (LJ) parameters of OPLS/2016 for the methyl moiety (Me) were modified for the fitting of ρ and γ s , whereas the parameters of the TIP4P-FB water model were used for the O atom without change. Taking into account the energetic cost of the enhanced dipole relative to the isolated molecule, the results from simulations with this model showed good agreement with experiments for ρ, α p , κ T , C p , and Δ H v- l . Also, the temperature dependence of γ s and ε is satisfactory in the interval between 260 and 360 K, and the critical point description is similar to that of OPLS/2016. It is shown that orientational correlations, described by the Kirkwood factor G k , play a prominent role in the appropriate description of dielectric constants in existing models; unfortunately, the enhancement of the dipole moment produced a low diffusion coefficient D MeOH ; thus, a compromise was required between a good reproduction of ε and an acceptable D MeOH . The use of a fourth site resulted in a significant improvement for water-methanol mixtures described with TIP4P-FB and MeOH-4P, respectively, but required the modification of the LJ geometric combination rule to allow a good description of the methanol molar-fraction dependence of ρ, ε, and methanol (water) diffusion coefficients D MeOH ( D H 2 O ) and excess volume of mixing Δ V mix in the entire range of composition. The resulting free energy of hydration Δ G hyd shows excellent agreement with experiments in the interval between 280 and 360 K.

  5. Methyl phosphate formation as a major degradation mode of direct methanol fuel cells with phosphoric acid based electrolytes

    Aili, David; Vassiliev, Anton; Jensen, Jens Oluf

    2015-01-01

    Phosphoric acid and phosphoric acid doped polymer membranes are widely used as electrolytes in hydrogen based fuel cells operating at elevated temperatures. Such electrolytes have been explored for direct oxidation of methanol to further increase the versatility of the systems, however......, with demonstrated lifetimes of only a few days to weeks. In this work the methyl phosphate formation from the acid and methanol is identified and proposed to be a major mechanism for the cell degradation. Proton conductivity and fuel cell durability tests validate the mechanism at high methanol contents....

  6. Cost Analysis of Direct Methanol Fuel Cell Stacks for Mass Production

    Mauro Francesco Sgroi

    2016-11-01

    Full Text Available Fuel cells are very promising technologies for efficient electrical energy generation. The development of enhanced system components and new engineering solutions is fundamental for the large-scale deployment of these devices. Besides automotive and stationary applications, fuel cells can be widely used as auxiliary power units (APUs. The concept of a direct methanol fuel cell (DMFC is based on the direct feed of a methanol solution to the fuel cell anode, thus simplifying safety, delivery, and fuel distribution issues typical of conventional hydrogen-fed polymer electrolyte fuel cells (PEMFCs. In order to evaluate the feasibility of concrete application of DMFC devices, a cost analysis study was carried out in the present work. A 200 W-prototype developed in the framework of a European Project (DURAMET was selected as the model system. The DMFC stack had a modular structure allowing for a detailed evaluation of cost characteristics related to the specific components. A scale-down approach, focusing on the model device and projected to a mass production, was used. The data used in this analysis were obtained both from research laboratories and industry suppliers specialising in the manufacturing/production of specific stack components. This study demonstrates that mass production can give a concrete perspective for the large-scale diffusion of DMFCs as APUs. The results show that the cost derived for the DMFC stack is relatively close to that of competing technologies and that the introduction of innovative approaches can result in further cost savings.

  7. Performance of an Active Micro Direct Methanol Fuel Cell Using Reduced Catalyst Loading MEAs

    D.S. Falcão

    2017-10-01

    Full Text Available The micro direct methanol fuel cell (MicroDMFC is an emergent technology due to its special interest for portable applications. This work presents the results of a set of experiments conducted at room temperature using an active metallic MicroDMFC with an active area of 2.25 cm2. The MicroDMFC uses available commercial materials with low platinum content in order to reduce the overall fuel cell cost. The main goal of this work is to provide useful information to easily design an active MicroDMFC with a good performance recurring to cheaper commercial Membrane Electrode Assemblies MEAs. A performance/cost analysis for each MEA tested is provided. The maximum power output obtained was 18.1 mW/cm2 for a hot-pressed MEA with materials purchased from Quintech with very low catalyst loading (3 mg/cm2 Pt–Ru at anode side and 0.5 mg/cm2 PtB at the cathode side costing around 15 euros. Similar power values are reported in literature for the same type of micro fuel cells working at higher operating temperatures and substantially higher cathode catalyst loadings. Experimental studies using metallic active micro direct methanol fuel cells operating at room temperature are very scarce. The results presented in this work are, therefore, very useful for the scientific community.

  8. Hybridization and control of a mobile direct methanol fuel cell system; Hybridisierung und Regelung eines mobilen Direktmethanol-Brennstoffzellen-Systems

    Wilhelm, Joerg Christoph

    2010-07-01

    Direct methanol fuel cells (DMFCs) are characterized by the fact that they directly convert the chemical energy of the liquid fuel methanol into electrical energy. Methanol has a high energy density and can be stored relatively easily. Due to these advantages, direct methanol fuel cell systems are suitable, for example, as a battery replacement for light-traction applications in the kW class. Since refuelling is much faster than recharging a battery, almost interruption-free operation is possible. The aim of this thesis is therefore to develop a direct methanol fuel cell system for light-traction applications. The systems technology development and characterization of a mobile direct methanol fuel cell system is initially examined in general and then applied to the example of a horizontal order picker, a type of forklift truck. A hybridization and control concept is developed for this type of truck. The procedure is structured into the theoretical characterization of the application, the development of theoretical concepts and a concluding systems analysis using data from the test stand and simulations. The characteristic driving cycle of the application results from the characterization. The concept development is based on key data such as maximum peak power during acceleration and braking as well as average power. The two-stage theoretical development of a hybridization concept is based on a pure fuel cell vehicle. A systems analysis of all possible concepts with respect to the criteria of fuel cell power, total system efficiency and dynamic fuel cell loading eventually leads to the preferred concept of indirect coupling. A cascade controller with map control, the control concept developed for this purpose, keeps the energy storage unit at a constant state of charge and provides for the fuel cell aging protection as well as aging detection. The driving cycle, operational states of the vehicle and the efficiencies of the individual components play a decisive role

  9. Quantitative NMR spectroscopy of binary liquid mixtures (aldehyde + alcohol) Part I: Acetaldehyde + (methanol or ethanol or 1-propanol)

    Jaubert, Silke; Maurer, Gerd

    2014-01-01

    Highlights: • Formation of hemiacetal/poly(oxymethylene) hemiacetals in liquid binary mixtures. • Acetaldehyde and a low molecular alcohol (methanol or ethanol or 1-propanol). • Quantitative 13 C NMR spectroscopy at temperatures between (255 and 295) K. • Hemiacetals are the predominant species. • (Acetaldehyde + methanol (50 + 50)) at 255 K: hemiacetal (polymers) >80% (≈10%). -- Abstract: Aldehydes react with alcohols to hemiacetals and poly(oxymethylene) hemiacetals. The chemical reaction equilibria of such reactions, in particular in the liquid state, can have an essential influence on the thermodynamic properties and related phenomena like, for example, on the vapour + liquid phase equilibrium. Therefore, thermodynamic models that aim to describe quantitatively such phase equilibria have to consider the chemical reaction equilibrium in the coexisting phases. This is well known in the literature for systems such as, for example, formaldehyde and methanol. However, experimental information on the chemical reaction equilibria in mixtures with other aldehydes (than formaldehyde) and alcohols is extremely scarce. Therefore, quantitative NMR spectroscopy was used to investigate the chemical reaction equilibria in binary mixtures of acetaldehyde and a single alcohol (here either methanol, ethanol or 1-propanol) at temperatures between (255 and 295) K. The results reveal that the majority of the constituents of the mixture is present as hemiacetal and the first two poly(oxymethylene) hemiacetals: in an equimolar mixture of (acetaldehyde + methanol or ethanol or 1-propanol), between about 90% at T = 255 K and about 75% at 295 K. The mole-fraction based chemical reaction equilibrium constants for the formation of those species were determined and some derived properties are reported

  10. Au/ZnS core/shell nanocrystals as an efficient anode photocatalyst in direct methanol fuel cells.

    Chen, Wei-Ta; Lin, Yin-Kai; Yang, Ting-Ting; Pu, Ying-Chih; Hsu, Yung-Jung

    2013-10-04

    Au/ZnS core/shell nanocrystals with controllable shell thicknesses were synthesized using a cysteine-assisted hydrothermal method. Incorporating Au/ZnS nanocrystals into the traditional Pt-catalyzed half-cell reaction led to a 43.3% increase in methanol oxidation current under light illumination, demonstrating their promising potential for metal/semiconductor hybrid nanocrystals as the anode photocatalyst in direct methanol fuel cells.

  11. A self-supported 40W direct methanol fuel cell system

    ... and maintains a constant methanol-feed concentration with thermal management in the system. ... During the operation, methanol ... catalyst poisoning.5–8 Accordingly, it is necessary to consider the operational characteristics of all the con-.

  12. Evaluation of sulfonated polysulfone/zirconium hydrogen phosphate composite membranes for direct methanol fuel cells

    Ozden, Adnan; Ercelik, Mustafa; Devrim, Yilser; Colpan, C. Ozgur; Hamdullahpur, Feridun

    2017-01-01

    Highlights: •Very thin SPSf/ZrP composite membranes were prepared by solution casting method. •The viability of SPSf/ZrP membranes for DMFCs was investigated for the first time. •Superior proton conductivity over Nafion ® 115 was achieved between 45–80 °C. •Desired membrane characteristics, along with low manufacturing cost were achieved. •Single cell DMFC performance was improved up to 13%. -- Abstract: Direct methanol fuel cell (DMFC) technology has advanced perceivably, but technical challenges remain that must be overcome for further performance improvements. Thus, in this study, sulfonated polysulfone/zirconium hydrogen phosphate (SPSf/ZrP) composite membranes with various sulfonation degrees (20%, 35%, and 42%) and a constant concentration of ZrP (2.5%) were prepared to mitigate the technical challenges associated with the use of conventional Nafion ® membranes in DMFCs. The composite membranes were investigated through Scanning Electron Microscopy (SEM), Electrochemical Impedance Spectroscopy (EIS), Thermogravimetric Analysis (TGA), oxidative stability and water uptake measurements, and single cell testing. Comparison was also made with Nafion ® 115. Single cell tests were performed under various methanol concentrations and cell temperatures. Stability characteristics of the DMFCs under charging and discharging conditions were investigated via 1200 min short-term stability tests. The response characteristics of the DMFCs under dynamic conditions were determined at the start-up and shut-down stages. Composite membranes with sulfonation degrees of 35% and 42% were found to be highly promising due to their advanced characteristics with respect to proton conductivity, water uptake, thermal resistance, oxidative stability, and methanol suppression. For the whole range of parameters studied, the maximum power density obtained for SPSf/ZrP-42 (119 mW cm −2 ) was found to be 13% higher than that obtained for Nafion ® 115 (105 mW cm −2 ).

  13. Mass transport of direct methanol fuel cell species in sulfonated poly(ether ether ketone) membranes

    Silva, V.S.; Ruffmann, B.; Vetter, S.; Boaventura, M.; Mendes, A.M.; Madeira, L.M.; Nunes, S.P.

    2006-01-01

    Homogeneous membranes based on sulfonated poly(ether ether ketone) (sPEEK) with different sulfonation degrees (SD) were prepared and characterized. In order to perform a critical analysis of the SD effect on the polymer barrier and mass transport properties towards direct methanol fuel cell species, proton conductivity, water/methanol pervaporation and nitrogen/oxygen/carbon dioxide pressure rise method experiments are proposed. This procedure allows the evaluation of the individual permeability coefficients in hydrated sPEEK membranes with different sulfonation degrees. Nafion[reg] 112 was used as reference material. DMFC tests were also performed at 50 deg. C. It was observed that the proton conductivity and the permeability towards water, methanol, oxygen and carbon dioxide increase with the sPEEK sulfonation degree. In contrast, the SD seems to not affect the nitrogen permeability coefficient. In terms of selectivity, it was observed that the carbon dioxide/oxygen selectivity increases with the sPEEK SD. In contrast, the nitrogen/oxygen selectivity decreases. In terms of barrier properties for preventing the DMFC reactants loss, the polymer electrolyte membrane based on the sulfonated poly(ether ether ketone) with SD lower or equal to 71%, although having slightly lower proton conductivity, presented much better characteristics for fuel cell applications compared with the well known Nafion[reg] 112. In terms of the DMFC tests of the studied membranes at low temperature, the sPEEK membrane with SD = 71% showed to have similar performance, or even better, as that of Nafion[reg] 112. However, the highest DMFC overall efficiency was achieved using sPEEK membrane with SD = 52%

  14. A Graphite Oxide Paper Polymer Electrolyte for Direct Methanol Fuel Cells

    Ravi Kumar

    2011-01-01

    Full Text Available A flow directed assembly of graphite oxide solution was used in the formation of free-standing graphene oxide paper of approximate thickness of 100 μm. The GO papers were characterised by XRD and SEM. Electrochemical characterization of the GO paper membrane electrode assembly revealed proton conductivities of 4.1 × 10−2 S cm−1 to 8.2 × 10−2 S cm−1 at temperatures of 25–90°C. A direct methanol fuel cell, at 60°C, gave a peak power density of 8 mW cm−2 at a current density of 35 mA cm−2.

  15. Synthesis of Pd₃Co₁@Pt/C core-shell catalysts for methanol-tolerant cathodes of direct methanol fuel cells.

    Aricò, Antonino S; Stassi, Alessandro; D'Urso, Claudia; Sebastián, David; Baglio, Vincenzo

    2014-08-18

    A composite Pd-based electrocatalyst consisting of a surface layer of Pt (5 wt.%) supported on a core Pd3Co1 alloy (95 wt.%) and dispersed as nanoparticles on a carbon black support (50 wt.% metal content) was prepared by using a sulphite-complex route. The structure, composition, morphology, and surface properties of the catalyst were investigated by XRD, XRF, TEM, XPS and low-energy ion scattering spectroscopy (LE-ISS). The catalyst showed an enrichment of Pt on the surface and a smaller content of Co in the outermost layers. These characteristics allow a decrease the Pt content in direct methanol fuel cell cathode electrodes (from 1 to 0.06 mg cm(-2)) without significant decay in performance, due also to a better tolerance to methanol permeated through the polymer electrolyte membrane. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Preparation of supported PtRu/C electrocatalyst for direct methanol fuel cells

    Jiang Luhua; Sun Gongquan; Zhao Xinsheng; Zhou Zhenhua; Yan Shiyou; Tang Shuihua; Wang Guoxiong; Zhou Bing; Xin Qin

    2005-01-01

    In this work, high-surface supported PtRu/C were prepared with Ru(NO)(NO 3 ) 3 and [Pt(H 2 NCH 2 CH 2 NH 2 ) 2 ]Cl 2 as the precursors and hydrogen as a reducing agent. XRD and TEM analyses showed that the PtRu/C catalysts with different loadings possessed small and homogeneous metal particles. Even at high metal loading (40 wt.% Pt, 20 wt.% Ru) the mean metal particle size is less than 4 nm. Meanwhile, the calculated Pt crystalline lattice parameter and Pt (2 2 0) peak position indicated that the geometric structure of Pt was modified by Ru atoms. Among the prepared catalysts, the lattice parameter of 40-20 wt.% PtRu/C contract most. Cyclic voltammetry (CV), chronoamperometry (CA), CO stripping and single direct methanol fuel cell tests jointly suggested that the 40-20 wt.% PtRu/C catalyst has the highest electrochemical activity for methanol oxidation

  17. Mass-produced multi-walled carbon nanotubes as catalyst supports for direct methanol fuel cells.

    Jang, In Young; Park, Ki Chul; Jung, Yong Chae; Lee, Sun Hyung; Song, Sung Moo; Muramatsu, Hiroyuki; Kim, Yong Jung; Endo, Morinobu

    2011-01-01

    Commercially mass-produced multi-walled carbon nanotubes, i.e., VGNF (Showa Denko Co.), were applied to support materials for platinum-ruthenium (PtRu) nanoparticles as anode catalysts for direct methanol fuel cells. The original VGNFs are composed of high-crystalline graphitic shells, which hinder the favorable surface deposition of the PtRu nanoparticles that are formed via borohydride reduction. The chemical treatment of VGNFs with potassium hydroxide (KOH), however, enables highly dispersed and dense deposition of PtRu nanoparticles on the VGNF surface. This capability becomes more remarkable depending on the KOH amount. The electrochemical evaluation of the PtRu-deposited VGNF catalysts showed enhanced active surface areas and methanol oxidation, due to the high dispersion and dense deposition of the PtRu nanoparticles. The improvement of the surface deposition states of the PtRu nanoparticles was significantly due to the high surface area and mesorporous surface structure of the KOH-activated VGNFs.

  18. Combinatorial approach toward high-throughput analysis of direct methanol fuel cells.

    Jiang, Rongzhong; Rong, Charles; Chu, Deryn

    2005-01-01

    A 40-member array of direct methanol fuel cells (with stationary fuel and convective air supplies) was generated by electrically connecting the fuel cells in series. High-throughput analysis of these fuel cells was realized by fast screening of voltages between the two terminals of a fuel cell at constant current discharge. A large number of voltage-current curves (200) were obtained by screening the voltages through multiple small-current steps. Gaussian distribution was used to statistically analyze the large number of experimental data. The standard deviation (sigma) of voltages of these fuel cells increased linearly with discharge current. The voltage-current curves at various fuel concentrations were simulated with an empirical equation of voltage versus current and a linear equation of sigma versus current. The simulated voltage-current curves fitted the experimental data well. With increasing methanol concentration from 0.5 to 4.0 M, the Tafel slope of the voltage-current curves (at sigma=0.0), changed from 28 to 91 mV.dec-1, the cell resistance from 2.91 to 0.18 Omega, and the power output from 3 to 18 mW.cm-2.

  19. Single wall carbon nanotube supports for portable direct methanol fuel cells.

    Girishkumar, G; Hall, Timothy D; Vinodgopal, K; Kamat, Prashant V

    2006-01-12

    Single-wall and multiwall carbon nanotubes are employed as carbon supports in direct methanol fuel cells (DMFC). The morphology and electrochemical activity of single-wall and multiwall carbon nanotubes obtained from different sources have been examined to probe the influence of carbon support on the overall performance of DMFC. The improved activity of the Pt-Ru catalyst dispersed on carbon nanotubes toward methanol oxidation is reflected as a shift in the onset potential and a lower charge transfer resistance at the electrode/electrolyte interface. The evaluation of carbon supports in a passive air breathing DMFC indicates that the observed power density depends on the nature and source of carbon nanostructures. The intrinsic property of the nanotubes, dispersion of the electrocatalyst and the electrochemically active surface area collectively influence the performance of the membrane electrode assembly (MEA). As compared to the commercial carbon black support, single wall carbon nanotubes when employed as the support for anchoring the electrocatalyst particles in the anode and cathode sides of MEA exhibited a approximately 30% enhancement in the power density of a single stack DMFC operating at 70 degrees C.

  20. Palladium-Based Catalysts as Electrodes for Direct Methanol Fuel Cells: A Last Ten Years Review

    Juan Carlos Calderón Gómez

    2016-08-01

    Full Text Available Platinum-based materials are accepted as the suitable electrocatalysts for anodes and cathodes in direct methanol fuel cells (DMFCs. Nonetheless, the increased demand and scarce world reserves of Pt, as well as some technical problems associated with its use, have motivated a wide research focused to design Pd-based catalysts, considering the similar properties between this metal and Pt. In this review, we present the most recent advancements about Pd-based catalysts, considering Pd, Pd alloys with different transition metals and non-carbon supported nanoparticles, as possible electrodes in DMFCs. In the case of the anode, different reported works have highlighted the capacity of these new materials for overcoming the CO poisoning and promote the oxidation of other intermediates generated during the methanol oxidation. Regarding the cathode, the studies have showed more positive onset potentials, as fundamental parameter for determining the mechanism of the oxygen reduction reaction (ORR and thus, making them able for achieving high efficiencies, with less production of hydrogen peroxide as collateral product. This revision suggests that it is possible to replace the conventional Pt catalysts by Pd-based materials, although several efforts must be made in order to improve their performance in DMFCs.

  1. Design, fabrication and performance of a mixed-reactant membraneless micro direct methanol fuel cell stack

    Abrego-Martínez, J. C.; Moreno-Zuria, A.; Cuevas-Muñiz, F. M.; Arriaga, L. G.; Sun, Shuhui; Mohamedi, Mohamed

    2017-12-01

    In the present work, we report the design, fabrication and evaluation of a membraneless mixed-reactant and air-breathing microfluidic direct methanol fuel cell (ML-μDMFC) stack operated in passive mode. The operation under mixed-reactant conditions was achieved by using a highly methanol-tolerant Ag/Pt/CP cathode with ultra-low Pt loading in alkaline medium. Prior to the fabrication of the stack, a flow simulation was made in order to study the behavior of the reactants stream in the microchannel through the 2 cells. Subsequently, the device was tested in passive mode using a mixture of 5 M MeOH +0.5 M KOH. The results showed that by connecting the 2 cells in series, it is possible to effectively double the voltage of a single ML-μDMFC, as well as increasing the absolute power by 75% with practically no cost increase. The stack was capable of operate continuously for more than 2 h with a single charge of 40 μL, producing an OCV of 0.89 V and a maximum power density of 3.33 mW mgPt-1. Additionally, the device exhibited good stability throughout a 10 h test.

  2. Ion pair reinforced semi-interpenetrating polymer network for direct methanol fuel cell applications.

    Fang, Chunliu; Julius, David; Tay, Siok Wei; Hong, Liang; Lee, Jim Yang

    2012-06-07

    This paper describes the synthesis of ion-pair-reinforced semi-interpenetrating polymer networks (SIPNs) as proton exchange membranes (PEMs) for the direct methanol fuel cells (DMFCs). Specifically, sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (SPPO), a linear polymer proton source, was immobilized in a brominated PPO (BPPO) network covalently cross-linked by ethylenediamine (EDA). The immobilization of SPPO in the SIPN network was accomplished not only by the usual means of mechanical interlocking but also by ion pair formation between the sulfonic acid groups of SPPO and the amine moieties formed during the cross-linking reaction of BPPO with EDA. Through the ion pair interactions, the immobilization of SPPO polymer in the BPPO network was made more effective, resulting in a greater uniformity of sulfonic acid cluster distribution in the membrane. The hydrophilic amine-containing cross-links also compensated for some of the decrease in proton conductivity caused by ion pair formation. The SIPN membranes prepared as such showed good proton conductivity, low methanol permeability, good mechanical properties, and dimensional stability. Consequently, the PPO based SIPN membranes were able to deliver a higher maximum power density than Nafion, demonstrating the potential of the SIPN structure for PEM designs.

  3. Development of a Direct Methanol Fuel Cell with Lightweight Disc Type Current Collectors

    Yean-Der Kuan

    2014-05-01

    Full Text Available The direct methanol fuel cell (DMFC adopts methanol solution as a fuel suitable for low power portable applications. A miniature, lightweight, passive air-breathing design is therefore desired. This paper presents a novel planar disc-type DMFC with multiple cells containing a novel developed lightweight current collector at both the anode and cathode sides. The present lightweight current collector adopts FR4 Glass/Epoxy as the substrate with the current collecting areas located at the corresponding membrane electrolyte assembly (MEA areas. The current collecting areas are fabricated by sequentially coating a corrosion resistant layer and electrical conduction layer via the thermal evaporation technique. The anode current collector has carved flow channels for fuel transport and production. The cathode current collector has drilled holes for passive air breathing. In order to ensure feasibility in the present concept a 3-cell prototype DMFC module with lightweight disc type current collectors is designed and constructed. Experiments were conducted to measure the cell performance. The results show that the highest cell power output is 54.88 mW·cm−2 and successfully demonstrate the feasibility of this novel design.

  4. Isothermal vapour-liquid equilibria data of methanol + propan-2-OL ...

    methylpropan-2-ol binary mixtures are investigated at 333.15k, using gas chromatographic technique. ... The y-x plots reveals that the mixtures methanol + propan-2-ol and methanol +2-methylpropan-2-ol deviate strongly from ideal solution behaviour.

  5. The electrolyte challenge for a direct methanol-air polymer electrolyte fuel cell operating at temperatures up to 200 C

    Savinell, Robert; Yeager, Ernest; Tryk, Donald; Landau, Uziel; Wainright, Jesse; Gervasio, Dominic; Cahan, Boris; Litt, Morton; Rogers, Charles; Scherson, Daniel

    1993-01-01

    Novel polymer electrolytes are being evaluated for use in a direct methanol-air fuel cell operating at temperatures in excess of 100 C. The evaluation includes tests of thermal stability, ionic conductivity, and vapor transport characteristics. The preliminary results obtained to date indicate that a high temperature polymer electrolyte fuel cell is feasible. For example, Nafion 117 when equilibrated with phosphoric acid has a conductivity of at least 0.4 Omega(exp -1)cm(exp -1) at temperatures up to 200 C in the presence of 400 torr of water vapor and methanol vapor cross over equivalent to 1 mA/cm(exp 2) under a one atmosphere methanol pressure differential at 135 C. Novel polymers are also showing similar encouraging results. The flexibility to modify and optimize the properties by custom synthesis of these novel polymers presents an exciting opportunity to develop an efficient and compact methanol fuel cell.

  6. Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOH) Process

    None

    1998-12-21

    he Liquid Phase Methanol (LPMEOW) Demonstration Project at Kingsport Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership) to produce methanol from coal-derived synthesis gas (syngas). Air Products and Chemicals, Inc. (Air Products) and Eastman Chemical Company (Eastman) formed the Partnership to execute the Demonstration Project. The LPMEOEP Process Demonstration Unit was built at a site located at the Eastman coal-to-chemicals complex in Kingsport. The LPMEOHW Demonstration Facility completed its first year of operation on 02 April 1998. The LPMEOW Demonstration Facility also completed the longest continuous operating run (65 days) on 21 April 1998. Catalyst activity, as defined by the ratio of the rate constant at any point in time to the rate constant for freshly reduced catalyst (as determined in the laboratory autoclave), was monitored throughout the reporting period. During a six-week test at a reactor temperature of 225oC and Balanced Gas flowrate of 700 KSCFH, the rate of decline in catalyst activity was steady at 0.29-0.36% per day. During a second one-month test at a reactor temperature of 220oC and a Balanced Gas flowrate of 550-600 KSCFH, the rate of decline in catalyst activity was 0.4% per day, which matched the pefiorrnance at 225"C, as well as the 4-month proof-of-concept run at the LaPorte AFDU in 1988/89. Beginning on 08 May 1998, the LPMEOW Reactor temperature was increased to 235oC, which was the operating temperature tier the December 1997 restart with the fresh charge of catalyst (50'Yo of design loading). The flowrate of the primary syngas feed stream (Balanced Gas) was also increased to 700-750 KSCFH. During two stable operating periods between 08 May and 09 June 1998, the average catalyst deactivation rate was 0.8% per day. Due to the scatter of the statistical analysis of the results, this test was extended to better

  7. A comparative study of approaches to direct methanol fuel cells modelling

    Oliveira, V.B.; Falcao, D.S.; Pinto, A.M.F.R. [Centro de Estudos de Fenomenos de Transporte, Departamento de Eng. Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Rangel, C.M. [Instituto Nacional de Engenharia, Tecnologia e Inovacao, Paco do Lumiar, 22,1649-038 (Portugal)

    2007-03-15

    Fuel cell modelling has received much attention over the past decade in an attempt to better understand the phenomena occurring within the cell. Mathematical models and simulation are needed as tools for design optimization of fuel cells, stacks and fuel cell power systems. Analytical, semi-empirical and mechanistic models for direct methanol fuel cells (DMFC) are reviewed. Effective models were until now developed describing the fundamental electrochemical and transport phenomena taking place in the cell. More research is required to develop models that can account for the two-phase flows occurring in the anode and cathode of the DMFC. The merits and demerits of the models are presented. Selected models of different categories are implemented and discussed. Finally, one of the selected simplified models is proposed as a computer-aided tool for real-time system level DMFC calculations. (author)

  8. SHAPE SELECTIVE NANO-CATALYSTS: TOWARD DIRECT METHANOL FUEL CELLS APPLICATIONS

    Murph, S.

    2010-06-16

    A series of bimetallic core-shell-alloy type Au-Pt nanomaterials with various morphologies, aspect ratios and compositions, were produced in a heterogenous epitaxial fashion. Gold nanoparticles with well-controlled particle size and shape, e.g. spheres, rods and cubes, were used as 'seeds' for platinum growth in the presence of a mild reducing agent, ascorbic acid and a cationic surfactant cethyltrimethyl ammonium bromide (CTAB). The reactions take place in air and water, and are quick, economical and amenable for scaling up. The synthesized nanocatalysts were characterized by electron microscopy techniques and energy dispersive X-ray analysis. Nafion membranes were embedded with the Au-Pt nanomaterials and analyzed by atomic force microscopy (AFM) and scanning electron microscopy (SEM) for their potential in direct methanol fuel cells applications.

  9. Experimental Investigation of a Direct Methanol Fuel Cell with Hilbert Fractal Current Collectors

    Jing-Yi Chang

    2014-01-01

    Full Text Available The Hilbert curve is a continuous type of fractal space-filling curve. This fractal curve visits every point in a square grid with a size of 2×2, 4×4, or any other power of two. This paper presents Hilbert fractal curve application to direct methanol fuel cell (DMFC current collectors. The current collectors are carved following first, second, and third order Hilbert fractal curves. These curves give the current collectors different free open ratios and opening perimeters. We conducted an experimental investigation into DMFC performance as a function of the free open ratio and opening perimeter on the bipolar plates. Nyquist plots of the bipolar plates are made and compared using electrochemical impedance spectroscopy (EIS experiments to understand the phenomena in depth. The results obtained in this paper could be a good reference for future current collector design.

  10. Catalyst inks and method of application for direct methanol fuel cells

    Zelenay, Piotr; Davey, John; Ren, Xiaoming; Gottesfeld, Shimshon; Thomas, Sharon C.

    2004-02-24

    Inks are formulated for forming anode and cathode catalyst layers and applied to anode and cathode sides of a membrane for a direct methanol fuel cell. The inks comprise a Pt catalyst for the cathode and a Pt--Ru catalyst for the anode, purified water in an amount 4 to 20 times that of the catalyst by weight, and a perfluorosulfonic acid ionomer in an amount effective to provide an ionomer content in the anode and cathode surfaces of 20% to 80% by volume. The inks are prepared in a two-step process while cooling and agitating the solutions. The final solution is placed in a cooler and continuously agitated while spraying the solution over the anode or cathode surface of the membrane as determined by the catalyst content.

  11. Micro direct methanol fuel cell with perforated silicon-plate integrated ionomer membrane

    Larsen, Jackie Vincent; Dalslet, Bjarke Thomas; Johansson, Anne-Charlotte Elisabeth Birgitta

    2014-01-01

    This article describes the fabrication and characterization of a silicon based micro direct methanol fuel cell using a Nafion ionomer membrane integrated into a perforated silicon plate. The focus of this work is to provide a platform for micro- and nanostructuring of a combined current collector...... at a perforation ratio of 40.3%. The presented fuel cells also show a high volumetric peak power density of 2 mW cm−3 in light of the small system volume of 480 μL, while being fully self contained and passively feed....... and catalytic electrode. AC impedance spectroscopy is utilized alongside IV characterization to determine the influence of the plate perforation geometries on the cell performance. It is found that higher ratios of perforation increases peak power density, with the highest achieved being 2.5 mW cm−2...

  12. Combined local current distribution measurements and high resolution neutron radiography of operating direct methanol fuel cells

    Schroeder, Alexander; Wippermann, Klaus [Forschungszentrum Juelich GmbH (Germany). Inst. of Energy Research, IEF-3: Fuel Cells; Sanders, Tilman [RWTH Aachen (DE). Inst. for Power Electronics and Electrical Drives (ISEA); Arlt, Tobias [Helmholtz Centre Berlin (Germany). Inst. for Applied Materials

    2010-07-01

    Neutron radiography allows the investigation of the local fluid distribution in direct methanol fuel cells (DMFCs) under operating conditions. Spatial resolutions in the order of some tens of micrometers at the full test cell area are achieved. This offers the possibility to study practice-oriented, large stack cells with an active area of several hundred cm{sup 2} as well as specially designed, small test cells with an area of some cm{sup 2}. Combined studies of high resolution neutron radiography and segmented cell measurements are especially valuable, because they enable a correlation of local fluid distribution and local performance [1, 2]. The knowledge of this interdependency is essential to optimise the water management and performance respecting a homogeneous fluid, current and temperature distribution and to achieve high performance and durability of DMFCs. (orig.)

  13. Effect of carbon derivatives in sulfonated poly(etherimide)-liquid crystal polymer composite for methanol vapor sensing

    Bag, Souvik; Rathi, Keerti; Pal, Kaushik

    2017-05-01

    A class of highly sensitive chemiresistive sensors is developed for methanol (MeOH) vapor detection in ambient atmosphere by introducing conductive nanofillers like carbon black, multi-wall carbon nanotubes, and reduced graphene oxide into sulfonated poly(etherimide) (PEI)/liquid crystal polymer (LCP) composite (sPEI-LCP). Polar composites are prepared by a sulfonation process for instantaneous enhancement in adsorption capability of the sensing films to the target analyte (MeOH). Sensing properties exhibit that polymer composite-based fabricated sensors are efficient for the detection of different concentration of methanol vapor from 300-1200 parts-per-million (ppm) at room temperature. The incorporation of nanofiller induces the dramatic change in sensing behavior of base composite film (sPEI-LCP). Thus, less mass fraction of nanofillers (i.e. 2 wt%) influences the nonlinear sensing behavior for the entire range of methanol vapor. The simple method and low fabrication cost of the prepared sensor are compelling reasons that methanol vapor sensor is suitable for environmental monitoring.

  14. Effect of fabrication and operating parameters on electrochemical property of anode and cathode for direct methanol fuel cells

    Liu, Guicheng; Zhou, Hongwei; Ding, Xianan; Li, Xinping; Zou, Dechun; Li, Xinyang; Wang, Xindong; Lee, Joong Kee

    2016-01-01

    Highlights: • A quick and simple method for optimizing assembly force of fuel cells. • Effect mechanisms of operating parameters on polarization of each electrode. • Working temperature is main factor to affect the optimal flow rates. • This paper is helpful to simulate the relation between operating parameters. - Abstract: A quick and simple method for optimizing assembly force of the direct methanol fuel cell has been introduced. Meanwhile, the effect mechanism of operating parameters on fuel cell performance and the properties of single anode and cathode have been intuitively investigated by a three-electrode system in this paper. The impedance curves indicate that internal resistance is the suitable intermediate to connect assembly torque and assembly force. The cathode polarization curve and limiting current density of methanol crossover are shown that the increasing methanol concentration markedly exacerbates the polarization in cathode due to serious methanol crossover phenomenon. Also, the higher cathode backpressure mainly improves cathode property, and lowers methanol crossover simultaneously. Finally, the summaries of peak power densities prove that the main factor that affected the optimal flow rates of methanol and oxygen is not the concentration or backpressure, but the working temperature.

  15. Design, fabrication and testing of an air-breathing micro direct methanol fuel cell with compound anode flow field

    Wang, Luwen; Zhang, Yufeng; Zhao, Youran; An, Zijiang; Zhou, Zhiping; Liu, Xiaowei

    2011-01-01

    An air-breathing micro direct methanol fuel cell (μDMFC) with a compound anode flow field structure (composed of the parallel flow field and the perforated flow field) is designed, fabricated and tested. To better analyze the effect of the compound anode flow field on the mass transfer of methanol, the compound flow field with different open ratios (ratio of exposure area to total area) and thicknesses of current collectors is modeled and simulated. Micro process technologies are employed to fabricate the end plates and current collectors. The performances of the μDMFC with a compound anode flow field are measured under various operating parameters. Both the modeled and the experimental results show that, comparing the conventional parallel flow field, the compound one can enhance the mass transfer resistance of methanol from the flow field to the anode diffusion layer. The results also indicate that the μDMFC with an anode open ratio of 40% and a thickness of 300 µm has the optimal performance under the 7 M methanol which is three to four times higher than conventional flow fields. Finally, a 2 h stability test of the μDMFC is performed with a methanol concentration of 7 M and a flow velocity of 0.1 ml min −1 . The results indicate that the μDMFC can work steadily with high methanol concentration.

  16. Mordenite/Nafion and analcime/Nafion composite membranes prepared by spray method for improved direct methanol fuel cell performance

    Prapainainar, Paweena; Du, Zehui; Kongkachuichay, Paisan; Holmes, Stuart M.; Prapainainar, Chaiwat

    2017-11-01

    The aim of this work was to improve proton exchange membranes (PEMs) used in direct methanol fuel cells (DMFCs). A membrane with a high proton conductivity and low methanol permeability was required. Zeolite filler in Nafion (NF matrix) composite membranes were prepared using two types of zeolite, mordenite (MOR) and analcime (ANA). Spray method was used to prepare the composite membranes, and properties of the membranes were investigated: mechanical properties, solubility, water and methanol uptake, ion-exchange capacity (IEC), proton conductivity, methanol permeability, and DMFC performance. It was found that MOR filler showed higher performance than ANA. The MOR/Nafion composite membrane gave better properties than ANA/Nafion composite membrane, including a higher proton conductivity and a methanol permeability that was 2-3 times lower. The highest DMFC performance (10.75 mW cm-2) was obtained at 70 °C and with 2 M methanol, with a value 1.5 times higher than that of ANA/Nafion composite membrane and two times higher than that of commercial Nafion 117 (NF 117).

  17. Enhancement of Hybrid SPEEK Based Polymer–Cyclodextrin-Silica Inorganic Membrane for Direct Methanol Fuel Cell Application

    Tutuk Djoko Kusworo

    2017-06-01

      Keywords: Direct Methanol Fuel Cell, Poly(ether ether ketone, cyclodextrin-silica, sulfonation, ionic conductivity. Article History: Received January 18th 2017; Received in revised form April 21st 2017; Accepted June 22nd 2017; Available online How to Cite This Article: Kusworo, T.D., Hakim, M.F. and Hadiyanto, H. (2017 Enhancement of Hybrid SPEEK Based Polymer–Cyclodextrin-Silica Inorganic Membrane for Direct Methanol Fuel Cell Application. International Journal of Renewable Energy Development, 6(2, 165-170. https://doi.org/10.14710/ijred.6.2.165-170

  18. Enrichment and detection of microorganisms involved in direct and indirect methanogenesis from methanol in an anaerobic thermophilic bioreactor.

    Roest, Kees; Altinbas, Mahmut; Paulo, Paula L; Heilig, H G H J; Akkermans, Antoon D L; Smidt, Hauke; de Vos, Willem M; Stams, Alfons J M

    2005-10-01

    To gain insight into the microorganisms involved in direct and indirect methane formation from methanol in a laboratory-scale thermophilic (55 degrees C) methanogenic bioreactor, reactor sludge was disrupted and serial dilutions were incubated in specific growth media containing methanol and possible intermediates of methanol degradation as substrates. With methanol, growth was observed up to a dilution of 10(8). However, when Methanothermobacter thermoautotrophicus strain Z245 was added for H2 removal, growth was observed up to a 10(10)-fold dilution. With H2/CO2 and acetate, growth was observed up to dilutions of 10(9) and 10(4), respectively. Dominant microorganisms in the different dilutions were identified by 16S rRNA-gene diversity and sequence analysis. Furthermore, dilution polymerase chain reaction (PCR) revealed a similar relative abundance of Archaea and Bacteria in all investigated samples, except in enrichment with acetate, which contained 100 times less archaeal DNA than bacterial DNA. The most abundant bacteria in the culture with methanol and strain Z245 were most closely related to Moorella glycerini. Thermodesulfovibrio relatives were found with high sequence similarity in the H2/CO2 enrichment, but also in the original laboratory-scale bioreactor sludge. Methanothermobacter thermoautotrophicus strains were the most abundant hydrogenotrophic archaea in the H2/CO2 enrichment. The dominant methanol-utilizing methanogen, which was present in the 10(8)-dilution, was most closely related to Methanomethylovorans hollandica. Compared to direct methanogenesis, results of this study indicate that syntrophic, interspecies hydrogen transfer-dependent methanol conversion is equally important in the thermophilic bioreactor, confirming previous findings with labeled substrates and specific inhibitors.

  19. Study of catalysis for solid oxide fuel cells and direct methanol fuel cells

    Jiang, Xirong

    Fuel cells offer the enticing promise of cleaner electricity with lower environmental impact than traditional energy conversion technologies. Driven by the interest in power sources for portable electronics, and distributed generation and automotive propulsion markets, active development efforts in the technologies of both solid oxide fuel cell (SOFC) and direct methanol fuel cell (DMFC) devices have achieved significant progress. However, current catalysts for fuel cells are either of low catalytic activity or extremely expensive, presenting a key barrier toward the widespread commercialization of fuel cell devices. In this thesis work, atomic layer deposition (ALD), a novel thin film deposition technique, was employed to apply catalytic Pt to SOFC, and investigate both Pt skin catalysts and Pt-Ru catalysts for methanol oxidation, a very important reaction for DMFC, to increase the activity and utilization levels of the catalysts while simultaneously reducing the catalyst loading. For SOFCs, we explored the use of ALD for the fabrication of electrode components, including an ultra-thin Pt film for use as the electrocatalyst, and a Pt mesh structure for a current collector for SOFCs, aiming for precise control over the catalyst loading and catalyst geometry, and enhancement in the current collect efficiency. We choose Pt since it has high chemical stability and excellent catalytic activity for the O2 reduction reaction and the H2 oxidation reaction even at low operating temperatures. Working SOFC fuel cells were fabricated with ALD-deposited Pt thin films as an electrode/catalyst layer. The measured fuel cell performance reveals that comparable peak power densities were achieved for ALD-deposited Pt anodes with only one-fifth of the Pt loading relative to a DC-sputtered counterpart. In addition to the continuous electrocatalyst layer, a micro-patterned Pt structure was developed via the technique of area selective ALD. By coating yttria-stabilized zirconia, a

  20. Optimization for microwave-assisted direct liquefaction of bamboo residue in glycerol/methanol mixtures

    Jiulong Xie; Jinqiu Qi; Chungyun Hse; Todd F. Shupe

    2015-01-01

    Bamboo residues were liquefied in a mixture of glycerol and methanol in the presence of sulfuric acid using microwave energy. We investigated the effects of liquefaction conditions, including glycerol/methanol ratio, liquefaction temperature, and reaction time on the conversion yield. The optimal liquefaction conditions were under the temperature of 120

  1. Dimensionally stable Nafion-polyethylene composite membranes for direct methanol fuel cell applications

    Yildirim, M.H.; Stamatialis, Dimitrios; Wessling, Matthias

    2008-01-01

    Nafion ® impregnated Solupor ®, microporous UHMWPE film, (N-PE), Nafion ®117 (N117) and a membrane prepared using a DE2020 Nafion ® dispersion (DE2020) were characterized with respect to their swelling degree (SD), methanol cross-over, proton conductivity and DMFC performance at various methanol

  2. Proton conducting semi-IPN based on Nafion and crosslinked poly(AMPS) for direct methanol fuel cell

    Cho, Ki-Yun; Jung, Ho-Young; Shin, Seung-Shik; Choi, Nam-Soon; Sung, Shi-Joon; Park, Jung-Ki; Choi, Jong-Ho; Park, Kyung-Won; Sung, Yung-Eun

    2004-01-01

    For direct methanol fuel cell, the proton conducting membrane based on semi-interpenetrating polymer networks (IPNs) of Nafion and crosslinked poly(AMPS) was prepared and characterized. The modification of Nafion with crosslinked poly(AMPS) such as hydrocarbon polymer changed the state of water in membranes. Without a significant increase of the membrane resistance, the semi-IPNs demonstrated a reduction of the methanol permeability, comparing to the native Nafion. And the maximum power density of AMPS60 increased as much as 22.2% compared with Nafion

  3. Preparation and properties of hybrid direct methanol fuel cell membranes by embedding organophosphorylated titania submicrospheres into a chitosan polymer matrix

    Wu, Hong [Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University, 92 Weijin Road, Nankai District, Tianjin 300072 (China); Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin University, Tianjin 300072 (China); Hou, Weiqiang; Wang, Jingtao; Xiao, Lulu; Jiang, Zhongyi [Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University, 92 Weijin Road, Nankai District, Tianjin 300072 (China)

    2010-07-01

    Organophosphorylated titania submicrospheres (OPTi) are prepared and incorporated into a chitosan (CS) matrix to fabricate hybrid membranes with enhanced methanol resistance and proton conductivity for application in direct methanol fuel cells (DMFC). The pristine monodispersed titania submicrospheres (TiO{sub 2}) of controllable particle size are synthesized through a modified sol-gel method and then phosphorylated by amino trimethylene phosphonic acid (ATMP) via chemical adsorption, which is confirmed by XPS, FTIR and TGA. The morphology and thermal property of the hybrid membranes are explored by SEM and TGA. The ionic cross-linking between the -PO{sub 3}H{sub 2} groups on OPTi and the -NH{sub 2} groups on CS lead to better compatibility between the inorganic fillers and the polymer matrix, as well as a decreased fractional free volume (FFV), which is verified by positron annihilation lifetime spectroscopy (PALS). The effects of particle size and content on the methanol permeability, proton conductivity, swelling and FFV of the membranes are investigated. Compared to pure CS membrane, the hybrid membranes exhibit an increased proton conductivity to an acceptable level of 0.01 S cm{sup -1} for DMFC application and a reduced methanol permeability of 5 x 10{sup -7} cm{sup 2} s{sup -1} at a 2 M methanol feed. (author)

  4. Preparation and properties of hybrid direct methanol fuel cell membranes by embedding organophosphorylated titania submicrospheres into a chitosan polymer matrix

    Wu, Hong; Hou, Weiqiang; Wang, Jingtao; Xiao, Lulu; Jiang, Zhongyi

    Organophosphorylated titania submicrospheres (OPTi) are prepared and incorporated into a chitosan (CS) matrix to fabricate hybrid membranes with enhanced methanol resistance and proton conductivity for application in direct methanol fuel cells (DMFC). The pristine monodispersed titania submicrospheres (TiO 2) of controllable particle size are synthesized through a modified sol-gel method and then phosphorylated by amino trimethylene phosphonic acid (ATMP) via chemical adsorption, which is confirmed by XPS, FTIR and TGA. The morphology and thermal property of the hybrid membranes are explored by SEM and TGA. The ionic cross-linking between the -PO 3H 2 groups on OPTi and the -NH 2 groups on CS lead to better compatibility between the inorganic fillers and the polymer matrix, as well as a decreased fractional free volume (FFV), which is verified by positron annihilation lifetime spectroscopy (PALS). The effects of particle size and content on the methanol permeability, proton conductivity, swelling and FFV of the membranes are investigated. Compared to pure CS membrane, the hybrid membranes exhibit an increased proton conductivity to an acceptable level of 0.01 S cm -1 for DMFC application and a reduced methanol permeability of 5 × 10 -7 cm 2 s -1 at a 2 M methanol feed.

  5. Pt-Fe catalyst nanoparticles supported on single-wall carbon nanotubes: Direct synthesis and electrochemical performance for methanol oxidation

    Ma, Xiaohui; Luo, Liqiang; Zhu, Limei; Yu, Liming; Sheng, Leimei; An, Kang; Ando, Yoshinori; Zhao, Xinluo

    2013-11-01

    Single-wall carbon nanotubes (SWCNTs) supported Pt-Fe nanoparticles have been prepared by one-step hydrogen arc discharge evaporation of carbon electrode containing both Pt and Fe metal elements. The formation of SWCNTs and Pt-Fe nanoparticles occur simultaneously during the evaporation process. High-temperature hydrogen treatment and hydrochloric acid soaking have been carried out to purify and activate those materials in order to obtain a new type of Pt-Fe/SWCNTs catalyst for methanol oxidation. The Pt-Fe/SWCNTs catalyst performs much higher electrocatalytic activity for methanol oxidation, better stability and better durability than a commercial Pt/C catalyst according to the electrochemical measurements, indicating that it has a great potential for applications in direct methanol fuel cells.

  6. Self-assembled platinum nanoparticles on sulfonic acid-grafted graphene as effective electrocatalysts for methanol oxidation in direct methanol fuel cells.

    Lu, Jinlin; Li, Yanhong; Li, Shengli; Jiang, San Ping

    2016-02-15

    In this article, sulfonic acid-grafted reduced graphene oxide (S-rGO) were synthesized using a one-pot method under mild conditions, and used as Pt catalyst supports to prepare Pt/S-rGO electrocatalysts through a self-assembly route. The structure, morphologies and physicochemical properties of S-rGO were examined in detail by techniques such as atomic force microscope (AFM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The S-rGO nanosheets show excellent solubility and stability in water and the average particle size of Pt nanoparticles supported on S-rGO is ~3.8 nm with symmetrical and uniform distribution. The electrocatalytic properties of Pt/S-rGO were investigated for methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). In comparison to Pt supported on high surface area Vulcan XC-72 carbon (Pt/VC) and Pt/rGO, the Pt/S-rGO electrocatalyst exhibits a much higher electrocatalytic activity, faster reaction kinetics and a better stability. The results indicate that Pt/S-rGO is a promising and effective electrocatalyst for MOR of DMFCs.

  7. Self-assembled platinum nanoparticles on sulfonic acid-grafted graphene as effective electrocatalysts for methanol oxidation in direct methanol fuel cells

    Lu, Jinlin; Li, Yanhong; Li, Shengli; Jiang, San Ping

    2016-02-01

    In this article, sulfonic acid-grafted reduced graphene oxide (S-rGO) were synthesized using a one-pot method under mild conditions, and used as Pt catalyst supports to prepare Pt/S-rGO electrocatalysts through a self-assembly route. The structure, morphologies and physicochemical properties of S-rGO were examined in detail by techniques such as atomic force microscope (AFM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The S-rGO nanosheets show excellent solubility and stability in water and the average particle size of Pt nanoparticles supported on S-rGO is ~3.8 nm with symmetrical and uniform distribution. The electrocatalytic properties of Pt/S-rGO were investigated for methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). In comparison to Pt supported on high surface area Vulcan XC-72 carbon (Pt/VC) and Pt/rGO, the Pt/S-rGO electrocatalyst exhibits a much higher electrocatalytic activity, faster reaction kinetics and a better stability. The results indicate that Pt/S-rGO is a promising and effective electrocatalyst for MOR of DMFCs.

  8. A Review on the Fabrication of Electro spun Polymer Electrolyte Membrane for Direct Methanol Fuel Cell

    Junoh, H.; Jaafar, J.; Norddin, M.N.A.M.; Ismail, A.F.; Othman, M.H.D.; Rahman, M.A.; Yusof, N.; Salleh, W.N.W.; Junoh, H.; Jaafar, J.; Norddin, M.N.A.M.; Ismail, A.F.; Othman, M.H.D.; Rahman, M.A.; Yusof, N.; Salleh, W.N.W.; Hamid Ilbeygi, H.

    2014-01-01

    Proton exchange membrane (PEM) is an electrolyte which behaves as important indicator for fuel cell’s performance. Research and development (R and D) on fabrication of desirable PEM have burgeoned year by year, especially for direct methanol fuel cell (DMFC). However, most of the R and Ds only focus on the parent polymer electrolyte rather than polymer inorganic composites. This might be due to the difficulties faced in producing good dispersion of inorganic filler within the polymer matrix, which would consequently reduce the DMFC’s performance. Electro spinning is a promising technique to cater for this arising problem owing to its more widespread dispersion of inorganic filler within the polymer matrix, which can reduce the size of the filler up to nano scale. There has been a huge development on fabricating electrolyte nano composite membrane, regardless of the effect of electro spun nano composite membrane on the fuel cell’s performance. In this present paper, issues regarding the R and D on electro spun sulfonated poly (ether ether ketone) (SPEEK)/inorganic nano composite fiber are addressed.

  9. Developments for improved direct methanol fuel cell stacks for portable power

    Cremers, C.; Stimming, U. [Bavarian Center for Applied Energy Research, ZAE Bayern, Abteilung 1, Walther-Meissner-Str. 6, D-85748 Garching (Germany); Technische Universitaet Muenchen, Department of Physics E19, James-Franck-Str. 1, D-85748 Garching (Germany); Scholz, M.; Seliger, W. [Bavarian Center for Applied Energy Research, ZAE Bayern, Abteilung 1, Walther-Meissner-Str. 6, D-85748 Garching (Germany); Racz, A. [Technische Universitaet Muenchen, Department of Physics E19, James-Franck-Str. 1, D-85748 Garching (Germany); Knechtel, W.; Rittmayr, J.; Grafwallner, F.; Peller, H. [ET EnergieTechnologie GmbH, Eugen-Saenger-Ring 4, D-85649 Brunnthal-Nord (Germany)

    2007-02-15

    Different aspects of the improvement of direct methanol fuel cell (DMFC) systems for portable power generation are investigated, in a project funded by the Bavarian state. The materials research focuses on the development of improved catalysts, in particular for the oxygen reduction reaction. Some recent results on supported ruthenium selenium catalysts are reported. In parallel, tests on other fuel cell materials are performed using MEAs made from industrial unsupported catalysts as the reference. These standard MEAs have catalyst loadings of about 11 mg cm{sup -2} and, at high air flux, can deliver current densities of about 500 mA cm{sup -2} and 100 mA cm{sup -2} at 110 C and 50 C, respectively. At low air flux and 50 C, current densities between 60 and 80 mA cm{sup -2} are possible rate at 500 mV. Using these MEAs, different commercial gas diffusion materials are tested as the cathode backing. Thus, it is found that the Sigracet materials by SGL Carbon are the most suitable for operation at a low air flux. Finally, a demonstration stack, comprised of up to ten cells, is developed using graphite PVDF compound bipolar plates by SGL Carbon. As will be reported, this stack shows a high homogeneity of cell voltages and stable operation under relevant conditions, using standard MEAs. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  10. A study on the dissymmetrical microporous layer structure of a direct methanol fuel cell

    Wang Tongtao; Lin Caishun; Fang Yong; Ye Feng; Miao Ruiying; Wang Xindong

    2008-01-01

    The effect of carbon type, carbon loading and microporous layer structure in the microporous layer on the performance of a direct methanol fuel cell (DMFC) at low temperature was investigated using electrochemical polarization techniques, electrochemical impedance spectroscopy, scanning electron microscope and other methods. Vulcan XC-72 carbon was found to be most suitable as a microporous layer for low temperature DMFC. Maximum fuel cell performance was obtained utilizing a microporous layer with carbon loading of 1.0 mg cm -2 when air was used as an oxidant. A membrane electrode assembly with 1.0 mg cm -2 Vulcan XC-72 carbon with 20 wt.% Teflon in the cathode and no microporous layer in the anode showed a maximum power density of 36.7 mW cm -2 at 35 deg. C under atmospheric pressure. The AC impedance study proved that a cell with a dissymmetrical microporous layer structure had lower internal resistance and mass transfer resistance, thus obtaining better performance

  11. Quaternized poly(vinyl alcohol)/alumina composite polymer membranes for alkaline direct methanol fuel cells

    Yang, Chun-Chen; Chiu, Shwu-Jer; Chien, Wen-Chen; Chiu, Sheng-Shin

    The quaternized poly(vinyl alcohol)/alumina (designated as QPVA/Al 2O 3) nanocomposite polymer membrane was prepared by a solution casting method. The characteristic properties of the QPVA/Al 2O 3 nanocomposite polymer membranes were investigated using thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), micro-Raman spectroscopy, and AC impedance method. Alkaline direct methanol fuel cell (ADMFC) comprised of the QPVA/Al 2O 3 nanocomposite polymer membrane were assembled and examined. Experimental results indicate that the DMFC employing a cheap non-perfluorinated (QPVA/Al 2O 3) nanocomposite polymer membrane shows excellent electrochemical performances. The peak power densities of the DMFC with 4 M KOH + 1 M CH 3OH, 2 M CH 3OH, and 4 M CH 3OH solutions are 28.33, 32.40, and 36.15 mW cm -2, respectively, at room temperature and in ambient air. The QPVA/Al 2O 3 nanocomposite polymer membranes constitute a viable candidate for applications on alkaline DMFC.

  12. Nanostructured Carbon Materials as Supports in the Preparation of Direct Methanol Fuel Cell Electrocatalysts

    María Jesús Lázaro

    2013-08-01

    Full Text Available Different advanced nanostructured carbon materials, such as carbon nanocoils, carbon nanofibers, graphitized ordered mesoporous carbons and carbon xerogels, presenting interesting features such as high electrical conductivity and extensively developed porous structure were synthesized and used as supports in the preparation of electrocatalysts for direct methanol fuel cells (DMFCs. The main advantage of these supports is that their physical properties and surface chemistry can be tailored to adapt the carbonaceous material to the catalytic requirements. Moreover, all of them present a highly mesoporous structure, diminishing diffusion problems, and both graphitic character and surface area can be conveniently modified. In the present work, the influence of the particular features of each material on the catalytic activity and stability was analyzed. Results have been compared with those obtained for commercial catalysts supported on Vulcan XC-72R, Pt/C and PtRu/C (ETEK. Both a highly ordered graphitic and mesopore-enriched structure of these advanced nanostructured materials resulted in an improved electrochemical performance in comparison to the commercial catalysts assayed, both towards CO and alcohol oxidation.

  13. Study on the water flooding in the cathode of direct methanol fuel cells.

    Im, Hun Suk; Kim, Sang-Kyung; Lim, Seongyop; Peck, Dong-Hyun; Jung, Doohwan; Hong, Won Hi

    2011-07-01

    Water flooding phenomena in the cathode of direct methanol fuel cells were analyzed by using electrochemical impedance spectroscopy. Two kinds of commercial gas diffusion layers with different PTFE contents of 5 wt% (GDL A5) and 20 wt% (GDL B20) were used to investigate the water flooding under various operating conditions. Water flooding was divided into two types: catalyst flooding and backing flooding. The cathode impedance spectra of each gas diffusion layer was obtained and compared under the same conditions. The diameter of the capacitive semicircle became larger with increasing current density for both, and this increase was greater for GDL B20 than GDL A5. Catalyst flooding is dominant and backing flooding is negligible when the air flow rate is high and current density is low. An equivalent model was suggested and fitted to the experimental data. Parameters for catalyst flooding and backing flooding were individually obtained. The capacitance of the catalyst layer decreases as the air flow rate decreases when the catalyst flooding is dominant.

  14. Highly Durable Direct Methanol Fuel Cell with Double-Layered Catalyst Cathode

    Jing Liu

    2015-01-01

    Full Text Available Polymer electrolyte membrane (PEM is one of the key components in direct methanol fuel cells. However, the PEM usually gets attacked by reactive oxygen species during the operation period, resulting in the loss of membrane integrity and formation of defects. Herein, a double-layered catalyst cathode electrode consisting of Pt/CeO2-C as inner catalyst and Pt/C as outer catalyst is fabricated to extend the lifetime and minimize the performance loss of DMFC. Although the maximum power density of membrane electrode assembly (MEA with catalyst cathode is slightly lower than that of the traditional one, its durability is significantly improved. No obvious degradation is evident in the MEA with double-layered catalyst cathode within durability testing. These results indicated that Pt/CeO2-C as inner cathode catalyst layer greatly improved the stability of MEA. The significant reason for the improved stability of MEA is the ability of CeO2 to act as free-radical scavengers.

  15. Three-dimensional graphene as gas diffusion layer for micro direct methanol fuel cell

    Zhu, Yingli; Zhang, Xiaojian; Li, Jianyu; Qi, Gary

    2018-05-01

    The gas diffusion layer (GDL), as an important structure of the membrane electrode assembly (MEA) of the direct methanol fuel cell (DMFC), provides a support layer for the catalyst and the fuel and the product channel. Traditionally, the material of GDL is generally carbon paper (CP). In this paper, a new material, namely three-dimensional graphene (3DG) is used as GDL for micro DMFC. The experimental results reveal that the performance of the DMFC has been improved significantly by application of 3DG. The peak powers increase from 25 mW to 31.2 mW and 32 mW by using 3DG as the anode and cathode GDL instead of CP, respectively. The reason may be the decrease of charge and mass transfer resistance of the cell. This means that the unique 3D porous architecture of the 3DG can provide lower contact resistance and sufficient fuel diffusion paths. The output performance of the cell will be further improved when porous metal current collectors is used.

  16. A Review on the Fabrication of Electrospun Polymer Electrolyte Membrane for Direct Methanol Fuel Cell

    Hazlina Junoh

    2015-01-01

    Full Text Available Proton exchange membrane (PEM is an electrolyte which behaves as important indicator for fuel cell’s performance. Research and development (R&D on fabrication of desirable PEM have burgeoned year by year, especially for direct methanol fuel cell (DMFC. However, most of the R&Ds only focus on the parent polymer electrolyte rather than polymer inorganic composites. This might be due to the difficulties faced in producing good dispersion of inorganic filler within the polymer matrix, which would consequently reduce the DMFC’s performance. Electrospinning is a promising technique to cater for this arising problem owing to its more widespread dispersion of inorganic filler within the polymer matrix, which can reduce the size of the filler up to nanoscale. There has been a huge development on fabricating electrolyte nanocomposite membrane, regardless of the effect of electrospun nanocomposite membrane on the fuel cell’s performance. In this present paper, issues regarding the R&D on electrospun sulfonated poly (ether ether ketone (SPEEK/inorganic nanocomposite fiber are addressed.

  17. Biodiesel production from Spirulina microalgae feedstock using direct transesterification near supercritical methanol condition.

    Mohamadzadeh Shirazi, Hamed; Karimi-Sabet, Javad; Ghotbi, Cyrus

    2017-09-01

    Microalgae as a candidate for production of biodiesel, possesses a hard cell wall that prevents intracellular lipids leaving out from the cells. Direct or in situ supercritical transesterification has the potential for destruction of microalgae hard cell wall and conversion of extracted lipids to biodiesel that consequently reduces the total energy consumption. Response surface methodology combined with central composite design was applied to investigate process parameters including: Temperature, Time, Methanol-to-dry algae, Hexane-to-dry algae, and Moisture content. Thirty-two experiments were designed and performed in a batch reactor, and biodiesel efficiency between 0.44% and 99.32% was obtained. According to fatty acid methyl ester yields, a quadratic experimental model was adjusted and the significance of parameters was evaluated using analysis of variance (ANOVA). Effects of single and interaction parameters were also interpreted. In addition, the effect of supercritical process on the ultrastructure of microalgae cell wall using scanning electron spectrometry (SEM) was surveyed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Solar Hybrid Hydrogen Production in Sunbelt and Shipping to Japan as a Liquid fuel of Methanol

    Tamaura, Y.; Hasegawa, N.; Kaneko, H.; Utamura, M.; Katayama, Y.; Onozaki, M.; Hasuike, H.

    2006-01-01

    Solar hybrid methanol (SH-methanol) production (6000 t/day) from natural gas and coal using H 2 and O 2 gases, which are produced by electrolysis with solar thermal power (Tokyo Tech Beam-down concentration solar power generation with molten salt heat-storage system) at Sunbelt in Australia was studied from the economical view point. This system is the combined system of O 2 -burning coal gasification (C+1/2O 2 =CO), natural gas reforming by O 2 -partial oxidation (CH 4 + 1/2O 2 = CO + 2H 2 ), and water decomposition by electrolysis with solar thermal power (H 2 O = H 2 + 1/2O 2 ). In this production system, the SH-methanol is produced with zero CO 2 emission, shipped to Japan by oil tanker, and can be used as solar hybrid hydrogen in Japan for fuel cell. The solar hybrid methanol production cost of 24 yen/kg (58 US dollars bbl crude oil equivalent, April, 2006) is obtained with the solar power cost of the Tokyo Tech Beam-down solar concentration solar power generation with molten salt heat-storage. This cost is lower than the crude oil (67 US dollars bbl crude oil equivalent, April, 2006) and LPG (72 US dollars/ bbl crude oil equivalent, January, 2006). (authors)

  19. Heat and mass transfer effects in a direct methanol fuel cell: A 1D model

    Oliveira, V.B.; Falcao, D.S.; Pinto, A.M.F.R. [Centro de Estudos de Fenomenos de Transporte, Departamento de Eng. Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Rangel, C.M. [INETI - Unidade de Electroquimica e Materiais, Paco do Lumiar, 22,1649-038 (Portugal)

    2008-07-15

    Models are a fundamental tool for the design process of fuel cells and fuel cell systems. In this work, a steady-state, one-dimensional model accounting for coupled heat and mass transfer, along with the electrochemical reactions occurring in the DMFC, is presented. The model output is the temperature profile through the cell and the water balance and methanol crossover between the anode and the cathode. The model predicts the correct trends for the influence of current density and methanol feed concentration on both methanol and water crossover. The model estimates the net water transfer coefficient through the membrane, {alpha}, a very important parameter to describe water management in the DMFC. Suitable operating ranges can be set up for different MEA structures maintaining the crossover of methanol and water within acceptable levels. The model is rapidly implemented and is therefore suitable for inclusion in real-time system level DMFC calculations. (author)

  20. Novel synthesis of methoxymethyl benzene by electrochemical coupling reaction of toluene with methanol in ionic liquid media.

    Chen, Fengtao; Wang, Bo; Ma, Hongzhu

    2009-06-15

    An ionic liquid (1-butyl-3-methylimidazolium dibutyl phosphate) was prepared and characterized by cyclic voltammogram (CV) and Fourier transform infrared spectrometer (FT-IR). The ionic liquid exhibited good catalytic activity for the electrochemical reaction of toluene with methanol assisted with a pair of porous graphite plane electrodes and product yield higher than 56% was observed. In addition, the electrochemical process was detected by UV-vis spectrum and the products were analyzed by gas chromatography/mass spectrometry (GC/MS). According to the experimental results, a possible free radical reaction mechanism was proposed. It may be concluded that a simply and feasible electrochemical coupling reaction at room temperature and atmospheric pressure may be possible. Compared with methyl tert-butyl ether (MTBE), the main product (methoxymethyl benzene) used as booster to improve fuel combustion was also studied.

  1. Structure optimization of cathode microporous layer for direct methanol fuel cells

    Liu, Guicheng; Ding, Xianan; Zhou, Hongwei; Chen, Ming; Wang, Manxiang; Zhao, Zhenxuan; Yin, Zhuang; Wang, Xindong

    2015-01-01

    Highlights: • Pore-forming technology was introduced to optimize microporous layer microstructure. • The water removal and gas mass transfer property of diffusion layer were improved. • The optimum DMFC performance reached 292 mW cm −2 at 80 °C. - Abstract: To obtain the cathode microporous layer (CML) with high mass transfer performance and high electronic conductivity, a pore-forming technology was introduced to optimize CML microstructure for direct methanol fuel cells. In this paper, the effects of carbon material type, carbon material loading and pore-forming agent loading in CML on fuel cell performance were discussed systematically. The results indicated that the optimized CML consisted of carbon nanotubes and ammonium oxalate with the loading of 1.5 and 3.5 mg cm −2 respectively. The fuel cell performance was improved by 30.3%, from 224 to 292 mW cm −2 at 80 °C under 0.3 MPa O 2 . Carbon nanotube was found to be the most suitable carbon material for the CML due to its great specific surface area and small particle size, resulting in increasing the number of the hydrophobic sites and the contact area between the support and the catalyst layer. The carbon material and pore-forming agent loading directly influenced the pore distribution and the contact resistance of membrane electrode assembly. The water removal capacity and the gas mass transfer property of diffusion layer were improved by optimizing the amount of micropore and macropore structures

  2. Valveless piezoelectric micropump for fuel delivery in direct methanol fuel cell (DMFC) devices

    Zhang, Tao; Wang, Qing-Ming [Department of Mechanical Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania, PA 15261 (United States)

    2005-01-10

    Fuel cells are being considered as an important technology that can be used for various power applications. For portable electronic devices such as laptops, digital cameras, cell phone, etc., the direct methanol fuel cell (DMFC) is a very promising candidate as a power source. Compared with conventional batteries, DMFC can provide a higher power density with a long-lasting life and recharging which is almost instant. However, many issues related to the design, fabrication and operation of miniaturized DMFC power systems still remain unsolved. Fuel delivery is one of the key issues that will determine the performance of the DMFC. To maintain a desired performance, an efficient fuel delivery system is required to provide an adequate amount of fuel for consumption and remove carbon dioxide generated from fuel cell devices at the same time. In this paper, a novel fuel delivery system combined with a miniaturized DMFC is presented. The core component of this system is a piezoelectric valveless micropump that can convert the reciprocating movement of a diaphragm activated by a piezoelectric actuator into a pumping effect. Nozzle/diffuser elements are used to direct the flow from inlet to outlet. As for DMFC devices, the micropump system needs to meet some specific requirements: low energy consumption but a sufficient fuel flow rate. Based on theoretical analysis, the effect of piezoelectric materials properties, driving voltage, driving frequency, nozzle/diffuser dimension, and other factors on the performance of the whole fuel cell system will be discussed. As a result, a viable design of a micropump system for fuel delivery can be achieved and some simulation results will be presented as well. (author)

  3. Static gas-liquid interfacial direct current discharge plasmas using ionic liquid cathode

    Kaneko, T.; Baba, K.; Hatakeyama, R.

    2009-01-01

    Due to the unique properties of ionic liquids such as their extremely low vapor pressure and high heat capacity, we have succeeded in creating the static and stable gas (plasmas)-liquid (ionic liquids) interfacial field using a direct current discharge under a low gas pressure condition. It is clarified that the ionic liquid works as a nonmetal liquid electrode, and furthermore, a secondary electron emission coefficient of the ionic liquid is larger than that of conventional metal electrodes. The plasma potential structure of the gas-liquid interfacial region, and resultant interactions between the plasma and the ionic liquid are revealed by changing a polarity of the electrode in the ionic liquid. By utilizing the ionic liquid as a cathode electrode, the positive ions in the plasma region are found to be irradiated to the ionic liquid. This ion irradiation causes physical and chemical reactions at the gas-liquid interfacial region without the vaporization of the ionic liquid.

  4. Surface-modified Y zeolite-filled chitosan membrane for direct methanol fuel cell

    Wu, Hong; Zheng, Bin; Zheng, Xiaohong; Wang, Jingtao; Yuan, Weikang; Jiang, Zhongyi [Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China)

    2007-11-15

    Hybrid membranes composed of chitosan (CS) as organic matrix and surface-modified Y zeolite as inorganic filler are prepared and their applicability for DMFC is demonstrated by methanol permeability, proton conductivity and swelling property. Y zeolite is modified using silane coupling agents, 3-aminopropyl-triethoxysilane (APTES) and 3-mercaptopropyl-trimethoxysilane (MPTMS), to improve the organic-inorganic interfacial morphology. The mercapto group on MPTMS-modified Y zeolite is further oxidized into sulfonic group. Then, the resultant surface-modified Y zeolites with either aminopropyl groups or sulfonicpropyl groups are mixed with chitosan in acetic acid solution and cast into membranes. The transitional phase generated between chitosan matrix and zeolite filler reduces or even eliminates the nonselective voids commonly exist at the interface. The hybrid membranes exhibit a significant reduction in methanol permeability compared with pure chitosan and Nafion117 membranes, and this reduction extent becomes more pronounced with the increase of methanol concentration. By introducing -SO{sub 3}H groups onto zeolite surface, the conductivity of hybrid membranes is increased up to 2.58 x 10{sup -2} S cm{sup -1}. In terms of the overall selectivity index ({beta} = {sigma}/P), the hybrid membrane is comparable with Nafion117 at low methanol concentration (2 mol L{sup -1}) and much better (three times) at high methanol concentration (12 mol L{sup -1}). (author)

  5. Application of green chemistry techniques to prepare electrocatalysts for direct methanol fuel cells.

    Shimizu, Kenichi; Wang, Joanna S; Wai, Chien M

    2010-03-25

    A series of green techniques for synthesizing carbon nanotube-supported platinum nanoparticles and their high electrocatalytic activity toward methanol fuel cell applications are reported. The techniques utilize either the supercritical fluid carbon dioxide or water as a medium for depositing platinum nanoparticles on surfaces of multiwalled or single-walled carbon nanotubes. The catalytic properties of the carbon nanotubes-supported Pt nanoparticle catalysts prepared by four different techniques are compared for anodic oxidation of methanol and cathodic reduction of oxygen using cyclic voltammetry. One technique using galvanic exchange of Pt(2+) in water with zerovalent iron present on the surfaces of as-grown single-walled carbon nanotubes produces a Pt catalyst that shows an unusually high catalytic activity for reduction of oxygen but a negligible activity for oxidation of methanol. This fuel-selective catalyst may have a unique application as a cathode catalyst in methanol fuel cells to alleviate the problems caused by crossover of methanol through the polymer electrolyte membrane.

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

    Sales, M Goreti F; Brandão, Lúcia

    2017-12-15

    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. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

  7. Enhanced heat transfer with corrugated flow channel in anode side of direct methanol fuel cells

    Heidary, H.; Abbassi, A.; Kermani, M.J.

    2013-01-01

    Highlights: • Effect of corrugated flow channel on the heat exchange of DMFC is studied. • Corrugated boundary (except rectangular type) increase heat transfer up to 90%. • Average heat transfer in rectangular-corrugated boundary is less than straight one. • In Re > 60, wavy shape boundary has highest heat transfer. • In Re < 60, triangular shape boundary has highest heat transfer. - Abstract: In this paper, heat transfer and flow field analysis in anode side of direct methanol fuel cells (DMFCs) is numerically studied. To enhance the heat exchange between bottom cold wall and core flow, bottom wall of fluid delivery channel is considered as corrugated boundary instead of straight (flat) one. Four different shapes of corrugated boundary are recommended here: rectangular shape, trapezoidal shape, triangular shape and wavy (sinusoidal) shape. The top wall of the channel (catalyst layer boundary) is taken as hot boundary, because reaction occurs in catalyst layer and the bottom wall of the channel is considered as cold boundary due to coolant existence. The governing equations are numerically solved in the domain by the control volume approach based on the SIMPLE technique (1972). A wide spectrum of numerical studies is performed over a range of various shape boundaries, Reynolds number, triangle block number, and the triangle block amplitude. The performed parametric studies show that corrugated channel with trapezoidal, triangular and wavy shape enhances the heat exchange up to 90%. With these boundaries, cooling purpose of reacting flow in anode side of DMFCs would be better than straight one. Also, from the analogy between the heat and mass transfer problems, it is expected that the consumption of reacting species within the catalyst layer of DMFCs enhance. The present work provides helpful guidelines to the bipolar plate manufacturers of DMFCs to considerably enhance heat transfer and performance of the anode side of DMFC

  8. MnO2/CNT supported Pt and PtRu nanocatalysts for direct methanol fuel cells.

    Zhou, Chunmei; Wang, Hongjuan; Peng, Feng; Liang, Jiahua; Yu, Hao; Yang, Jian

    2009-07-07

    Pt/MnO2/carbon nanotube (CNT) and PtRu/MnO2/CNT nanocomposites were synthesized by successively loading hydrous MnO2 and Pt (or PtRu alloy) nanoparticles on CNTs and were used as anodic catalysts for direct methanol fuel cells (DMFCs). The existence of MnO2 on the surface of CNTs effectively increases the proton conductivity of the catalyst, which then could remarkably improve the performance of the catalyst in methanol electro-oxidation. As a result, Pt/MnO2/CNTs show higher electrochemical active surface area and better methanol electro-oxidation activity, compared with Pt/CNTs. As PtRu alloy nanoparticles were deposited on the surface of MnO2/CNTs instead of Pt, the PtRu/MnO2/CNT catalyst shows not only excellent electro-oxidation activity to methanol with forward anodic peak current density of 901 A/gPt but also good CO oxidation ability with lower preadsorbed CO oxidation onset potential (0.33 V vs Ag/AgCl) and peak potential (0.49 V vs Ag/AgCl) at room temperature.

  9. Ab initio molecular dynamics study of temperature and pressure-dependent infrared dielectric functions of liquid methanol

    C. C. Wang

    2017-03-01

    Full Text Available The temperature and pressure-dependent dielectric functions of liquids are of great importance to the thermal radiation transfer and the diagnosis and control of fuel combustion. In this work, we apply the state-of-the-art ab initio molecular dynamics (AIMD method to calculate the infrared dielectric functions of liquid methanol at 183–573 K and 0.1–160 MPa in the spectral range 10−4000 cm−1, and study the temperature and pressure effects on the dielectric functions. The AIMD approach is validated by the Infrared Variable Angle Spectroscopic Ellipsometry (IR-VASE experimental measurements at 298 K and 0.1 MPa, and the proposed IR-VASE method is verified by comparison with paper data of distilled water. The results of the AIMD approach agrees well with the experimental values of IR-VASE. The experimental and theoretical analyses indicate that the temperature and pressure exert a noticeable influence on the infrared dielectric functions of liquid methanol. As temperature increases, the average molecular dipole moment decreases. The amplitudes of dominant absorption peaks reduce to almost one half as temperature increases from 183 to 333 K at 0.1 MPa and from 273 to 573 K at 160 MPa. The absorption peaks below 1500 cm–1 show a redshift, while those centered around 3200 cm–1 show a blueshift. Moreover, larger average dipole moments are observed as pressure increases. The amplitudes of dominant absorption peaks increase to almost two times as pressure increases from 1 to 160 MPa at 373 K.

  10. An Investigation of Palladium Oxygen Reduction Catalysts for the Direct Methanol Fuel Cell

    G. F. Álvarez

    2011-01-01

    Full Text Available A comparative study of Pd and Pt was carried out in DMFC using different methanol concentrations and under different operating conditions. Cell performance was compared at methanol concentrations of 1, 3, 5, and 7 M and at temperatures of 20, 40, and 60°C. Homemade Pd nanoparticles were prepared on Vulcan XC-72R using ethylene glycol as the reducing agent at pH 11. The resulting catalyst, Pd/C, with metal nanoparticles of approximately 6 nm diameter, was tested as a cathode catalyst in DMFC. At methanol concentrations of 5 M and higher, the Pd cathode-based cell performed better than that with Pt at 60°C with air.

  11. Surface tailored single walled carbon nanotubes as catalyst support for direct methanol fuel cell

    Kireeti, Kota V. M. K.; Jha, Neetu

    2017-10-01

    A strategy for tuning the surface property of Single Walled Carbon Nanotubes (SWNTs) for enhanced methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) along with methanol tolerance is presented. The surface functionality is tailored using controlled acid and base treatment. Acid treatment leads to the attachment of carboxylic carbon (CC) fragments to SWNT making it hydrophilic (P3-SWNT). Base treatment of P3-SWNT with 0.05 M NaOH reduces the CCs and makes it hydrophobic (P33-SWNT). Pt catalyst supported on the P3-SWNT possesses enhanced MOR whereas that supported on P33-SWNT not only enhances ORR kinetics but also possess good tolerance towards methanol oxidation as verified by the electrochemical technique.

  12. Development of a direct methanol fuel cell system for the power segment below 5 kW; Entwicklung eines Direkt-Methanol-Brennstoffzellensystems der Leistungsklasse kleiner 5 kW

    Noelke, M.

    2006-10-20

    The attractiveness of electrical conversion of liquid methanol in a fuel cell is defined by its simple storage and high energy density. Therefore, direct-methanol fuel cell (DMFC) qualifies for applications in portable systems and mobile application in the kW-class. The goal of this work is to develop and demonstrate an improved and optimized peripheral DMFC system compared to the current level of technology. The selected mobile application is the retrofit of the energy supply of a ''Scooter'' with a fuel cell system. The required size reduction and the simplification of the DMFC system are realized by an integrated concept, which combines ideally the peripheral system and the fuel cell. A profound analysis of the stack and the peripheral components is a prerequisite for an optimized design. A detailed modelling and understanding of the stack behaviour establish the starting point of this work. The influence of the most important operating parameters like stack temperature, cell voltage, current density, air ratio and methanol concentration is captured accurately by the developed model and validated by experimental data. This shapes the frame work of the following system design approach. For this the clearly defined task of the peripheral system are investigated individually for alternatives and the best option is selected for the final solution. For selecting the right pumps and blowers available products and prototypes are characterized and checked for the system requirements. The investigation and the modelling of the exhaust gas condenser lead to an optimized component design for the ''Scooter'' DMFC design. Additionally, the integration of the anode loop is accomplished consisting of the supply lines, the circulating pump, the gas separator and the exhaust line. The direct coupling of the fuel cell with a lithium-ion battery as an option for electrical conditioning is investigated. In the system modelling the influence

  13. Feasibility of corona discharge ion mobility spectrometry for direct analysis of samples extracted by dispersive liquid-liquid microextraction.

    Jafari, Mohammad T; Riahi, Farhad

    2014-05-23

    The capability of corona discharge ionization ion mobility spectrometry (CD-IMS) for direct analysis of the samples extracted by dispersive liquid-liquid microextraction (DLLME) was investigated and evaluated, for the first time. To that end, an appropriate new injection port was designed and constructed, resulting in possibility of direct injection of the known sample volume, without tedious sample preparation steps (e.g. derivatization, solvent evaporation, and re-solving in another solvent…). Malathion as a test compound was extracted from different matrices by a rapid and convenient DLLME method. The positive ion mobility spectra of the extracted malathion were obtained after direct injection of carbon tetrachloride or methanol solutions. The analyte responses were compared and the statistical results revealed the feasibility of direct analysis of the extracted samples in carbon tetrachloride, resulting in a convenient methodology. The coupled method of DLLME-CD-IMS was exhaustively validated in terms of sensitivity, dynamic range, recovery, and enrichment factor. Finally, various real samples of apple, river and underground water were analyzed, all verifying the feasibility and success of the proposed method for the easy extraction of the analyte using DLLME separation before the direct analysis by CD-IMS. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Ni2P Makes Application of the PtRu Catalyst Much Stronger in Direct Methanol Fuel Cells.

    Chang, Jinfa; Feng, Ligang; Liu, Changpeng; Xing, Wei

    2015-10-12

    PtRu is regarded as the best catalyst for direct methanol fuel cells, but the performance decay resulting from the loss of Ru seriously hinders commercial applications. Herein, we demonstrated that the presence of Ni2 P largely reduces Ru loss, which thus makes the application of PtRu much stronger in direct methanol fuel cells. Outstanding catalytic activity and stability were observed by cyclic voltammetry. Upon integrating the catalyst material into a practical direct methanol fuel cell, the highest maximum power density was achieved on the PtRu-Ni2P/C catalyst among the reference catalysts at different temperatures. A maximum power density of 69.9 mW cm(-2) at 30 °C was obtained on PtRu-Ni2P/C, which is even higher than the power density of the state-of-the-art commercial PtRu catalyst at 70 °C (63.1 mW cm(-2)). Moreover, decay in the performance resulting from Ru loss was greatly reduced owing to the presence of Ni2 P, which is indicative of very promising applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Characterization and fuel cell performance analysis of polyvinylalcohol-mordenite mixed-matrix membranes for direct methanol fuel cell use

    Uctug, Fehmi Goerkem, E-mail: gorkem.uctug@bahcesehir.edu.t [University of Manchester, School of Chemical Engineering and Analytical Science, M60 1QD (United Kingdom); Holmes, Stuart M. [University of Manchester, School of Chemical Engineering and Analytical Science, M60 1QD (United Kingdom)

    2011-10-01

    Highlights: > We investigated the availability of PVA-mordenite membranes for DMFC use. > We measured the methanol permeability of PVA-mordenite membranes via pervaporation. > We did the fuel cell testing of these membranes, which had not been done before. > We showed that PVA-mordenite membranes have poorer DMFC performance than Nafion. > Membrane performance can be improved by increasing the proton conductivity of PVA. - Abstract: Polyvinylalcohol-mordenite (PVA-MOR) mixed matrix membranes were synthesized for direct methanol fuel cell (DMFC) use. For the structural and the morphological characterization, Scanning Electron Microscopy and Thermal Gravimetric Analysis methods were used. Zeolite distribution within the polymer matrix was found to be homogeneous. An impedance spectroscope was used to measure the proton conductivity. In order to obtain information about methanol permeation characteristics, swelling tests and a series of pervaporation experiments were carried out. 60-40 wt% PVA-MOR membranes were found to give the optimum transport properties. Proton conductivity of these membranes was found to be slightly lower than that of Nafion117{sup TM} whereas their methanol permeability was at least two orders of magnitude lower than Nafion117{sup TM}. DMFC performance of the PVA-MOR membranes was also measured. The inferior DMFC performance of PVA-MOR membranes was linked to drying in the fuel cell medium and the consequent proton conductivity loss. Their performance was improved by adding a dilute solution of sulfuric acid into the feed methanol solution. Future studies on the improvement of the proton conductivity of PVA-MOR membranes, especially via sulfonation of the polymer matrix, can overcome the low-performance problem associated with insufficient proton conductivity.

  16. Characterization and fuel cell performance analysis of polyvinylalcohol-mordenite mixed-matrix membranes for direct methanol fuel cell use

    Uctug, Fehmi Goerkem; Holmes, Stuart M.

    2011-01-01

    Highlights: → We investigated the availability of PVA-mordenite membranes for DMFC use. → We measured the methanol permeability of PVA-mordenite membranes via pervaporation. → We did the fuel cell testing of these membranes, which had not been done before. → We showed that PVA-mordenite membranes have poorer DMFC performance than Nafion. → Membrane performance can be improved by increasing the proton conductivity of PVA. - Abstract: Polyvinylalcohol-mordenite (PVA-MOR) mixed matrix membranes were synthesized for direct methanol fuel cell (DMFC) use. For the structural and the morphological characterization, Scanning Electron Microscopy and Thermal Gravimetric Analysis methods were used. Zeolite distribution within the polymer matrix was found to be homogeneous. An impedance spectroscope was used to measure the proton conductivity. In order to obtain information about methanol permeation characteristics, swelling tests and a series of pervaporation experiments were carried out. 60-40 wt% PVA-MOR membranes were found to give the optimum transport properties. Proton conductivity of these membranes was found to be slightly lower than that of Nafion117 TM whereas their methanol permeability was at least two orders of magnitude lower than Nafion117 TM . DMFC performance of the PVA-MOR membranes was also measured. The inferior DMFC performance of PVA-MOR membranes was linked to drying in the fuel cell medium and the consequent proton conductivity loss. Their performance was improved by adding a dilute solution of sulfuric acid into the feed methanol solution. Future studies on the improvement of the proton conductivity of PVA-MOR membranes, especially via sulfonation of the polymer matrix, can overcome the low-performance problem associated with insufficient proton conductivity.

  17. Covalent-ionically cross-linked polyetheretherketone proton exchange membrane for direct methanol fuel cell

    Luo, H

    2010-08-01

    Full Text Available cross-linked PEEK-WC membrane, this covalent-ionically cross-linked PEEK-WC membrane exhibits extremely reduced water uptake and methanol permeability, but just slightly sacrificed proton conductivity. The proton conductivity of the covalent...

  18. Controllable deposition of platinum nanoparticles on single-wall carbon nanohorns as catalyst for direct methanol fuel cells.

    Niu, Ben; Xu, Wei; Guo, Zhengduo; Zhou, Nengzhi; Liu, Yang; Shi, Zujin; Lian, Yongfu

    2012-09-01

    Uniform and well dispersed platinum nanoparticles were successfully deposited on single-walled carbon nanohorns with the assistance of 4,4-dipydine and ion liquids, respectively. In particular, the size of platinum nanoparticles could be controlled in a very narrow range (2.2 to 2.5 nm) when ion liquids were applied. The crystalline nature of these platinum nanoparticles was confirmed by high resolution transmission electron microscopy observation and X-ray power diffraction analysis, and two species of platinum Pt(0) and Pt(II) were detected by X-ray photoelectron spectroscopy. Electrochemical studies revealed that thus obtained nanocomposites had much better electrocatalytic activity for the methanol oxidation than those prepared with carbon nanotubes as supporter.

  19. Liquid-Phase Co-Exfoliated Graphene/MoS2 Nanocomposite for Methanol Gas Sensing.

    Zhang, Shao-Lin; Yue, Hongyan; Liang, Xishuang; Yang, Woo-Chul

    2015-10-01

    We developed an efficient method to co-exfoliate graphite and MoS2 to fabricate graphene/MoS2 nanocomposite. The size, morphology, and crystal structure of the graphene/MoS2 nanocomposite were carefully examined. The as-prepared graphene/MoS2 nanocomposite was fabricated into thin film sensor by a facile drop casting method and tested with methanol gas in various concentrations. The sensitivity, response time, and repeatability of the graphene/MoS2 nanocomposite sensor towards methanol gas were systematically investigated. A pure MoS2 based thin film sensor was also prepared and compared with the nanocomposite sensor to better understand the synergetic effect in the sensing performance. Our research demonstrated that compositing MoS2 with graphene could overcome the shortcoming of MoS2 as a sensor material and bring in a promising gas-sensing performance with a quicker response/recovery time and an enhanced sensitivity. Moreover, this composited material with a distinct structure and an excellent electronic property is expected to have potential application in various fields, such as optoelectronic.

  20. A “4-cell” modular passive DMFC (direct methanol fuel cell) stack for portable applications

    Wang, Luwen; He, Mingyan; Hu, Yue; Zhang, Yufeng; Liu, Xiaowei; Wang, Gaofeng

    2015-01-01

    A “4-cell” modular passive DMFC (direct methanol fuel cell) stack, which can be freely combined and applied to various electronic devices, is designed, fabricated and tested. Two PCB (printed circuit board) based accessories are designed and fabricated for electrically connecting and mechanically assembling the “4-cell” modules. The maximum power density of the “4-cell” module is 27 mW cm −2 at 5 M methanol concentration. The steady-state performances of the modular stacks with different numbers of modules are tested. The extra power loss of the multiple module stacks due to inter-module electrical connections is predicted by mathematical fitting method. The fitting results indicate that the efficiencies of the multiple module stacks are all above 90% up to 10 modules. The dynamic performances of the modular stacks are also investigated for portable applications. The results show that the modular stacks exhibit good responsiveness and reproducibility at high loading current (>100 mA). Finally, the modular stacks are successfully applied to drive the experimental fan and charge the mobile phone. - Highlights: • A “4-cell” modular passive DMFC (direct methanol fuel cell) stack is designed, fabricated and tested. • This modular DMFC stack can assemble more single cells with high efficiency. • The modular stack exhibit good responsiveness and reproducibility for portable application

  1. Bimetallic Nickel/Ruthenium Catalysts Synthesized by Atomic Layer Deposition for Low-Temperature Direct Methanol Solid Oxide Fuel Cells.

    Jeong, Heonjae; Kim, Jun Woo; Park, Joonsuk; An, Jihwan; Lee, Tonghun; Prinz, Fritz B; Shim, Joon Hyung

    2016-11-09

    Nickel and ruthenium bimetallic catalysts were heterogeneously synthesized via atomic layer deposition (ALD) for use as the anode of direct methanol solid oxide fuel cells (DMSOFCs) operating in a low-temperature range. The presence of highly dispersed ALD Ru islands over a porous Ni mesh was confirmed, and the Ni/ALD Ru anode microstructure was observed. Fuel cell tests were conducted using Ni-only and Ni/ALD Ru anodes with approximately 350 μm thick gadolinium-doped ceria electrolytes and platinum cathodes. The performance of fuel cells was assessed using pure methanol at operating temperatures of 300-400 °C. Micromorphological changes of the anode after cell operation were investigated, and the content of adsorbed carbon on the anode side of the operated samples was measured. The difference in the maximum power density between samples utilizing Ni/ALD Ru and Pt/ALD Ru, the latter being the best catalyst for direct methanol fuel cells, was observed to be less than 7% at 300 °C and 30% at 350 °C. The improved electrochemical activity of the Ni/ALD Ru anode compared to that of the Ni-only anode, along with the reduction of the number of catalytically active sites due to agglomeration of Ni and carbon formation on the Ni surface as compared to Pt, explains this decent performance.

  2. A durable PtRu/C catalyst with a thin protective layer for direct methanol fuel cells.

    Shimazaki, Yuzuru; Hayasaka, Sho; Koyama, Tsubasa; Nagao, Daisuke; Kobayashi, Yoshio; Konno, Mikio

    2010-11-15

    A methanol oxidation catalyst with improved durability in acidic environments is reported. The catalyst consists of PtRu alloy nanoparticles on a carbon support that were stabilized with a silane-coupling agent. The catalyst was prepared by reducing ions of Pt and Ru in the presence of a carbon support and the silane-coupling agent. The careful choice of preparatory conditions such as the concentration of the silane-coupling agent and solution pH resulted in the preparation of catalyst in which the PtRu nanoparticles were dispersively adsorbed onto the carbon support. The catalytic activity was similar to that of a commercial catalyst and was unchanged after immersion in sulfuric acid solution for 1000 h, suggesting the high durability of the PtRu catalyst for the anode of direct methanol fuel cells. Copyright © 2010 Elsevier Inc. All rights reserved.

  3. Graphene-cobaltite-Pd hybrid materials for use as efficient bifunctional electrocatalysts in alkaline direct methanol fuel cells.

    Sharma, Chandra Shekhar; Awasthi, Rahul; Singh, Ravindra Nath; Sinha, Akhoury Sudhir Kumar

    2013-12-14

    Hybrid materials comprising of Pd, MCo2O4 (where M = Mn, Co or Ni) and graphene have been prepared for use as efficient bifunctional electrocatalysts in alkaline direct methanol fuel cells. Structural and electrochemical characterizations were carried out using X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, chronoamperometry and cyclic, CO stripping, and linear sweep voltammetries. The study revealed that all the three hybrid materials are active for both methanol oxidation (MOR) and oxygen reduction (ORR) reactions in 1 M KOH. However, the Pd-MnCo2O4/GNS hybrid electrode exhibited the greatest MOR and ORR activities. This active hybrid electrode has also outstanding stability under both MOR and ORR conditions, while Pt- and other Pd-based catalysts undergo degradation under similar experimental conditions. The Pd-MnCo2O4/GNS hybrid catalyst exhibited superior ORR activity and stability compared to even Pt in alkaline solutions.

  4. Highly dispersed Pt-Ni nanoparticles on nitrogen-doped carbon nanotubes for application in direct methanol fuel cells.

    Jiang, Shujuan; Ma, Yanwen; Tao, Haisheng; Jian, Guoqiang; Wang, Xizhang; Fan, Yining; Zhu, Jianmin; Hu, Zheng

    2010-06-01

    Binary Pt-Ni alloyed nanoparticles supported on nitrogen-doped carbon nanotubes (NCNTs) have been facilely constructed without pre-modification by making use of the active sites in NCNTs due to the N-participation. So-obtained binary Pt-Ni alloyed nanoparticles have been highly dispersed on the outer surface of the support with the size of about 3-4 nm. The electrochemical properties of the catalysts for methanol oxidation have been systematically evaluated. Binary Pt-Ni alloyed composites with molar ratio (Pt:Ni) of 3:2 and 3:1 present enhanced electrocatalytic activities and improved tolerance to CO poisoning as well as the similar stability, in comparison with the commercial Pt/C catalyst and the monometallic Pt/NCNTs catalysts. These results imply that so-constructed nanocomposite catalysts have the potential for applications in direct methanol fuel cells.

  5. Numerical investigation of liquid methanol evaporation and oxy-combustion inside a button-cell ITM reactor

    Nemitallah, Medhat A.; Habib, Mohamed A.

    2017-01-01

    Highlights: • Analysis of liquid methanol evaporation and oxy-combustion in an ITM reactor. • A semi-empirical model is applied after fitting with the available LNO membrane data. • Influences of inlet fuel fraction, inlet gas temperature and inlet sweep flux are studied. • High combustion efficiency is encountered at moderate inlet gas temperatures. • High fuel concentration at low inlet sweep flow resulted in high oxygen flux. - Abstract: A numerical study is conducted to investigate the performance of a button-cell LNO-ITM reactor utilizing the soot-free oxygenated liquid methanol under oxy-combustion condition. The Euler-Lagrange approach is utilized to solve discrete phase model. Taylor analogy breakup (TAB) model is used due to its convenience with the cases of low injection speed. A plain orifice atomizer is used for fuel atomization and CO_2 is used as sweep gas. A semi-empirical oxygen permeation model (ABn model) is validated with the available experimental data and is, then, applied in the present model. Over a wide range of inlet fuel concentrations, the results showed increase in oxygen permeation flux of about five times in cases of reacting conditions as compared to the cases of non-reacting cases. The results showed high oxygen permeation flux at low inlet fuel concentrations due to the improvement in the oxygen to fuel ratio toward the stoichiometric conditions. At inlet gas temperatures of 1223 K, 1123 K, 1023 K and 923 K, the combustion temperature approached 1423 K, 1347 K, 1284 K and 1231 K, respectively, indicating an average combustion efficiency of 43% at moderate inlet gas temperatures. High fuel concentration at low inlet sweep flow resulted in high oxygen flux and high combustion temperature.

  6. Nafion titania nanotubes nanocomposite electrolytes for high-temperature direct methanol fuel cells

    Cele, NP

    2012-01-01

    Full Text Available electrolytes membranes. This promotes to study the Nafion/TNTs nanocomposite membranes behaviour with the aim to improve Nafion properties such as fuel permeability and thermal and mechanical stability. Nafion, whose primary structure consists of acid... membrane properties, further investigations were carried out. In this study, the effects of TiO2 nanotubes on Nafion properties such as water uptake, thermal stability, methanol (MeOH) permeability, and ion conductivity were investigated...

  7. Direct liquid content measurement applicable for He II space cryostats

    Wanner, M.

    1988-01-01

    A direct calorimetric method for content measurement in the He II cryostat ISO was assessed. A well defined heat pulse into the He II bath causes a small temperature increase which can be measured and directly correlated to the liquid mass through the He II specific heat. To study this method under the potential zero gravity constraints of disconnected liquid volumes a setup was established for investigating heat transfer between separated liquid volumes. The results for different fluid configurations confirm that even for completely disconnected volumes the heat is almost immediately distributed throughout the whole liquid by evaporation and recondensation

  8. High temperature transport properties of polyphosphazene membranes for direct methanol fuel cells

    Xiangyang Zhou; Chalkova, E. [Pennsylvania State University (United States). The Energy Institute; Weston, J.; Lvov, S.N. [Pennsylvania State University (United States). The Energy Institute; Pennsylvania State University (United States). Department of Energy and Geo-Environment Engineering; Hofmann, M.A.; Ambler, C.M.; Allcock, H.R. [Pennsylvania State University (United States). Department of Chemistry

    2003-06-30

    Experimental methods for studying the conductivity and methanol permeability of proton conductive polymers over a wide range of temperatures have been developed. The proton conductivity and methanol permeability of several polymer electrolyte membranes including sulfonated and phosphonated poly[(aryloxy)phosphazenes] was determined at temperatures up to 120 {sup o}C. Nafion 117 membranes were tested using the same methods in order to determine the reliability of the methods. Although the conductivities of the polyphosphazene membranes were either similar to or lower than that of the Nafion 117 membranes, they continue to hold promise for fuel cell applications. We observed similar activation energies of proton conduction for Nafion 117, and for sulfonated and phosphonated polyphosphazene membranes. However, the methanol permeability of a sulfonated membrane was about 8 times lower than that of the Nafion 117 membrane at room temperature although the values were comparable at 120 {sup o}C. The permeability of a phosphonated phosphazene derivative was about 40 times lower than that of the Nafion 117 membrane at room temperature and about 9 times lower at 120 {sup o}C. This is a significant improvement over the behavior of Nafion 117. (author)

  9. High temperature transport properties of polyphosphazene membranes for direct methanol fuel cells

    Zhou Xiangyang; Weston, Jamie; Chalkova, Elena; Hofmann, Michael A.; Ambler, Catherine M.; Allcock, Harry R.; Lvov, Serguei N

    2003-06-30

    Experimental methods for studying the conductivity and methanol permeability of proton conductive polymers over a wide range of temperatures have been developed. The proton conductivity and methanol permeability of several polymer electrolyte membranes including sulfonated and phosphonated poly[(aryloxy)phosphazenes] was determined at temperatures up to 120 deg. C. Nafion 117 membranes were tested using the same methods in order to determine the reliability of the methods. Although the conductivities of the polyphosphazene membranes were either similar to or lower than that of the Nafion 117 membranes, they continue to hold promise for fuel cell applications. We observed similar activation energies of proton conduction for Nafion 117, and for sulfonated and phosphonated polyphosphazene membranes. However, the methanol permeability of a sulfonated membrane was about 8 times lower than that of the Nafion 117 membrane at room temperature although the values were comparable at 120 deg. C. The permeability of a phosphonated phosphazene derivative was about 40 times lower than that of the Nafion 117 membrane at room temperature and about 9 times lower at 120 deg. C. This is a significant improvement over the behavior of Nafion 117.

  10. High temperature transport properties of polyphosphazene membranes for direct methanol fuel cells

    Zhou Xiangyang; Weston, Jamie; Chalkova, Elena; Hofmann, Michael A.; Ambler, Catherine M.; Allcock, Harry R.; Lvov, Serguei N.

    2003-01-01

    Experimental methods for studying the conductivity and methanol permeability of proton conductive polymers over a wide range of temperatures have been developed. The proton conductivity and methanol permeability of several polymer electrolyte membranes including sulfonated and phosphonated poly[(aryloxy)phosphazenes] was determined at temperatures up to 120 deg. C. Nafion 117 membranes were tested using the same methods in order to determine the reliability of the methods. Although the conductivities of the polyphosphazene membranes were either similar to or lower than that of the Nafion 117 membranes, they continue to hold promise for fuel cell applications. We observed similar activation energies of proton conduction for Nafion 117, and for sulfonated and phosphonated polyphosphazene membranes. However, the methanol permeability of a sulfonated membrane was about 8 times lower than that of the Nafion 117 membrane at room temperature although the values were comparable at 120 deg. C. The permeability of a phosphonated phosphazene derivative was about 40 times lower than that of the Nafion 117 membrane at room temperature and about 9 times lower at 120 deg. C. This is a significant improvement over the behavior of Nafion 117

  11. Novel proton exchange membrane based on crosslinked poly(vinyl alcohol) for direct methanol fuel cells

    Liu, Chien-Pan; Dai, Chi-An; Chao, Chi-Yang; Chang, Shoou-Jinn

    2014-03-01

    In this study, we report the synthesis and the characterization of poly (vinyl alcohol) based proton conducting membranes. In particular, we describe a novel physically and chemically PVA/HFA (poly (vinyl alcohol)/hexafluoroglutaric acid) blending membranes with BASANa (Benzenesulfonic acid sodium salt) and GA (Glutaraldehyde) as binary reaction agents. The key PEM parameters such as ion exchange capacity (IEC), water uptake, proton conductivity, and methanol permeability were controlled by adjusting the chemical composition of the membranes. The IEC value of the membrane is found to be an important parameter in affecting water uptake, conductivity as well as the permeability of the resulting membrane. Plots of the water uptake, conductivity, and methanol permeability vs. IEC of the membranes show a distinct change in the slope of their curves at roughly the same IEC value which suggests a transition of structural changes in the network. The proton conductivities and the methanol permeability of all the membranes are in the range of 10-3-10-2 S cm-1 and 10-8-10-7 cm2 s-1, respectively, depending on its binary crosslinking density, and it shows great selectivity compared with those of Nafion®-117. The membranes display good mechanical properties which suggest a good lifetime usage of the membranes applied in DMFCs.

  12. Energy efficiency of a direct-injection internal combustion engine with high-pressure methanol steam reforming

    Poran, Arnon; Tartakovsky, Leonid

    2015-01-01

    This article discusses the concept of a direct-injection ICE (internal combustion engine) with thermo-chemical recuperation realized through SRM (steam reforming of methanol). It is shown that the energy required to compress the reformate gas prior to its injection into the cylinder is substantial and has to be accounted for. Results of the analysis prove that the method of reformate direct-injection is unviable when the reforming is carried-out under atmospheric pressure. To reduce the energy penalty resulted from the gas compression, it is suggested to implement a high-pressure reforming process. Effects of the injection timing and the injector's flow area on the ICE-SRM system's fuel conversion efficiency are studied. The significance of cooling the reforming products prior to their injection into the engine-cylinder is demonstrated. We show that a direct-injection ICE with high-pressure SRM is feasible and provides a potential for significant efficiency improvement. Development of injectors with greater flow area shall contribute to further efficiency improvements. - Highlights: • Energy needed to compress the reformate is substantial and has to be accounted for. • Reformate direct-injection is unviable if reforming is done at atmospheric pressure. • Direct-injection engine with high-pressure methanol reforming is feasible. • Efficiency improvement by 12–14% compared with a gasoline-fed engine was shown

  13. Diamond nanoparticles as a support for Pt and PtRu catalysts for direct methanol fuel cells.

    La-Torre-Riveros, Lyda; Guzman-Blas, Rolando; Méndez-Torres, Adrián E; Prelas, Mark; Tryk, Donald A; Cabrera, Carlos R

    2012-02-01

    Diamond in nanoparticle form is a promising material that can be used as a robust and chemically stable catalyst support in fuel cells. It has been studied and characterized physically and electrochemically, in its thin film and powder forms, as reported in the literature. In the present work, the electrochemical properties of undoped and boron-doped diamond nanoparticle electrodes, fabricated using the ink-paste method, were investigated. Methanol oxidation experiments were carried out in both half-cell and full fuel cell modes. Platinum and ruthenium nanoparticles were chemically deposited on undoped and boron doped diamond nanoparticles through the use of NaBH(4) as reducing agent and sodium dodecyl benzene sulfonate (SDBS) as a surfactant. Before and after the reduction process, samples were characterized by electron microscopy and spectroscopic techniques. The ink-paste method was also used to prepare the membrane electrode assembly with Pt and Pt-Ru modified undoped and boron-doped diamond nanoparticle catalytic systems, to perform the electrochemical experiments in a direct methanol fuel cell system. The results obtained demonstrate that diamond supported catalyst nanomaterials are promising for methanol fuel cells.

  14. Partial sulfonation of PVdF-co-HFP: A preliminary study and characterization for application in direct methanol fuel cell

    Das, Suparna; Kumar, Piyush; Dutta, Kingshuk; Kundu, Patit Paban

    2014-01-01

    Highlights: • Synthesis of sulfonated PVdF-co-HFP by reacting with chlorosulfonic acid. • Maximum degree of sulfonation and best properties were obtained for 7 h reaction. • A maximum water uptake value of 20% was obtained. • A maximum IEC value of 0.42 meq g −1 was obtained. • A methanol permeability of 2.44 × 10 −7 cm 2 s −1 was obtained. - Abstract: Sulfonation of PVdF-co-HFP was conducted by treating the copolymer with chlorosulfonic acid. The efficiency of this sulfonated copolymer towards application as a polymer electrolyte membrane in direct methanol fuel cell (DMFC) was evaluated. For this purpose, we determined the thermal stability, water uptake, ion exchange capacity (IEC), methanol crossover, and proton conductivity of the prepared membranes as functions of duration and degree of sulfonation. The characteristic aromatic peaks obtained in the FT-IR spectra confirmed the successful sulfonation of PVdF-co-HFP. The effect of sulfonation on the semi-crystalline nature of pure PVdF-co-HFP was determined from XRD analysis. Water uptake results indicated that a sulfonation time of 7 h produced maximum water uptake value of about 20%, with a corresponding IEC and proton conductivity values of about 0.42 meq g −1 and 0.00375 S cm −1 respectively. The maximum current density was recorded to be 30 mA cm −2 at 0.2 V potential

  15. Electrical enhancement of direct methanol fuel cells by metal-plasma ion implantation Pt-Ru/C multilayer catalysts.

    Weng, Ko-Wei; Chen, Yung-Lin; Chen, Ya-Chi; Lin, Tai-Nan

    2009-02-01

    Direct methanol fuel cells (DMFC) have been widely studied owing to their simple cell configuration, high volume energy density, short start-up time, high operational reliability and other favorable characteristics. However, major limitations include high production cost, poisoning of the catalyst and methanol crossover. This study adopts a simple technique for preparing Pt-Ru/C multilayer catalysts, including magnetron sputtering (MS) and metal-plasma ion implantation (MPII). The Pt catalysts were sputtered onto the gas diffusion layer (GDL), followed by the implantation of Ru catalysts using MPII (at an accelerating voltage of 20 kV and an implantation dose of 1 x 10(16) ions/cm2). Pt-Ru is repeatedly processed to prepare Pt-Ru/C multilayer catalysts. The catalyst film structure and microstructure were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electronic microscopy (SEM), respectively. The cell performance was tested using a potential stat/galvano-stat. The results reveal that the membrane electrode assembly (MEA) of four multilayer structures enhances the cell performance of DMFC. The measured power density is 2.2 mW/cm2 at a methanol concentration of 2 M, with an OCV of 0.493 V.

  16. Co-deposition of Pt and ceria anode catalyst in supercritical carbon dioxide for direct methanol fuel cell applications

    You, Eunyoung; Guzmán-Blas, Rolando; Nicolau, Eduardo; Aulice Scibioh, M.; Karanikas, Christos F.; Watkins, James J.; Cabrera, Carlos R.

    2012-01-01

    Pt and mixed Pt-ceria catalysts were deposited onto gas diffusion layers using supercritical fluid deposition (SFD) to fabricate thin layer electrodes for direct methanol fuel cells. Dimethyl (1,5-cyclooctadiene) platinum (II) (CODPtMe 2 ) and tetrakis (2,2,6,6-tetramethyl 3,5-heptanedionato) cerium (IV) (Ce(tmhd) 4 ) were used as precursors. Hydrogen-assisted Pt deposition was performed in compressed carbon dioxide at 60 °C and 17.2 MPa to yield high purity Pt on carbon-black based gas diffusion layers. During the preparation of the mixed Pt-ceria catalyst, hydrogen reduction of CODPtMe 2 to yield Pt catalyzed the deposition of ceria from Ce(tmhd) 4 enabling co-deposition at 150 °C. The catalyst layers were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscope-energy dispersive spectral (SEM-EDS) analyses. Their electrochemical performance toward methanol oxidation was examined in half cell mode using a three electrode assembly as well as in fuel cell mode. The thin layer electrodes formed via SFD exhibited higher performance in fuel cell operations compared to those prepared by the conventional brush-paint method. Furthermore, the Pt-ceria catalyst with an optimized composition exhibited greater methanol oxidation activity than pure platinum.

  17. Highly stable ionic-covalent cross-linked sulfonated poly(ether ether ketone) for direct methanol fuel cells

    Lei, Linfeng; Zhu, Xingye; Xu, Jianfeng; Qian, Huidong; Zou, Zhiqing; Yang, Hui

    2017-05-01

    A novel ionic cross-linked sulfonated poly(ether ether ketone) containing equal content of sulfonic acid and pendant tertiary amine groups (TA-SPEEK) has been initially synthesized for the application in direct methanol fuel cells (DMFCs). By adjusting the ratio of p-xylene dibromide to tertiary amine groups of TA-SPEEK, a series of ionic-covalent cross-linked membranes (C-SPEEK-x) with tunable degree of cross-linking are prepared. Compared with the pristine membrane, the ionic and ionic-covalent cross-linked proton exchange membranes (PEMs) exhibit reduced methanol permeability and improved mechanical properties, dimensional and oxidative stability. The proton conductivity and methanol selectivity of protonated TA-SPEEK and C-SPEEK-x at 25 °C is up to 0.109 S cm-1 and 3.88 × 105 S s cm-3, respectively, which are higher than that of Nafion 115. The DMFC incorporating C-SPEEK-25 exhibits a maximum power density as high as 35.3 mW cm-2 with 4 M MeOH at 25 °C (31.8 mW cm-2 for Nafion 115). Due to the highly oxidative stability of the membrane, no obvious performance degradation of the DMFC is observed after more than 400 h operation, indicating such cost-effective ionic-covalent cross-linked membranes have substantial potential as alternative PEMs for DMFC applications.

  18. Vertically aligned carbon nanotubes/carbon fiber paper composite to support Pt nanoparticles for direct methanol fuel cell application

    Zhang, Jing; Yi, Xi-bin; Liu, Shuo; Fan, Hui-Li; Ju, Wei; Wang, Qi-Chun; Ma, Jie

    2017-03-01

    Vertically aligned carbon nanotubes (VACNTs) grown on carbon fiber paper (CFP) by plasma enhanced chemical vapor deposition is introduced as a catalyst support material for direct methanol fuel cells (DMFCs). Well dispersed Pt nanoparticles on VACNTs surface are prepared by impregnation-reduction method. The VACNTs on CFP possess well-maintained alignment, large surface area and good electrical conductivity, which leading to the formation of Pt particles with a smaller size and enhance the Pt utilization rate. The structure and nature of resulting Pt/VACNTs/CFP catalysts for methanol oxidation are investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD) and scanning electron microscope (SEM). With the aid of VACNTs, well-dispersed Pt catalysts enable the reversibly rapid redox kinetic since electron transport efficiently passes through a one-dimensional pathway, which leads to enhance the catalytic activity and Pt utilization rate. Compared with the Pt/XC-72/CFP electrode, the electrochemical measurements results display that the Pt/VACNTs/CFP catalyst shows much higher electrocatalytic activity and better stability for methanol oxidation. In addition, the oxidation current from 200 to 1200 s decayed more slowly for the Pt/VACNTs/CFP than that of the Pt/XC-72/CFP catalysts, indicating less accumulation of adsorbed CO species. All those results imply that the Pt/VACNTs/CFP has a great potential for applications in DMFCs.

  19. Enhanced activity and durability of platinum anode catalyst by the modification of cobalt phosphide for direct methanol fuel cells

    Li, Xiang; Wang, Hongjuan; Yu, Hao; Liu, Ziwu; Wang, Haihui; Peng, Feng

    2015-01-01

    Graphical abstract: A novel Pt/CoP/CNTs electrocatalyst with has been designed and prepared, which exhibits high activity and stability for methanol oxidation reaction. - Highlights: • Pt-cobalt phosphide catalyst supported on carbon nanotubes (Pt/CoP/CNTs) is designed. • Pt/CoP/CNTs exhibit high activity and stability for methanol oxidation reaction(MOR). • The effect of CoP content on electrocatalytic performances for MOR is studied. • CoP decreases the Pt particle size and increases the electrochemical surface areas. • The interaction between Pt and CoP is evidenced by X-ray photoelectron spectroscopy. - Abstract: In this study, carbon nanotubes (CNTs) supported Pt-cobalt phosphide (CoP) electrocatalyst (Pt/CoP/CNTs) is designed and prepared for methanol oxidation (MOR) for the first time. The modification of CoP decreases the Pt particle size significantly and increases the electrochemical surface areas due to the interaction between Pt and CoP, which is evidenced by transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Among all these catalysts, Pt/4%CoP/CNTs catalyst exhibits the best MOR activity of 1600 mA mg −1 Pt , which is six times that of Pt/CNTs. Moreover, this catalyst also exhibits the higher onset current density and steady current density than the other Pt-based catalysts. The work provides a promising method to develop the highly active and stable Pt-based catalyst for direct methanol fuel cells.

  20. Catalytic methanol dissociation

    Alcinikov, Y.; Fainberg, V.; Garbar, A.; Gutman, M.; Hetsroni, G.; Shindler, Y.; Tatrtakovsky, L.; Zvirin, Y.

    1998-01-01

    Results of the methanol dissociation study on copper/potassium catalyst with alumina support at various temperatures are presented. The following gaseous and liquid products at. The catalytic methanol dissociation is obtained: hydrogen, carbon monoxide, carbon dioxide, methane, and dimethyl ether. Formation rates of these products are discussed. Activation energies of corresponding reactions are calculated

  1. Polypyrrole layered SPEES/TPA proton exchange membrane for direct methanol fuel cells

    Neelakandan, S.; Kanagaraj, P. [PG & Research Department of Chemistry, Polymeric Materials Research Lab, Alagappa Government Arts College, Karaikudi 630003 (India); Sabarathinam, R.M. [Functional Material Division, Central Electrochemical Research Institute, Karaikudi 630006 (India); Nagendran, A., E-mail: nagimmm@yahoo.com [PG & Research Department of Chemistry, Polymeric Materials Research Lab, Alagappa Government Arts College, Karaikudi 630003 (India)

    2015-12-30

    Graphical abstract: - Highlights: • A series of Ppy layered SPEES/TPA composite membranes were prepared. • SPEES/TPA-Ppy hybrid membranes displayed efficient methanol resistance than Nafion 117. • SPEES/TPA-Ppy4 membrane exhibits highest relative selectivity of 2.86 × 104 S cm{sup 3} s. • Increasing Ppy layer on membrane surface reduces the leaching out of tungstophosphoric acid. - Abstract: Hybrid membranes based on sulfonated poly(1,4-phenylene ether ether sulfone) (SPEES)/tungstophosphoric acid (TPA) were prepared. SPEES/TPA membrane surfaces were modified with polypyrrole (Ppy) by in situ polymerization method to reduce the TPA leaching. The morphology and electrochemical property of the surface coated membranes were studied by SEM, AFM, water uptake, ion exchange capacity, proton conductivity, methanol permeability and tensile strength. The water uptake and the swelling ratio of the surface coated membranes decreased with increasing the Ppy layer. The surface roughness of the hybrid membrane was decreased with an increase in Ppy layer on the membrane surface. The methanol permeability of SPEES/TPA-Ppy4 hybrid membrane was significantly suppressed and found to be 2.1 × 10{sup −7} cm{sup 2} s{sup −1}, which is 1.9 times lower than pristine SPEES membrane. The SPEES/TPA-Ppy4 membrane exhibits highest relative selectivity (2.86 × 10{sup 4} S cm{sup −3} s) than the other membrane with low TPA leaching. The tensile strength of hybrid membranes was improved with the introduction of Ppy layer. Combining their lower swelling ratio, high thermal stability and selectivity, SPEES/TPA-Ppy4 membranes could be a promising material as PEM for DMFC applications.

  2. Polypyrrole layered SPEES/TPA proton exchange membrane for direct methanol fuel cells

    Neelakandan, S.; Kanagaraj, P.; Sabarathinam, R.M.; Nagendran, A.

    2015-01-01

    Graphical abstract: - Highlights: • A series of Ppy layered SPEES/TPA composite membranes were prepared. • SPEES/TPA-Ppy hybrid membranes displayed efficient methanol resistance than Nafion 117. • SPEES/TPA-Ppy4 membrane exhibits highest relative selectivity of 2.86 × 104 S cm"3 s. • Increasing Ppy layer on membrane surface reduces the leaching out of tungstophosphoric acid. - Abstract: Hybrid membranes based on sulfonated poly(1,4-phenylene ether ether sulfone) (SPEES)/tungstophosphoric acid (TPA) were prepared. SPEES/TPA membrane surfaces were modified with polypyrrole (Ppy) by in situ polymerization method to reduce the TPA leaching. The morphology and electrochemical property of the surface coated membranes were studied by SEM, AFM, water uptake, ion exchange capacity, proton conductivity, methanol permeability and tensile strength. The water uptake and the swelling ratio of the surface coated membranes decreased with increasing the Ppy layer. The surface roughness of the hybrid membrane was decreased with an increase in Ppy layer on the membrane surface. The methanol permeability of SPEES/TPA-Ppy4 hybrid membrane was significantly suppressed and found to be 2.1 × 10"−"7 cm"2 s"−"1, which is 1.9 times lower than pristine SPEES membrane. The SPEES/TPA-Ppy4 membrane exhibits highest relative selectivity (2.86 × 10"4 S cm"−"3 s) than the other membrane with low TPA leaching. The tensile strength of hybrid membranes was improved with the introduction of Ppy layer. Combining their lower swelling ratio, high thermal stability and selectivity, SPEES/TPA-Ppy4 membranes could be a promising material as PEM for DMFC applications.

  3. Controllable pt nanoparticle deposition on carbon nanotubes as an anode catalyst for direct methanol fuel cells.

    Mu, Yongyan; Liang, Hanpu; Hu, Jinsong; Jiang, Li; Wan, Lijun

    2005-12-01

    We report a novel process to prepare well-dispersed Pt nanoparticles on CNTs. Pt nanoparticles, which were modified by the organic molecule triphenylphosphine, were deposited on multiwalled carbon nanotubes by the organic molecule, which acts as a cross linker. By manipulating the relative ratio of Pt nanoparticles and multiwalled carbon nanotubes in solution, Pt/CNT composites with different Pt content were achieved. The so-prepared Pt/CNT composite materials show higher electrocatalytic activity and better tolerance to poisoning species in methanol oxidation than the commercial E-TEK catalyst, which can be ascribed to the high dispersion of Pt nanoparticles on the multiwalled carbon nanotube surface.

  4. High methanol oxidation activity of electrocatalysts supported by directly grown nitrogen-containing carbon nanotubes on carbon cloth

    Wang, C.-H.; Shih, H.-C.; Tsai, Y.-T.; Du, H.-Y.; Chen, L.-C.; Chen, K.-H.

    2006-01-01

    The microstructure and electrochemical activity of the Pt-Ru supported by nitrogen-containing carbon nanotubes (CN x NTs) directly grown on the carbon cloth have been investigated. The CN x NTs directly grown on the carbon cloth (CN x NTs-carbon cloth composite electrode) were synthesized using microwave-plasma-enhanced chemical vapour deposition first and then use as the template to support the Pt-Ru nanoclusters subsequently sputtered on. The ferricyanide/ferrocyanide redox reaction in cyclic voltammetry (CV) measurements showed a faster electron transfer on the CN x NTs-carbon cloth composite electrode than the one with carbon cloth alone. Comparing their methanol oxidation abilities, it is found that the Pt-Ru nanoclusters supported by the CN x NTs-carbon cloth composite electrode have considerably higher electrocatalytic activity than the carbon cloth counterpart. This result suggests high performance of the CN x NTs-carbon cloth composite electrode, and demonstrates its suitability for direct methanol fuel cell applications

  5. High methanol oxidation activity of electrocatalysts supported by directly grown nitrogen-containing carbon nanotubes on carbon cloth

    Wang, C.-H. [Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan (China); Shih, H.-C. [Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan (China); Institue of Materials Science and Nano Technology, Chinese Culture University, Taipei, Taiwan (China); Tsai, Y.-T. [Institue of Materials Science and Nano Technology, Chinese Culture University, Taipei, Taiwan (China); Du, H.-Y. [Institue of Materials Science and Nano Technology, Chinese Culture University, Taipei, Taiwan (China); Chen, L.-C. [Center for Condensed Matter Sciences, National Taiwan University, Taipei, Taiwan (China); Chen, K.-H. [Center for Condensed Matter Sciences, National Taiwan University, Taipei, Taiwan (China) and Institue of Atomic and Molecular Science, Academia Sinica, Taipei, Taiwan (China)]. E-mail: chenkh@pub.iams.sinica.edu.tw

    2006-12-01

    The microstructure and electrochemical activity of the Pt-Ru supported by nitrogen-containing carbon nanotubes (CN {sub x} NTs) directly grown on the carbon cloth have been investigated. The CN {sub x} NTs directly grown on the carbon cloth (CN {sub x} NTs-carbon cloth composite electrode) were synthesized using microwave-plasma-enhanced chemical vapour deposition first and then use as the template to support the Pt-Ru nanoclusters subsequently sputtered on. The ferricyanide/ferrocyanide redox reaction in cyclic voltammetry (CV) measurements showed a faster electron transfer on the CN {sub x} NTs-carbon cloth composite electrode than the one with carbon cloth alone. Comparing their methanol oxidation abilities, it is found that the Pt-Ru nanoclusters supported by the CN {sub x} NTs-carbon cloth composite electrode have considerably higher electrocatalytic activity than the carbon cloth counterpart. This result suggests high performance of the CN {sub x} NTs-carbon cloth composite electrode, and demonstrates its suitability for direct methanol fuel cell applications.

  6. (Solid + liquid) phase diagram for (indomethacin + nicotinamide)-methanol or methanol/ethyl acetate mixture and solubility behavior of 1:1 (indomethacin + nicotinamide) co-crystal at T = (298.15 and 313.15) K

    Sun, Xiaowei; Yin, Qiuxiang; Ding, Suping; Shen, Zhiming; Bao, Ying; Gong, Junbo; Hou, Baohong; Hao, Hongxun; Wang, Yongli; Wang, Jingkang; Xie, Chuang

    2015-01-01

    Highlights: • Ternary phase diagrams of (IMC + NCT)-methanol or methanol/ethyl acetate mixture at T = (298.15 and 313.15) K were measured. • The effects of temperature and introduced ethyl acetate on solid phase stability were discussed. • Solubility of (IMC + NCT) cocrystals was first correlated using a model considering solubility product and complexation. • Solubility of (IMC + NCT) cocrystals as a function of co-former concentration was evaluated. - Abstract: (Solid + liquid) equilibrium data for indomethacin (IMC) and nicotinamide (NCT) in both methanol (MeOH) and methanol/ethyl acetate (EA) mixture were determined using a static method at T = (298.15 and 313.15) K under atmospheric pressure. The 1:1 (IMC + NCT) co-crystal and IMC·MeOH were found in both systems under conditions investigated. The solubility of the 1:1 (IMC + NCT) co-crystal was correlated using a mathematical model consisting of both solubility product and a complexation process. Solubility of (IMC + NCT) co-crystals as a function of co-former (NCT) concentration was evaluated. It was found that temperature has a significant effect on the formation of methanol solvate in the systems investigated. Solvate formation could be suppressed either by increasing temperature or using solvent mixtures. Additionally, the solvent mixture could level out the solubility differences between IMC and NCT, resulting in larger and more symmetric regions for the (IMC + NCT) co-crystal, which would be helpful to the development of the co-crystallization process for the 1:1 (IMC + NCT) co-crystal

  7. Three dimensional graphene foam supported platinum-ruthenium bimetallic nanocatalysts for direct methanol and direct ethanol fuel cell applications

    Kung, Chih-Chien; Lin, Po-Yuan; Xue, Yuhua; Akolkar, Rohan; Dai, Liming; Yu, Xiong; Liu, Chung-Chiun

    2014-06-01

    A novel composite material of hierarchically structured platinum-ruthenium (PtRu) nanoparticles grown on large surface area three dimensional graphene foam (3D GF) is reported. 3D GF was incorporated with PtRu bimetallic nanoparticles as an electrochemical nanocatalyst for methanol and ethanol oxidation. PtRu/3D GF nanocatalyst showed a higher tolerance to poisoning by CO and exhibited improved catalytic activity for both methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR). Cyclic voltammetry (CV) results and long-term cycling stability tests demonstrated that GF provided a promising platform for the development of electrochemical nanocatalysts. Specifically, PtRu/3D GF nanocatalyst showed excellent catalytic activity toward MOR and EOR compared with PtRu/Graphene (Commercial graphene), PtRu/C (Vulcan XC-72R carbon), and PtRu alone. The crystal size of PtRu on 3D GF was reduced to 3.5 nm and its active surface area was enhanced to 186.2 m2 g-1. Consequently, the MOR and EOR rates were nearly doubled on PtRu/3D GF compared to those on PtRu/Graphene.

  8. Passively operated vapor-fed direct methanol fuel cells for portable applications

    Eccarius, Steffen; Krause, Falko; Agert, Carsten [Fraunhofer Institute for Solar Energy Systems ISE, Department of Energy Systems, Heidenhofstrasse 2, 79110 Freiburg (Germany); Beard, Kevin [Department of Chemical Engineering, University of South Carolina, Columbia (United States)

    2008-08-01

    The impact of structural parameters and operating conditions has not been researched yet for vapor-fed operation of a DMFC at near-ambient conditions. Thus, a detailed parameter study that included reference cell measurements to assess anode and cathode losses separately was performed. Among other parameters like temperature or air stoichiometry, different opening ratios that controlled evaporation of methanol into the vapor chamber were examined. Water management was found to be a critical parameter for a vapor-fed DMFC. Depletion of water inside the anode catalyst layer, especially at higher current densities, decreased performance of the fuel cell substantially. Back diffusion of water from the cathode to the anode was examined. A micro-structured cathode electrode that increased water back diffusion due to a reduced mass transfer resistance was developed and investigated. Finally, efficiencies and heat losses of a vapor-fed DMFC were determined. (author)

  9. Platinum-gold nanoclusters as catalyst for direct methanol fuel cells.

    Giorgi, L; Giorgi, R; Gagliardi, S; Serra, E; Alvisi, M; Signore, M A; Piscopiello, E

    2011-10-01

    Nanosized platinum-gold alloys clusters have been deposited on gas diffusion electrode by sputter deposition. The deposits were characterized by FE-SEM, TEM and XPS in order to verify the formation of alloy nanoparticles and to study the influence of deposition technique on the nanomorphology. The deposition by sputtering process allowed a uniform distribution of metal particles on porous surface of carbon supports. Typical island growth mode was observed with the formation of a dispersed metal nanoclusters (mean size about 5 nm). Cyclic voltammetry was used to determine the electrochemical active surface and the electrocatalytic performance of the PtAu electrocatalysts for methanol oxidation reaction. The data were re-calculated in the form of mass specific activity (MSA). The sputter-catalyzed electrodes showed higher performance and stability compared to commercial catalysts.

  10. Nafion Titania Nanotubes Nanocomposite Electrolytes for High-Temperature Direct Methanol Fuel Cells

    Nonhlanhla Precious Cele

    2012-01-01

    Full Text Available Nafion-based nanocomposite membranes containing various amounts of titania nanotubes (TNTs as an inorganic filler have been prepared using melt-mixing method and have been investigated for proton exchange membrane applications. The one-dimensional TNTs have been prepared from potassium hydroxide using hydrothermal route and conventional heating. Nafion R1100 in a protonated form was used, and TNT contents were in a range of 0.5–2.0 wt%. The acid-treated composite membranes, at lowest inorganic additive content, exhibited improved properties in terms of thermal stability and methanol (MeOH permeability. The best performing nanocomposite was the membrane containing only 0.5 wt% TNTs showing ionic conductivity value of 7.2×10-2 S·cm-1 at 26°C and 100% of relative humidity.

  11. The influence of methanol on the chemical state of PtRu anodes in a high-temperature direct methanol fuel cell studied in situ by synchrotron-based near-ambient pressure x-ray photoelectron spectroscopy

    Saveleva, Viktoriia A; Savinova, Elena R; Daletou, Maria K

    2017-01-01

    Synchrotron radiation-based near-ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) has recently become a powerful tool for the investigation of interfacial phenomena in electrochemical power sources such as batteries and fuel cells. Here we present an in situ NAP-XPS study of the anode of a high-temperature direct methanol fuel cell with a phosphoric acid-doped hydrocarbon membrane, which reveals an enhanced flooding of the Pt 3 Ru anode with phosphoric acid in the presence of methanol. An analysis of the electrode surface composition depending on the cell voltage and on the presence of methanol reveals the strong influence of the latter on the extent of Pt oxidation and on the transformation of Ru into Ru (IV) hydroxide. (paper)

  12. The influence of methanol on the chemical state of PtRu anodes in a high-temperature direct methanol fuel cell studied in situ by synchrotron-based near-ambient pressure x-ray photoelectron spectroscopy

    Saveleva, Viktoriia A.; Daletou, Maria K.; Savinova, Elena R.

    2017-01-01

    Synchrotron radiation-based near-ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) has recently become a powerful tool for the investigation of interfacial phenomena in electrochemical power sources such as batteries and fuel cells. Here we present an in situ NAP-XPS study of the anode of a high-temperature direct methanol fuel cell with a phosphoric acid-doped hydrocarbon membrane, which reveals an enhanced flooding of the Pt3Ru anode with phosphoric acid in the presence of methanol. An analysis of the electrode surface composition depending on the cell voltage and on the presence of methanol reveals the strong influence of the latter on the extent of Pt oxidation and on the transformation of Ru into Ru (IV) hydroxide.

  13. LiquidPower-1. Development and proof-of-concept of core methanol reformer for stationary and motive fuel cell systems and hydrogen refuelling stations. Final report

    Krogsgaard, J.; Mortensen, Henrik [H2 Logic A/S, Herning (Denmark); Skipper, T. [Dantherm Power A/S, Hobro (Denmark)

    2013-03-15

    LiquidPower-1 has developed laboratory test systems for methanol reforming and tested reformers from four different suppliers. This has contributed to determining the state-of-the-art level for methanol reforming and enabled an update of the LiquidPower R and D Roadmap onwards a commercialisation of the technology. The project has achieved the following results: 1) A detailed technical specification of methanol reformers for the fuel cell back-up power and hydrogen refueling station markets has been conducted; 2) Laboratory test systems for methanol reformers has been developed and established at Dantherm Power and H2 Logic; 3) Initial test of reformers from four suppliers has been conducted - with two suppliers being selected for continued tests; 4) Extensive laboratory tests conducted of reformers from two suppliers, with the aim to determine state-of-the-art for price, efficiency, capacity and lifetime. Several errors and break-downs were experienced during the test period, which revealed a need for further R and D to improve lifetime and stability; 5) The LiquidPower F and U Roadmap has been updated. Reformer TCO targets (Total Cost of Operation) for each of the markets have been calculated including updated targets for efficiency and cost. These targets also serve as the main ones to be pursued as part of the continued R and D roadmap execution. Compared to the previous edition of the Roadmap, the project has confirmed the viability of methanol reforming, but also revealed that stability and lifetime needs to be addressed and solved before commencing commercialization of the technology. If the Roadmap is successful a commercialization can commence beyond 2015. (Author)

  14. Characterization of direct methanol fuel cell (DMFC) applications with H{sub 2}SO{sub 4} modified chitosan membrane

    Osifo, Peter O.; Masala, Aluwani [Department of Chemical Engineering, Vaal University of Technology, Andries Potgieter Bolevald, P/Bag X021, Vanderbijlpark 1900, Gauteng (South Africa)

    2010-08-01

    Chitosan (Chs) flakes were prepared from chitin materials that were extracted from the exoskeleton of Cape rock lobsters in South Africa. The Chs flakes were prepared into membranes and the Chs membranes were modified by cross-linking with H{sub 2}SO{sub 4}. The cross-linked Chs membranes were characterized for the application in direct methanol fuel cells. The Chs membrane characteristics such as water uptake, thermal stability, proton resistance and methanol permeability were compared to that of high performance conventional Nafion 117 membranes. Under the temperature range studied 20-60 C, the membrane water uptake for Chs was found to be higher than that of Nafion. Thermal analysis revealed that Chs membranes could withstand temperature as high as 230 C whereas Nafion 117 membranes were stable to 320 C under nitrogen. Nafion 117 membranes were found to exhibit high proton resistance of 284 s cm{sup -1} than Chs membranes of 204 s cm{sup -1}. The proton fluxes across the membranes were 2.73 mol cm{sup -2} s{sup -1} for Chs- and 1.12 mol cm{sup -2} s{sup -1} Nafion membranes. Methanol (MeOH) permeability through Chs membrane was less, 1.4 x 10{sup -6} cm{sup 2} s{sup -1} for Chs membranes and 3.9 x 10{sup -6} cm{sup 2} s{sup -1} for Nafion 117 membranes at 20 C. Chs and Nafion membranes were fabricated into membrane electrode assemblies (MAE) and their performances measure in a free-breathing commercial single cell DMFC. The Nafion membranes showed a better performance as the power density determined for Nafion membranes of 0.0075 W cm{sup -2} was 2.7 times higher than in the case of Chs MEA. (author)

  15. Durability and efficiency tests for direct methanol fuel cell's long-term performance assessment

    Yeh, Pulin; Chang, Chu Hsiang; Shih, Naichien; Yeh, Naichia

    2016-01-01

    This research assessed the long-term performance of direct methanol fuel cells. The experiment was performed at room temperature using 0.51 mol/L ∼0.651 mol/L methanol with a fuel consumption rate of 0.8 ± 0.1 cc/Wh at stack temperature of 60 °C–70 °C. DuPont Nafion115 proton exchange membrane was used as the base material of MEA (membrane electrode assembly), which is then examined via a series of processes that include I−V curve test, humidity cycle test, load cycle test, and hydrogen penetration test. The study employs membrane modification and cell structure adjustment approaches to reduce the methanol crossover in the cathode and identify the cell performance effect of the carbon paper gas diffusion layer. The test results indicated an efficiency of 25% can be achieved with a three-piece MEA assembly. According to the durability test, the stack power-generation efficiency has maintained at 15%–25% level. With such efficiency, the stack voltage output has been able to stay above 7.8-V for over 5000 h. This result is in line with industry standard. - Highlights: • Assess DMFC performance under non-optimal conditions for production readiness. • Output of 26-cell DMFC stack stays beyond 7.8v after 5000 operation hours. • Power-generation efficiency of 26-cell DMFC stack maintains between 15%–20%.

  16. Transient Response and Steady-State Analysis of the Anode of Direct Methanol Fuel Cells Based on Dual-Site Kinetics

    Lei Xing

    2011-01-01

    Full Text Available An intrinsic time-dependent one-dimensional (1D model and a macro two-dimensional (2D model for the anode of the direct methanol fuel cell (DMFC are presented. The two models are based on the dual-site mechanism, which includes the coverage of intermediate species of methanol, OH, and CO (θM, θOH,Ru, and θCO,Pt on the surface of Pt and Ru. The intrinsic 1D model focused on the analysis of the effects of operating temperature, methanol concentration, and overpotential on the transient response. The macro 2D model emphasises the dimensionless distributions of methanol concentration, overpotential and current density in the catalyst layer which were affected by physical parameters such as thickness, specific area, and operating conditions such as temperature, bulk methanol concentration, and overpotential. The models were developed and solved in the PDEs module of COMSOL Multiphysics, giving good agreement with experimental data. The dimensionless distributions of methanol concentration, overpotential, and current density and the efficiency factor were calculated quantitatively. The models can be used to give accurate simulations for the polarisations of methanol fuel cell.

  17. Novel manufacturing process for direct methanol fuel cells (DMFC) by defined layer structures; Neuartiges Herstellungsverfahren fuer Direkt-Methanol-Brennstoffzellen (DMFC) durch definierte Schichtstrukturen

    Frey, Thomas

    2007-07-17

    A novel method to prepare membrane electrode assemblies (MEA) for direct methanol fuel cells (DMFC) by a layer-upon-layer fabrication onto a porous substrate is presented. The novel preparation technique is based on a single method for the fabrication of the whole MEA, e.g. spraying one functional layer onto the other, and therefore simplifies its preparation considerably. It also permits new fuel cell designs with in-plane serial connection of single cells. The new concept offers high flexibility in the choice of cell geometry as well as superior control of the structural parameters. Layer thickness, composition, catalyst and ionomer loadings can easily be varied and adapted. Cells fabricated with the new concept are especially suited for low power micro fuel cells operated at ambient conditions. In this work, process parameters enabling such a layer-upon-layer MEA preparation have been developed. Advanced catalyst inks and electrolyte solutions were formulated as precursors for each functional layer. Nafion {sup registered} as well as polyaryl-based polymers were investigated for the fabrication of dense electrolyte layers. Catalyst layers were prepared from inks containing Pt and PtRu-black catalysts which were suspended in suitable solvents with diluted proton-conducting electrolytes. The critical parameters for the layer build-up were identified and optimized afterwards. Various candidate materials for the porous substrate were characterized and selected for further investigation. Experiments and calculation models led to a concept and an advanced design for a serially connected multi-cells unit on the substrate. The inplane conductivity of the electrodes turned out to be the critical parameter resulting in high ohmic losses especially when the electrodes were applied on non-conductive substrates. Various conductive coatings were tested to selectively increase the conductivity of non-conductive substrates, which are prerequisite for serial connection. Only

  18. Liquid–Liquid Equilibrium in Ternary Systems N,N-dimethylformamide + 2-methylpentane + Methanol and N,N-dimethylformamide + Methylcyclohexane + Methanol

    Bendová, Magdalena; Řehák, K.; Matouš, J.; Novák, J.P.

    2006-01-01

    Roč. 239, č. 1 (2006), s. 16-25 ISSN 0378-3812 Institutional research plan: CEZ:AV0Z40720504 Keywords : liquid-liquid equilibrium * critical curves * regular solution model Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.680, year: 2006

  19. Characterization of Liquid Fuel Evaporation of a Lifted Methanol Spray Flame in a Vitiated Coflow Burner

    Cabra, Ricardo; Dibble, Robert W.; Chen, Jyh-Yuan

    2002-01-01

    An experimental investigation of lifted spray flames in a coflow of hot, vitiated gases is presented. The vitiated coflow burner is a spray flame that issues into a coaxial flow of hot combustion products from a lean, premixed H2/Air flame. The spray flame in a vitiated coflow emulates the combustion that occurs in many advanced combustors without the detailed fluid mechanics. Two commercially available laser diagnostic systems are used to characterize the spray flame and to demonstrate the vitiated coflow burner's amenability to optical investigation. The Ensemble Particle Concentration and Size (EPCS) system is used to measure the path-average droplet size distribution and liquid volume fraction at several axial locations while an extractive probe instrument named the Real-time Fuel-air Analyzer (RFA) is used to measure the air to fuel ratio downstream of the spray nozzle with high temporal and spatial resolution. The effect of coflow conditions (stoichiometry) and dilution of the fuel with water was studied with the EPCS optical system. As expected, results show that water retards the evaporation and combustion of fuels. Measurements obtained by the RFA extractive probe show that while the Delavan manufactured nozzle does distribute the fuel over the manufacturer specified spray angle, it unfortunately does not distribute the fuel uniformly, providing conditions that may result in the production of unwanted NOx. Despite some limitations due to the inherent nature of the experimental techniques, the two diagnostics can be readily applied to spray flames in the vitiated coflow environment.

  20. Controlled synthesis of Pt/CS/PW12-GNs composite as an anodic electrocatalyst for direct methanol fuel cells

    Li, Zhongshui; Lei, Fengling; Ye, Lingting; Zhang, Xiaofeng; Lin, Shen

    2015-01-01

    Controlled assembly in aqueous solution was used to synthesize the well-organized Pt/CS/PW 12 -GNs composite. By the aid of linear cationic polysaccharide chitosan, 2-D distribution worm-like Pt nanoparticles with their length and width of 15–20 and 3–4 nm, respectively, were formed on the surface of CS/PW 12 -GNs using HCOOH as a reducing agent at room temperature. The introduction of CS leads to well dispersion of worm-like Pt nanoparticles, the electroactivity of H 3 PW 12 O 40 (PW 12 ) alleviates CO poisoning toward Pt particles, and graphene nanosheets (GNs) ensure excellent electrical conductivity of the composites. The combined action among different components results in significantly enhanced catalytic activity of Pt/CS/PW 12 -GNs toward methanol oxidation and better tolerance of CO. The as-synthesized Pt/CS/PW 12 -GNs exhibit the forward peak current density of 445 mA mg −1 , which is much higher than that (220 mA mg −1 ) for Pt/C-JM (the commercially available Johnson Matthey Hispec4000 catalyst, simplified as Pt/C-JM) and some recently reported Pt/graphene-based nanomaterials. The construction of 2-D distribution worm-like Pt nanoparticles and facile wet chemical synthesis strategy provide a promising way to develop superior performance electrocatalysts for direct methanol fuel cells applications

  1. Controlled synthesis of Pt/CS/PW{sub 12}-GNs composite as an anodic electrocatalyst for direct methanol fuel cells

    Li, Zhongshui; Lei, Fengling; Ye, Lingting; Zhang, Xiaofeng; Lin, Shen, E-mail: shenlin@fjnu.edu.cn [Fujian Normal University, College of Chemistry & Chemical Engineering (China)

    2015-04-15

    Controlled assembly in aqueous solution was used to synthesize the well-organized Pt/CS/PW{sub 12}-GNs composite. By the aid of linear cationic polysaccharide chitosan, 2-D distribution worm-like Pt nanoparticles with their length and width of 15–20 and 3–4 nm, respectively, were formed on the surface of CS/PW{sub 12}-GNs using HCOOH as a reducing agent at room temperature. The introduction of CS leads to well dispersion of worm-like Pt nanoparticles, the electroactivity of H{sub 3}PW{sub 12}O{sub 40} (PW{sub 12}) alleviates CO poisoning toward Pt particles, and graphene nanosheets (GNs) ensure excellent electrical conductivity of the composites. The combined action among different components results in significantly enhanced catalytic activity of Pt/CS/PW{sub 12}-GNs toward methanol oxidation and better tolerance of CO. The as-synthesized Pt/CS/PW{sub 12}-GNs exhibit the forward peak current density of 445 mA mg{sup −1}, which is much higher than that (220 mA mg{sup −1}) for Pt/C-JM (the commercially available Johnson Matthey Hispec4000 catalyst, simplified as Pt/C-JM) and some recently reported Pt/graphene-based nanomaterials. The construction of 2-D distribution worm-like Pt nanoparticles and facile wet chemical synthesis strategy provide a promising way to develop superior performance electrocatalysts for direct methanol fuel cells applications.

  2. Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cell Stacks

    Valdez, Thomas I.; Firdosy, S.; Koel, B. E.; Narayanan, S. R.

    2005-01-01

    Dissolution of ruthenium was observed in the 80-cell stack. Duration testing was performed in single cell MEAs to determine the pathway of cell degradation. EDAX analysis on each of the single cell MEAs has shown that the Johnson Matthey commercial catalyst is stable in DMFC operation for 250 hours, no ruthenium dissolution was observed. Changes in the hydrophobicity of the cathode backing papers was minimum. Electrode polarization analysis revealed that the MEA performance loss is attributed to changes in the cathode catalyst layer. Ruthenium migration does not seem to occur during cell operation but can occur when methanol is absent from the anode compartment, the cathode compartment has access to air, and the cells in the stack are electrically connected to a load (Shunt Currents). The open-to-air cathode stack design allowed for: a) The MEAs to have continual access to oxygen; and b) The stack to sustain shunt currents. Ruthenium dissolution in a DMFC stack can be prevented by: a) Developing an internally manifolded stacks that seal reactant compartments when not in operation; b) Bringing the cell voltages to zero quickly when not in operation; and c) Limiting the total number of cells to 25 in an effort to limit shunt currents.

  3. Isolated Fe sites in Metal Organic Framework catalyze the direct conversion of methane to methanol

    Osadchii, Dmitrii

    2018-05-10

    Hybrid materials bearing organic and inorganic motives have been extensively discussed as playgrounds for the implementation of atomically resolved inorganic sites within a confined environment, with an exciting similarity to enzymes. Here, we present the successful design of a site-isolated mixed-metal Metal Organic Framework that mimics the reactivity of soluble methane monooxygenase enzyme reactivity and demonstrates the potential of this strategy to overcome current challenges in selective methane oxidation. We describe the synthesis and characterisation of an Fe-containing MOF that comprises the desired antiferromagnetically cou-pled high spin species in a coordination environment closely resembling that of the enzyme. An electrochemi-cal synthesis method is used to build the microporous MOF matrix while integrating, with an exquisite con-trol, the atomically dispersed Fe active sites in the crystalline scaffold. The model mimics the catalytic C-H activation behaviour of the enzyme to produce methanol, and shows that the key to this reactivity is the for-mation of isolated oxo-bridged Fe units.

  4. Isolated Fe sites in Metal Organic Framework catalyze the direct conversion of methane to methanol

    Osadchii, Dmitrii; Olivos Suarez, Alma Itzel; Szé csé nyi, Á gnes; Li, Guanna; Nasalevich, Maxim A.; Dugulan, A Iulian; Serra-Crespo, Pablo; Hensen, Emiel J. M.; Veber, Sergey L.; Fedin, Matvey V.; Sankar, Gopinathan; Pidko, Evgeny A; Gascon, Jorge

    2018-01-01

    Hybrid materials bearing organic and inorganic motives have been extensively discussed as playgrounds for the implementation of atomically resolved inorganic sites within a confined environment, with an exciting similarity to enzymes. Here, we present the successful design of a site-isolated mixed-metal Metal Organic Framework that mimics the reactivity of soluble methane monooxygenase enzyme reactivity and demonstrates the potential of this strategy to overcome current challenges in selective methane oxidation. We describe the synthesis and characterisation of an Fe-containing MOF that comprises the desired antiferromagnetically cou-pled high spin species in a coordination environment closely resembling that of the enzyme. An electrochemi-cal synthesis method is used to build the microporous MOF matrix while integrating, with an exquisite con-trol, the atomically dispersed Fe active sites in the crystalline scaffold. The model mimics the catalytic C-H activation behaviour of the enzyme to produce methanol, and shows that the key to this reactivity is the for-mation of isolated oxo-bridged Fe units.

  5. CoPd x oxygen reduction electrocatalysts for polymer electrolyte membrane and direct methanol fuel cells

    Mustain, William E.; Kepler, Keith; Prakash, Jai

    2007-01-01

    The electrochemical activity of carbon-supported cobalt-palladium alloy electrocatalysts of various compositions have been investigated for the oxygen reduction reaction in a 5 cm 2 single cell polymer electrolyte membrane fuel cell. The polarization experiments have been conducted at various temperatures between 30 and 60 deg. C and the reduction performance compared with data from a commercial Pt catalyst under identical conditions. Investigation of the catalytic activity of the CoPd x PEMFC system with varying composition reveals that a nominal cobalt-palladium atomic ratio of 1:3, CoPd 3 , exhibits the best performance of all studied catalysts, exhibiting a catalytic activity comparable to the commercial Pt catalyst. The ORR on CoPd 3 has a low activation energy, 52 kJ/mol, and a Tafel slope of approximately 60 mV/decade, indicating that the rate-determining step is a chemical step following the first electron transfer step and may involve the breaking of the oxygen bond. The CoPd 3 catalyst also exhibits excellent chemical stability, with the open circuit cell voltage decreasing by only 3% and the observed current decreasing by only 10% at 0.8 V over 25 h. The CoPd 3 catalyst also exhibits superior tolerance to methanol crossover poisoning than Pt

  6. Direct measurement of tritium in urine by liquid scintillation method

    Zhang Caihong; Wen Qinghua; Chen Kefei; Li Huaixin

    1999-01-01

    The author introduces the method for direct measurement of tritium concentration in urine using liquid scintillation. Effects of sampling containers, store patterns and storage time are studied. Meanwhile, results of two methods are compared with direct measurement method and oxidation distillation method. The results shows that direct measurement method is a economic and simple method, which can meet the need of determination of urine tritium for NPP workers. There is no significant difference compared with the data obtained by oxidation distillation method

  7. Electrochemical characterization of nano-sized Pd-based catalysts as cathode materials in direct methanol fuel cells.

    Choi, M; Han, C; Kim, I T; An, J C; Lee, J J; Lee, H K; Shim, J

    2011-01-01

    To improve the catalytic activity of palladium (Pd) as a cathode catalyst in direct methanol fuel cells (DMFCs), we prepared palladium-titanium oxide (Pd-TiO2) catalysts which the Pd and TiO2 nanoparticles were simultaneously impregnated on carbon. We selected Pd and TiO2 as catalytic materials because of their electrochemical stability in acid solution. The crystal structure and the loading amount of Pd and TiO2 on carbon were characterized by X-ray diffraction (XRD) and energy dispersive X-ray microanalysis (EDX). The electrochemical characterization of Pd-TiO2/C catalysts for the oxygen reduction reaction was carried out in half and single cell systems. The catalytic activities of the Pd-TiO2 catalysts were strongly influenced by the TiO2 content. In the single cell test, the Pd-TiO2 catalysts showed very comparable performance to the Pt catalyst.

  8. Investigation of methanol oxidation on a highly active and stable Pt–Sn electrocatalyst supported on carbon–polyaniline composite for application in a passive direct methanol fuel cell

    Amani, Mitra [Department of Chemical Engineering, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Kazemeini, Mohammad [Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran (Iran, Islamic Republic of); Hamedanian, Mahboobeh [Department of Chemistry, Faculty of Science, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Pahlavanzadeh, Hassan [Department of Chemical Engineering, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Gharibi, Hussein, E-mail: h.gharibi@utah.edu [Department of Chemistry, Faculty of Science, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Department of Material Science & Engineering, 122 S Campus Drive, University of Utah, Salt Lake City, UT 84112 (United States)

    2015-08-15

    Highlights: • PtSn/C-PANI performed superior in the MOR compared with a commercial PtRu/C. • Catalytic activity of PtRu/C was highly reduced during the accelerated durability test. • Anode of the PtSn/C-PANI in a passive DMFC lowered methanol crossover by 30%. - Abstract: Polyaniline fiber (PANI) was synthesized and utilized to fabricate a vulcan–polyaniline (C-PANI) composite. Pt/C-PANI and PtSn/C-PANI electro-catalysts with different Pt:Sn atomic ratios were prepared by the impregnation method. These electro-catalysts, along with commercial PtRu/C (Electrochem), were characterized with respect to their structural and electrochemical properties in methanol oxidation reaction (MOR). PtSn(70:30)/C-PANI showed excellent performance in MOR, the obtained maximum current density being about 40% and 50% higher than that for PtRu/C and Pt/C-PANI, respectively. It was also found that the CO tolerance and stability of PtSn(70:30)/C-PANI was considerably higher than that of PtRu/C. Finally, the performance of these two materials was compared in a passive direct methanol fuel cell (DMFC). The DMFC test results demonstrated that the membrane electrode assembly (MEA) prepared using PtSn(70:30)/C-PANI anode catalyst performed more satisfactorily in terms of maximum power density and lower methanol crossover.

  9. Direct laser writing for nanoporous liquid core laser sensors

    Grossmann, Tobias; Christiansen, Mads Brøkner; Peterson, Jeffrey

    2012-01-01

    We report the fabrication of nanoporous liquid core lasers via direct laser writing based on two-photon absorption in combination with thiolene-chemistry. As gain medium Rhodamine 6G was embedded in the nanoporous polybutadiene matrix. The lasing devices with thresholds of 19 µJ/mm2 were measured...

  10. Bioinspired one-dimensional materials for directional liquid transport.

    Ju, Jie; Zheng, Yongmei; Jiang, Lei

    2014-08-19

    One-dimensional materials (1D) capable of transporting liquid droplets directionally, such as spider silks and cactus spines, have recently been gathering scientists' attention due to their potential applications in microfluidics, textile dyeing, filtration, and smog removal. This remarkable property comes from the arrangement of the micro- and nanostructures on these organisms' surfaces, which have inspired chemists to develop methods to prepare surfaces with similar directional liquid transport ability. In this Account, we report our recent progress in understanding how this directional transport works, as well our advances in the design and fabrication of bioinspired 1D materials capable of transporting liquid droplets directionally. To begin, we first discuss some basic theories on droplet directional movement. Then, we discuss the mechanism of directional transport of water droplets on natural spider silks. Upon contact with water droplets, the spider silk undergoes what is known as a wet-rebuilt, which forms periodic spindle-knots and joints. We found that the resulting gradient of Laplace pressure and surface free energy between the spindle-knots and joints account for the cooperative driving forces to transport water droplets directionally. Next, we discuss the directional transport of water droplets on desert cactus. The integration of multilevel structures of the cactus and the resulting integration of multiple functions together allow the cactus spine to transport water droplets continuously from tip to base. Based on our studies of natural spider silks and cactus spines, we have prepared a series of artificial spider silks (A-SSs) and artificial cactus spines (A-CSs) with various methods. By changing the surface roughness and chemical compositions of the artificial spider silks' spindle-knots, or by introducing stimulus-responsive molecules, such as thermal-responsive and photoresponsive molecules, onto the spindle-knots, we can reversibly manipulate

  11. The Methanol Economy Project

    Olah, George [Univ. of Southern California, Los Angeles, CA (United States); Prakash, G. K. [Univ. of Southern California, Los Angeles, CA (United States)

    2014-02-01

    The Methanol Economy Project is based on the concept of replacing fossil fuels with methanol generated either from renewable resources or abundant natural (shale) gas. The full methanol cycle was investigated in this project, from production of methanol through bromination of methane, bireforming of methane to syngas, CO2 capture using supported amines, co-electrolysis of CO2 and water to formate and syngas, decomposition of formate to CO2 and H2, and use of formic acid in a direct formic acid fuel cell. Each of these projects achieved milestones and provided new insights into their respective fields.

  12. Improvement on performance and efficiency of direct methanol fuel cells using hydrocarbon-based membrane electrode assembly

    Kim, Joon-Hee; Yang, Min-Jee; Park, Jun-Young

    2014-01-01

    Highlights: • Faradaic efficiency and water transfer coefficient (WTC) of DMFC MEAs are calculated based on mass balance measurements. • Faradaic efficiency of the HC-based MEAs is generally improved over the Nafion-based MEAs. • Nafion-based MEAs show a WTC of 3, whereas the HC-based MEAs show a very low WTC of -2. • Low WTC of the HC-based MEAs indicates the back-diffusion of water from the cathode to the anode. • Performance of HC-based MEAs is improved as the fuel stoichiometry increases, maintaining high Faradaic efficiency. - Abstract: In order to improve the energy efficiency (fuel efficiency and electrical power) of direct methanol fuel cells (DMFCs), the hydrocarbon (HC) membrane-based membrane electrode assemblies (MEAs) are investigated under various operating conditions. The MEAs are then compared with the conventional Nafion-based MEA in terms of their efficiency and performance. The Faradaic efficiency and water transfer coefficient (WTC) are calculated based on mass balance measurements. The Faradaic efficiency of the HC-based MEAs is improved over the Nafion-based MEAs since methanol crossover decreased. The performance of HC-based MEAs shows strong dependency on the anode stoichiometry at high current densities probably because of the limited mass transport of fuel, which is not observed for the Nafion-based MEAs. The Nafion-based MEAs show a WTC of 3, whereas the HC-based MEAs show a very low WTC of −2, indicating the back-diffusion of water from the cathode to the anode. This may have limited mass transport by interrupting proton conduction at high current densities. The performance of HC-based MEAs at high current densities is improved as the fuel stoichiometry increases; High Faradaic efficiency is maintained by decreasing the cathode stoichiometry

  13. Methanol from biomass and hydrogen

    Anon.

    1989-01-01

    For Hawaii in the near term, the only liquid fuels indigenous sources will be those that can be made from biomass, and of these, methanol is the most promising. In addition, hydrogen produced by electrolysis can be used to markedly increase the yield of biomass methanol. This paper calculates cost of producing methanol by an integrated system including a geothermal electricity facility plus a plant producing methanol by gasifying biomass and adding hydrogen produced by electrolysis. Other studies cover methanol from biomass without added hydrogen and methanol from biomass by steam and carbon dioxide reforming. Methanol is made in a two-step process: the first is the gasification of biomass by partial oxidation with pure oxygen to produce carbon oxides and hydrogen, and the second is the reaction of gases to form methanol. Geothermal steam is used to generate the electricity used for the electrolysis to produce the added hydrogen

  14. Online stable carbon isotope ratio measurement in formic acid, acetic acid, methanol and ethanol in water by high performance liquid chromatography-isotope ratio mass spectrometry

    Tagami, Keiko; Uchida, Shigeo

    2008-01-01

    A suitable analysis condition was determined for high performance liquid chromatography-isotope ratio mass spectrometry (HPLC-IRMS) while making sequential measurements of stable carbon isotope ratios of δ 13 C in formic acid, acetic acid, methanol and ethanol dissolved in water. For this online column separation method, organic reagents are not applicable due to carbon contamination; thus, water and KH 2 PO 4 at low concentrations were tested as mobile phase in combination with a HyPURITY AQUASTAR TM column. Formic acid, acetic acid, methanol and ethanol were separated when 2 mM KH 2 PO 4 aqueous solution was used. Under the determined analysis condition for HPLC-IRMS, carbon concentrations could be measured quantitatively as well as carbon isotope ratio when carbon concentration was higher than 0.4 mM L for each chemical

  15. Direct analysis of formate in human plasma, serum and whole blood by in-line coupling of microdialysis to capillary electrophoresis for rapid diagnosis of methanol poisoning

    Kubáň, P. (Pavel); Boček, P. (Petr)

    2013-01-01

    A microdialytic device was in-line coupled to capillary electrophoresis for direct injection of blood samples. Its performance was demonstrated on rapid analysis of formic acid in various blood samples including serum samples of a patient diagnosed with acute methanol poisoning.

  16. Direct synthesis of silver nanoparticles in ionic liquid

    Corrêa, Cíntia M.; Bizeto, Marcos A.; Camilo, Fernanda F.

    2016-01-01

    Ionic liquids have structural organization at nanoscale that can trigger the spontaneous ordering of structures in nanoscopic range. Due to this characteristic, several metal nanoparticles have been prepared in this media. In this paper, we describe the direct preparation of silver nanoparticles in the following imidazolium ionic liquids: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dimethyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, and in citrate tetrabutylammonium, that is an ionic liquid that acts as solvent and reducing agent at the same time. We also evaluated the morphology of the nanoparticles and the stability of the dispersions. Spherical silver nanoparticles with surface Plasmon bands in the range of 400–430 nm were produced in all the ionic liquids, with the only exception for the 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide that produced a black precipitate. The best results were obtained by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and citrate tetrabutylammonium ionic liquids. The former resulted in concentrated spherical silver nanoparticles dispersion (ca. 1.0 mM of Ag) with diameters ranging from 6 to 12 nm and by adding polyvinylpyrrolidone (PVP) to the dispersions they became stable for at least 1 month. The citrate tetrabutylammonium ionic liquid produced even more concentrated dispersion of spherical silver nanoparticles with diameters ranging from 2 to 6 nm. These dispersions were quite stable without the need of PVP, since the Plasmon band in the electronic absorption spectra remained unaltered for months after the preparation. The citrate tetrabutylammonium ionic liquid offers a slow kinetic for the silver nanoparticle formation as the citrate is a milder reducing agent than borohydride.Graphical Abstract

  17. Direct synthesis of silver nanoparticles in ionic liquid

    Corrêa, Cíntia M.; Bizeto, Marcos A.; Camilo, Fernanda F., E-mail: ffcamilo@unifesp.br [Universidade Federal de São Paulo, Laboratório de Materiais Híbridos, Departamento de Ciências Exatas e da Terra, Instituto de Ciências Ambientais, Químicas e Farmacêuticas (Brazil)

    2016-05-15

    Ionic liquids have structural organization at nanoscale that can trigger the spontaneous ordering of structures in nanoscopic range. Due to this characteristic, several metal nanoparticles have been prepared in this media. In this paper, we describe the direct preparation of silver nanoparticles in the following imidazolium ionic liquids: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dimethyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, and in citrate tetrabutylammonium, that is an ionic liquid that acts as solvent and reducing agent at the same time. We also evaluated the morphology of the nanoparticles and the stability of the dispersions. Spherical silver nanoparticles with surface Plasmon bands in the range of 400–430 nm were produced in all the ionic liquids, with the only exception for the 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide that produced a black precipitate. The best results were obtained by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and citrate tetrabutylammonium ionic liquids. The former resulted in concentrated spherical silver nanoparticles dispersion (ca. 1.0 mM of Ag) with diameters ranging from 6 to 12 nm and by adding polyvinylpyrrolidone (PVP) to the dispersions they became stable for at least 1 month. The citrate tetrabutylammonium ionic liquid produced even more concentrated dispersion of spherical silver nanoparticles with diameters ranging from 2 to 6 nm. These dispersions were quite stable without the need of PVP, since the Plasmon band in the electronic absorption spectra remained unaltered for months after the preparation. The citrate tetrabutylammonium ionic liquid offers a slow kinetic for the silver nanoparticle formation as the citrate is a milder reducing agent than borohydride.Graphical Abstract.

  18. Bio-refinery system in a pulp mill for methanol production with comparison of pressurized black liquor gasification and dry gasification using direct causticization

    Naqvi, Muhammad; Yan, Jinyue; Dahlquist, Erik

    2012-01-01

    Black liquor gasification (BLG) for bio-fuel or electricity production at the modern pulp mills is a field in continuous evolution and the efforts are considerably driven by the climate change, fuel security, and renewable energy. This paper evaluates and compares two BLG systems for methanol production: (i) oxygen blown pressurized thermal BLG; and (ii) dry BLG with direct causticization, which have been regarded as the most potential technology candidates for the future deployment. A key objective is to assess integration possibilities of BLG technologies with the reference Kraft pulp mill producing 1000 air dried tonnes (ADt) pulp/day replacing conventional recovery cycle. The study was performed to compare the systems’ performance in terms of potential methanol production, energy efficiency, and potential CO 2 reductions. The results indicate larger potential of black liquor conversion to methanol from the pressurized BLG system (about 77 million tonnes/year of methanol) than the dry BLG system (about 30 million tonnes/year of methanol) utilizing identical amount of black liquor available worldwide (220 million tDS/year). The potential CO 2 emissions reduction from the transport sector is substantially higher in pressurized BLG system (117 million tonnes/year CO 2 reductions) as compared to dry BLG system (45 million tonnes/year CO 2 reductions). However, the dry BLG system with direct causticization shows better results when considering consequences of additional biomass import. In addition, comparison of methanol production via BLG with other bio-refinery products, e.g. hydrogen, dimethyl ether (DME) and bio-methane, has also been discussed.

  19. Improved Charge Transfer in a Mn2O3@Co1.2Ni1.8O4 Hybrid for Highly Stable Alkaline Direct Methanol Fuel Cells with Good Methanol Tolerance.

    Liu, Yan; Chen, Yuanzhen; Li, Sai; Shu, Chenyong; Fang, Yuan; Song, Bo

    2018-03-21

    A three-dimensional Mn 2 O 3 @Co 1.2 Ni 1.8 O 4 hybrid was synthesized via facile two-step processes and employed as a cathode catalyst in direct methanol fuel cells (DMFCs) for the first time. Because of the unique architecture with ultrathin and porous nanosheets of the Co 1.2 Ni 1.8 O 4 shell, this composite exhibits better electrochemical performance than the pristine Mn 2 O 3 . Remarkably, it shows excellent methanol tolerance, even in a high concentration solution. The DMFC was assembled with Mn 2 O 3 @Co 1.2 Ni 1.8 O 4 , polymer fiber membranes, and PtRu/C as the cathode, membrane, and anode, respectively. The power densities of 57.5 and 70.5 mW cm -2 were recorded at 18 and 28 °C, respectively, especially the former is the best result reported in the literature at such a low temperature. The stability of the Mn 2 O 3 @Co 1.2 Ni 1.8 O 4 catalyzed cathode was evaluated, and the results show that this compound possesses excellent stability in a high methanol concentration. The improved electrochemical activity could be attributed to the narrow band gap of the hybrid, which accelerates the electrons jumping from the valence band to the conduction band. Therefore, Mn III could be oxidized into Mn IV more easily, simultaneously providing an electron to the absorbed oxygen.

  20. Determination of isoorientin levels in rat plasma after oral administration of Vaccinum bracteatum Thunb. methanol extract by high-performance liquid chromatography-tandem mass spectrometry.

    Kim, Min-Ji; Kwon, Seung-Hwan; Jang, Choon-Gon; Maeng, Han-Joo

    2018-01-15

    A simple, sensitive and rapid liquid chromatography tandem mass spectrometry method (LC-MS/MS) was developed and validated for the determination of plasma isoorientin levels in rats. After simple protein precipitation using methanol, chromatographic analysis was performed using a Synergi 4μ polar-RP 80A column (150 × 2.0 mm, 4μm) under isocratic conditions and a mobile phase consisting of 0.1% formic acid in water and methanol (80:20, v/v) at a flow rate of 0.2 mL/min. In positive electrospray ionization mode, the protonated precursor and product ion transitions of isoorientin (m/z 449.0 → 299.1) and of puerarin (the internal standard; m/z 417.1 → 297.1) were acquired by multiple reaction monitoring. Calibration curves obtained for plasma showed good linearity over the concentration range 1-1000 ng/mL. The lower limit of quantification was 1 ng/mL. Intra- and inter-day precisions were within 8.8% relative standard deviation. Accuracies ranged from 92.1 and 109.7%. The isoorientin stability in rat plasma under typical handling/storage conditions also found to be acceptable. The developed method was applied successfully to a pharmacokinetic study of isoorientin orally administered as the methanol extract of Vaccinium bracteatum Thunb. or administered as pure isoorientin. Copyright © 2018 John Wiley & Sons, Ltd.

  1. Directional Scattering of Semiconductor Nanoparticles Embedded in a Liquid Crystal

    Braulio García-Cámara

    2014-04-01

    Full Text Available Light scattering by semiconductor nanoparticles has been shown to be more complex than was believed until now. Both electric and magnetic responses emerge in the visible range. In addition, directional effects on light scattering of these nanoparticles were recently obtained. In particular, zero backward and minimum-forward scattering are observed. These phenomena are very interesting for several applications such as, for instance, optical switches or modulators. The strong dependence of these phenomena on the properties of both the particle and the surrounding medium can be used to tune them. The electrical control on the optical properties of liquid crystals could be used to control the directional effects of embedded semiconductor nanoparticles. In this work, we theoretically analyze the effects on the directional distribution of light scattering by these particles when the refractive index of a surrounded liquid crystal changes from the ordinary to the extraordinary configuration. Several semiconductor materials and liquid crystals are studied in order to optimize the contrast between the two states.

  2. Development and characterization of a novel air-breathing micro direct methanol fuel cell stack for portable applications

    Liu, Xiaowei; Zhang, Bo; Zhang, Yufeng; He, Hong; Li, Jianmin; Wang, Shibo; Yuan, Zhenyu; Deng, Huichao

    2010-01-01

    An air-breathing 10-cell micro direct methanol fuel cell (µDMFC) stack with four anode feeding patterns is designed, fabricated and tested. For a better understanding of the operational characteristics of both the single cell and the stack, a two-dimensional numerical model is established and calculated. Employing micro-stamping technology, the current collectors of each single cell are microfabricated on the stainless steel plate with a thickness of 300 µm. The single µDMFC is first tested under various operating parameters. On the basis of the simulation and experimental observation of the single cell performance, the µDMFC stack performance is thoroughly analyzed with different anode feeding patterns. The results indicate that the µDMFC stack with pattern B can ensure the uniform performance of each single cell and generate the highest power output. With pattern B, further experiments are carried out to investigate the influence of the anode flow rate on the stack performance. As a result, the µDMFC stack achieves the best performance with the maximum power density of about 24.75 mW cm −2 at 5.0 ml min −1 . Finally, the stack is successfully applied to two electronic devices of different rated power

  3. Pt and Ru X-ray absorption spectroscopy of PtRu anode catalysts in operating direct methanol fuel cells.

    Stoupin, Stanislav; Chung, Eun-Hyuk; Chattopadhyay, Soma; Segre, Carlo U; Smotkin, Eugene S

    2006-05-25

    In situ X-ray absorption spectroscopy, ex situ X-ray fluorescence, and X-ray powder diffraction enabled detailed core analysis of phase segregated nanostructured PtRu anode catalysts in an operating direct methanol fuel cell (DMFC). No change in the core structures of the phase segregated catalyst was observed as the potential traversed the current onset potential of the DMFC. The methodology was exemplified using a Johnson Matthey unsupported PtRu (1:1) anode catalyst incorporated into a DMFC membrane electrode assembly. During DMFC operation the catalyst is essentially metallic with half of the Ru incorporated into a face-centered cubic (FCC) Pt alloy lattice and the remaining half in an amorphous phase. The extended X-ray absorption fine structure (EXAFS) analysis suggests that the FCC lattice is not fully disordered. The EXAFS indicates that the Ru-O bond lengths were significantly shorter than those reported for Ru-O of ruthenium oxides, suggesting that the phases in which the Ru resides in the catalysts are not similar to oxides.

  4. Effect of the thickness of the anode electrode catalyst layers on the performance in direct methanol fuel cells

    Glass, Dean E.; Olah, George A.; Prakash, G. K. Surya

    2017-06-01

    For the large scale fuel cell manufacture, the catalyst loading and layer thickness are critical factors affecting the performance and cost of membrane electrode assemblies (MEAs). The influence of catalyst layer thicknesses at the anode of a PEM based direct methanol fuel cell (DMFC) has been investigated. Catalysts were applied with the drawdown method with varied thicknesses ranging from 1 mil to 8 mils (1 mil = 25.4 μm) with a Pt/Ru anode loading of 0.25 mg cm-2 to 2.0 mg cm-2. The MEAs with the thicker individual layers (8 mils and 4 mils) performed better overall compared to the those with the thinner layers (1 mil and painted). The peak power densities for the different loading levels followed an exponential decrease of Pt/Ru utilization at the higher loading levels. The highest power density achieved was 49 mW cm-2 with the 4 mil layers at 2.0 mg cm-2 catalyst loading whereas the highest normalized power density was 116 mW mg-1 with the 8 mil layers at 0.25 mg cm-2 loading. The 8 mil drawdowns displayed a 50% and 23% increase in normalized power density compared to the 1 mil drawdowns at 0.25 mg cm-2 and 0.5 mg cm-2 loadings, respectively.

  5. Electrochemical impedance spectroscopy analysis of a thin polymer film-based micro-direct methanol fuel cell

    Schulz, Tobias; Weinmüller, Christian; Nabavi, Majid; Poulikakos, Dimos

    A single cell micro-direct methanol fuel cell (micro-DMFC) was investigated using electrochemical impedance spectroscopy. The electrodes consisted of thin, flexible polymer (SU8) film microchannel structures fabricated in-house using microfabrication techniques. AC impedance spectroscopy was used to separate contributions to the overall cell polarization from the anode, cathode and membrane. A clear distinction between the different electrochemical phenomena occurring in the micro-DMFC, especially the distinction between double layer charging and Faradaic reactions was shown. The effect of fuel flow rate, temperature, and anode flow channel structure on the impedance of the electrode reactions and membrane/electrode double layer charging were investigated. Analysis of impedance data revealed that the performance of the test cell was largely limited by the presence of intermediate carbon monoxide in the anode reaction. Higher temperatures increase cell performance by enabling intermediate CO to be oxidized at much higher rates. The results also revealed that serpentine anode flow microchannels show a lower tendency to intermediate CO coverage and a more stable cell behavior than parallel microchannels.

  6. Direct Evidence for Maser Emission from the 36.2 GHz Class I Transition of Methanol in NGC253

    Chen, Xi; Ellingsen, Simon P.; Shen, Zhi-Qiang; McCarthy, Tiege P.; Zhong, Wei-Ye; Deng, Hui

    2018-04-01

    Observations made with the Jansky Very large Array (JVLA) at an angular resolution of ∼0.″1 have detected class I methanol maser emission from the 36.2 GHz transition toward the starburst galaxy NGC 253. The methanol emission is detected toward four sites which lie within the regions of extended methanol emission detected in previous lower angular resolution (a few arcseconds) observations. The peak flux densities of the detected compact components are in the range 3–9 mJy beam‑1. Combining the JVLA data with single-dish observations from the Shanghai Tianma Radio Telescope (TMRT) and previous interferometric observations with the Australia Telescope Compact Array (ATCA), we show that the 36.2 GHz class I methanol emission consists of both extended and compact structures, with typical scales of ∼6″ (0.1 kpc) and ∼0.″05 (1 pc), respectively. The strongest components have a brightness temperature of >103 K, much higher than the maximum kinetic temperature (∼100 K) of the thermal methanol emission from NGC 253. Therefore, these observations conclusively demonstrate for the first time the presence of maser emission from a class I methanol transition in an external galaxy.

  7. On the effects of assembly compression on the performance of liquid-feed DMFCs under methanol-limiting conditions: A 2D numerical study

    García-Salaberri, P. A.; Vera, M.

    2015-07-01

    The influence of assembly compression on the performance of liquid-feed DMFCs under methanol-limiting conditions is explored by means of a 2D/1D multiphysics across-the-channel model. The numerical formulation incorporates a comprehensive 2D description of the anode GDL, including two-phase phenomena, non-uniform anisotropic transport properties, and electrical contact resistances at the GDL/BPP interface. GDL effective properties are evaluated using empirical data corresponding to Toray® carbon paper. A simplified but physically sound 1D description, locally coupled to the 2D anode GDL model, is adopted to describe transport processes in the MPLs, membrane and cathode GDL, whereas the catalyst layers are treated as infinitely thin surfaces. Good agreement is found between the numerical results and previous experimental data. The interplay between assembly compression, bipolar plate material, and channel configuration is also investigated. The results show that there is an optimum GDL compression ratio in terms of overall power density, the optimal compression level being strongly dependent on bipolar plate material. Beyond the optimum, the detrimental effect of compression is larger in non-parallel flow fields due to the additional reduction of methanol transported by under-rib convection. The results suggest that, under certain conditions, this transport mechanism could be more important than diffusion in the anode of liquid-feed DMFCs.

  8. Direct drive acceleration of planar liquid deuterium targets

    Sethian, J.D.; Bodner, S.E.; Colombant, D.G.; Dahlburg, J.P.; Obenschain, S.P.; Pawley, C.J.; Serlin, V.; Gardner, J.H.; Aglitskiy, Y.; Chan, Y.; Deniz, A.V.; Lehecka, T.; Klapisch, M.

    1999-01-01

    The Nike laser (∼2 - 3 kJ, ∼10 14 W/cm 2 ) has been used to ablatively accelerate planar liquid deuterium targets. These experiments are designed to test some aspects of a high gain direct drive target design. The target consists of a low-density foam that is filled with liquid deuterium and covered with a thin polyimide membrane. The measured target trajectory agrees well with one-dimensional (1D) simulations. The growth of the areal mass modulations were measured with a new, 1.26 keV x-ray backlighter. The modulations appear later and grow to a smaller amplitude when the foot of the laser pulse is made spatially smoother. A thin layer of gold on the front of the target reduces the modulations. The results are compared with 2D modeling

  9. Facile synthesis of Pt–Pd bimetallic nanoparticles by plasma discharge in liquid and their electrocatalytic activity toward methanol oxidation in alkaline media

    Kim, Sung-Min; Lee, Yu-Jin [Center for Surface Technology and Applications, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of); Department of Materials Engineering, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of); Kim, Jung-Wan [Center for Surface Technology and Applications, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of); Division of Bioengineering, InCheon National University, Incheon, 406-772 (Korea, Republic of); Lee, Sang-Yul, E-mail: sylee@kau.ac.kr [Center for Surface Technology and Applications, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of); Department of Materials Engineering, Korea Aerospace University, Gyeonggi-do, 412-791 (Korea, Republic of)

    2014-12-01

    The Pt–Pd bimetallic nanoparticles for direct methanol fuel cell applications were successfully prepared by plasma discharge in aqueous solution. The obtained nanoparticles were characterized by energy dispersive X-ray spectroscopy, X-ray diffraction spectroscopy, and transmission electron microscopy. During plasma discharge, the nanoparticles were produced from the erosion of electrodes. It was noted that the erosion amount of anode electrodes was much greater than that of cathode electrodes so that the composition of Pt–Pd bimetallic nanoparticles could be changed with different power types and electrode configurations. Diffraction patterns fitted from Gaussian devolution indicated that the crystalline phase of Pt{sub 40}Pd{sub 60} products was composed of pure Pt, pure Pd and Pt–Pd alloy phases. The morphology of synthesized nanoparticles showed that nanowires connected with quasi-spherical nanoparticles with 2–3 nm in diameter were observed and large spherical particles with > 50 nm in diameter were also detected intermittently. The cyclic voltammetric measurement and continuous potential scan demonstrated that Pt{sub 40}Pd{sub 60} had much higher catalytic activity and better resistance to CO poisoning than Pt{sub 94}Pd{sub 6} and Pt{sub 1}Pd{sub 99} for methanol oxidation. These results indicate that the Pt{sub 40}Pd{sub 60} could be an excellent candidate for the direct methanol fuel cell applications.

  10. Liquid−Liquid Equilibria in Ternary Systems of Hexafluoroisopropanol plus Perfluorocarbon plus Water or Methanol at 298.15 K

    Strejc, M.; Řehák, K.; Beier, Petr; Morávek, P.

    2014-01-01

    Roč. 59, č. 11 (2014), s. 3510-3516 ISSN 0021-9568 Institutional support: RVO:61388963 Keywords : liquid-liquid equilibrium * perfluorocarbons * hexafluoroisopropanol Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.037, year: 2014

  11. Effects of piston surface treatments on performance and emissions of a methanol-fueled, direct injection, stratified charge engine

    West, B.; Green, J.B. [Oak Ridge National Lab., TN (United States)

    1994-07-01

    The purpose of this study was to investigate the effects of thermal barrier coatings and/or surface treatments on the performance and emissions of a methanol-fueled, direct-injection, stratified-charge (DISC) engine. A Ricardo Hydra Mark III engine was used for this work and in previous experiments at Oak Ridge National Laboratory (ORNL). The primary focus of the study was to examine the effects of various piston insert surface treatments on hydrocarbon (HC) and oxides of nitrogen (NO{sub x}) emissions. Previous studies have shown that engines of this class have a tendency to perform poorly at low loads and have high unburned fuel emissions. A blank aluminum piston was modified to employ removable piston bowl inserts. Four different inserts were tested in the experiment: aluminum, stainless steel with a 1.27-mm (0.050-in.) air gap (to act as a thermal barrier), and two stainless steel/air-gap inserts with coatings. Two stainless steel inserts were dimensionally modified to account for the coating thickness (1.27-mm) and coated identically with partially stabilized zirconia (PSZ). One of the coated inserts then had an additional seal-coat applied. The coated inserts were otherwise identical to the stainless steel/air-gap insert (i.e., they employed the same 1.27-mm air gap). Thermal barrier coatings were employed in an attempt to increase combustion chamber surface temperatures, thereby reducing wall quenching and promoting more complete combustion of the fuel in the quench zone. The seal-coat was applied to the zirconia to reduce the surface porosity; previous research suggested that despite the possibly higher surface temperatures obtainable with a ceramic coating, the high surface area of a plasma-sprayed coating may actually allow fuel to adhere to the surface and increase the unburned fuel emissions and fuel consumption.

  12. Platinum and palladium nano-structured catalysts for polymer electrolyte fuel cells and direct methanol fuel cells.

    Long, Nguyen Viet; Thi, Cao Minh; Yong, Yang; Nogami, Masayuki; Ohtaki, Michitaka

    2013-07-01

    In this review, we present the synthesis and characterization of Pt, Pd, Pt based bimetallic and multi-metallic nanoparticles with mixture, alloy and core-shell structure for nano-catalysis, energy conversion, and fuel cells. Here, Pt and Pd nanoparticles with modified nanostructures can be controllably synthesized via chemistry and physics for their uses as electro-catalysts. The cheap base metal catalysts can be studied in the relationship of crystal structure, size, morphology, shape, and composition for new catalysts with low cost. Thus, Pt based alloy and core-shell catalysts can be prepared with the thin Pt and Pt-Pd shell, which are proposed in low and high temperature proton exchange membrane fuel cells (PEMFCs), and direct methanol fuel cells (DMFCs). We also present the survey of the preparation of Pt and Pd based catalysts for the better catalytic activity, high durability, and stability. The structural transformations, quantum-size effects, and characterization of Pt and Pd based catalysts in the size ranges of 30 nm (1-30 nm) are presented in electro-catalysis. In the size range of 10 nm (1-10 nm), the pure Pt catalyst shows very large surface area for electro-catalysis. To achieve homogeneous size distribution, the shaped synthesis of the polyhedral Pt nanoparticles is presented. The new concept of shaping specific shapes and morphologies in the entire nano-scale from nano to micro, such as polyhedral, cube, octahedra, tetrahedra, bar, rod, and others of the nanoparticles is proposed, especially for noble and cheap metals. The uniform Pt based nanosystems of surface structure, internal structure, shape, and morphology in the nanosized ranges are very crucial to next fuel cells. Finally, the modifications of Pt and Pd based catalysts of alloy, core-shell, and mixture structures lead to find high catalytic activity, durability, and stability for nano-catalysis, energy conversion, fuel cells, especially the next large-scale commercialization of next

  13. Interaction of Liquid Film Flow of Direct Vessel Injection Under the Cross Directional Gas Flow

    Kim, Han-sol; Lee, Jae-young [Handong Global University, Pohang (Korea, Republic of); Euh, Dong-Jin [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2015-10-15

    In order to obtain a proper scaling law of the flow, local information of the flow was investigated experimentally and also numerically. A series of experiments were conducted in the 1/20 modified linear scaled plate type test rig to analyze a liquid film from ECC water injection through the DVI nozzle to the downcomer wall. The present study investigates liquid film flow generated in a downcomer of direct vessel injection (DVI) system which is employed as an emergency core cooling (ECC) system during a loss of coolant accident in the Korea nuclear power plant APR1400. During the late reflooding, complicated multi-phase flow phenomena including the wavy film flow, film breakup, entrainment, liquid film shift due to interfacial drag and gas jet impingement occur. A confocal chromatic sensor was used to measure the local instantaneous liquid film thickness and a hydraulic jump in the film flow and boundaries of the film flow. It was found that CFD analysis results without surface tension model showed some difference with the data in surface tension dominated flow region. For the interaction between a liquid film and gas shear flow, CFD results make a good agreement with the real liquid film dynamics in the case of low film Reynolds number or low Weber number flow. In the 1/20 scaled plate type experiment and simulation, the deformed spreading profile results seem to accord with each other at the relatively low We and Re regime.

  14. Self-Healing Proton-Exchange Membranes Composed of Nafion-Poly(vinyl alcohol) Complexes for Durable Direct Methanol Fuel Cells.

    Li, Yixuan; Liang, Liang; Liu, Changpeng; Li, Yang; Xing, Wei; Sun, Junqi

    2018-04-30

    Proton-exchange membranes (PEMs) that can heal mechanical damage to restore original functions are important for the fabrication of durable and reliable direct methanol fuel cells (DMFCs). The fabrication of healable PEMs that exhibit satisfactory mechanical stability, enhanced proton conductivity, and suppressed methanol permeability via hydrogen-bonding complexation between Nafion and poly(vinyl alcohol) (PVA) followed by postmodification with 4-carboxybenzaldehyde (CBA) molecules is presented. Compared with pure Nafion, the CBA/Nafion-PVA membranes exhibit enhanced mechanical properties with an ultimate tensile strength of ≈20.3 MPa and strain of ≈380%. The CBA/Nafion-PVA membrane shows a proton conductivity of 0.11 S cm -1 at 80 °C, which is 1.2-fold higher than that of a Nafion membrane. The incorporated PVA gives the CBA/Nafion-PVA membranes excellent proton conductivity and methanol resistance. The resulting CBA/Nafion-PVA membranes are capable of healing mechanical damage of several tens of micrometers in size and restoring their original proton conductivity and methanol resistance under the working conditions of DMFCs. The healing property originates from the reversibility of hydrogen-bonding interactions between Nafion and CBA-modified PVA and the high chain mobility of Nafion and CBA-modified PVA. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Direct methanol fuel cells: Pt-Ni/C binary electrocatalysts; Celulas a combutivel de metanol direto: eletrocatalisadores binarios de Pt-Ni/C

    Salgado, Jose Ricardo Cezar; Antolini, Ermete; Santos, Ana Maria dos; Gonzalez, Ernesto Rafael [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Inst. de Quimica], e-mail: salgado@iqsc.usp.br

    2004-07-01

    Direct methanol fuel cells use platinum alloys as more efficient catalysts than platinum. In the case of binary alloys, the second metal affects several properties of platinum, like the interatomic distance, the electronic density and the capacity of forming oxygenated species at lower potentials. In this work, Pt-Ni catalysts supported on high surface area carbon (Pt-Ni/C) were prepared and characterized, and tested as catalysts in the anode and the cathode in direct methanol fuel cells. In both cases the performance of the material was better than that of Pt/C, and comparing the two situations it was better when the material was used in the cathode. The improved performance in the cathode was attributed to the nickel that forms a true alloy with platinum, while the better performance in the anode was attributed to the presence of nickel oxides. (author)

  16. Highly water-dispersible, mixed ionic-electronic conducting, polymer acid-doped polyanilines as ionomers for direct methanol fuel cells.

    Murthy, Arun; Manthiram, Arumugam

    2011-06-28

    Highly water-dispersible polymer acid-doped polyanilines have been synthesized and evaluated as an alternative for expensive Nafion ionomers in the anode of direct methanol fuel cells (DMFC). These polymers as ionomers lead to higher performance in single cell DMFC compared to Nafion ionomers due to mixed ionic-electronic conduction, water dispersibility, and co-catalytic activity. This journal is © The Royal Society of Chemistry 2011

  17. Synthesis and properties of a novel sulfonated poly(arylene ether ketone sulfone) membrane with a high β-value for direct methanol fuel cell applications

    Xu, Jingmei; Ma, Li; Han, Hailan; Ni, Hongzhe; Wang, Zhe; Zhang, Huixuan

    2014-01-01

    Highlights: • Introduction of carboxyl groups into copolymers resulted in extensive hydrogen bond. • The C-SPAEKS membranes had obviously hydrophilic/hydrophobic phase separation. • The membranes showed low methanol permeability and high β values. • The membranes exhibited good thermal property and desirable mechanical performance. - Abstract: Sulfonated poly(arylene ether ketone sulfone) membranes containing carboxylic acid groups (C-SPAEKS) with different degrees of sulfonation were synthesized by the nucleophilic aromatic substitution reactions of 4-carboxylphenyl hydroquinone (4C-PH), bisphenol A, 3,3′-disulfonated 4,4′-dichlorodiphenyl sulfone, and 4,4′-difluorobenzophenone. The Fourier transform infrared and 1 H NMR analyses of C-SPAEKS revealed the presence of carboxylic acid groups in the C-SPAEKS membranes. The membranes exhibited a low swelling degree and methanol crossover level. The effects of different degrees of sulfonation on the water uptake, proton conductivity, and methanol permeability coefficient of the membranes were studied. The maximum proton conductivity of C-SPAEKS-80 membrane at room temperature was 0.069 S cm −1 , which was higher than that of Nafion ® 117 membrane. The methanol permeability coefficient of C-SPAEKS-80 membrane was 9.15 × 10 −7 cm 2 s −1 at 20 °C, much lower than that of Nafion 117 membrane (22.9 × 10 −7 cm 2 s −1 ). Furthermore, the carboxyl group-containing membranes exhibited a high β-value, further confirming that this series of membranes possess excellent comprehensive performance and can be applied in direct methanol fuel cells

  18. Photocatalytic conversion of methane to methanol

    Taylor, C.E.; Noceti, R.P.; D`Este, J.R. [Pittsburgh Energy Technology Center, PA (United States)

    1995-12-31

    A long-term goal of our research group is the exploration of novel pathways for the direct oxidation of methane to liquid fuels, chemicals, and intermediates. The use of three relatively abundant and inexpensive reactants, light, water, and methane, to produce methanol is attractive. The products of reaction, methanol and hydrogen, are both commercially desirable, methanol being used as is or converted to a variety of other chemicals, and the hydrogen could be utilized in petroleum and/or chemical manufacturing. Methane is produced as a by-product of coal gasification. Depending upon reactor design and operating conditions, up to 18% of total gasifier product may be methane. In addition, there are vast proven reserves of geologic methane in the world. Unfortunately, a large fraction of these reserves are in regions where there is little local demand for methane and it is not economically feasible to transport it to a market. There is a global research effort under way in academia, industry, and government to find methods to convert methane to useful, more readily transportable and storable materials. Methanol, the initial product of methane oxidation, is a desirable product of conversion because it retains much of the original energy of the methane while satisfying transportation and storage requirements. Investigation of direct conversion of methane to transportation fuels has been an ongoing effort at PETC for over 10 years. One of the current areas of research is the conversion of methane to methanol, under mild conditions, using light, water, and a semiconductor photocatalyst. The use of three relatively abundant and inexpensive reactants, light, water, and methane, to produce methanol, is attractive. Research in the laboratory is directed toward applying the techniques developed for the photocatalytic splitting of the water and the photochemical conversion of methane.

  19. Pt-Ru/CeO2/carbon nanotube nanocomposites: an efficient electrocatalyst for direct methanol fuel cells.

    Sun, Zhenyu; Wang, Xiang; Liu, Zhimin; Zhang, Hongye; Yu, Ping; Mao, Lanqun

    2010-07-20

    Pt-Ru/CeO(2)/multiwalled carbon nanotube (MWNT) electrocatalysts were prepared using a rapid sonication-facilitated deposition method and were characterized by X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS), transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), and voltammetry. Morphological characterization by TEM revealed that CeO(2) nanoparticles (NPs) were in intimate contact with Pt-Ru NPs, and both were highly dispersed on the exteriors of nanotubes with a small size and a very narrow size distribution. Compared with the Pt-Ru/MWNT and Pt/MWNT electrocatalysts, the as-prepared Pt-Ru/CeO(2)/MWNT exhibited a significantly improved electrochemically active surface area (ECSA) and a remarkably enhanced activity toward methanol oxidation. The effects of the Pt-Ru loading and the Pt-to-Ru molar ratio on the electrocatalytic activity of Pt-Ru/CeO(2)/MWNT for methanol oxidation were investigated. We found that a maximum activity toward methanol oxidation reached at the 10 wt % of Pt-Ru loading and 1:1 of Pt-to-Ru ratio. Moreover, the role of CeO(2) in the catalysts for the enhancement of methanol oxidation was discussed in terms of both bifunctional mechanism and electronic effects.

  20. Enhanced activity of Pt/CNTs anode catalyst for direct methanol fuel cells using Ni2P as co-catalyst

    Li, Xiang; Luo, Lanping; Peng, Feng; Wang, Hongjuan; Yu, Hao

    2018-03-01

    The direct methanol fuel cell is a promising energy conversion device because of the utilization of the state-of-the-art platinum (Pt) anode catalyst. In this work, novel Pt/Ni2P/CNTs catalysts were prepared by the H2 reduction method. It was found that the activity and stability of Pt for methanol oxidation reaction (MOR) could be significantly enhanced while using nickel phosphide (Ni2P) nanoparticles as co-catalyst. X-ray photoelectron spectroscopy revealed that the existence of Ni2P affected the particle size and electronic distribution of Pt obviously. Pt/CNTs catalyst, Pt/Ni2P/CNTs catalysts with different Ni2P amount were synthesized, among which Pt/6%Ni2P/CNTs catalyst exhibited the best MOR activity of 1400 mAmg-1Pt, which was almost 2.5 times of the commercial Pt/C-JM catalyst. Moreover, compared to other Pt-based catalysts, this novel Pt/Ni2P/CNTs catalyst also exhibited higher onset current density and better steady current density. The result of this work may provide positive guidance to the research on high efficiency and stability of Pt-based catalyst for direct methanol fuel cells.

  1. Direct methanol fuel cell with extended reaction zone anode: PtRu and PtRuMo supported on graphite felt

    Bauer, Alex; Gyenge, Előd L.; Oloman, Colin W.

    Pressed graphite felt (thickness ∼350 μm) with electrodeposited PtRu (43 g m -2, 1.4:1 atomic ratio) or PtRuMo (52 g m -2, 1:1:0.3 atomic ratio) nanoparticle catalysts was investigated as an anode for direct methanol fuel cells. At temperatures above 333 K the fuel cell performance of the PtRuMo catalyst was superior compared to PtRu. The power density was 2200 W m -2 with PtRuMo at 5500 A m -2 and 353 K while under the same conditions PtRu yielded 1925 W m -2. However, the degradation rate of the Mo containing catalyst formulation was higher. Compared to conventional gas diffusion electrodes with comparable PtRu catalyst composition and load, the graphite felt anodes gave higher power densities mainly due to the extended reaction zone for methanol oxidation.

  2. Optimum concentration gradient of the electrocatalyst, Nafion® and poly(tetrafluoroethylene) in a membrane-electrode-assembly for enhanced performance of direct methanol fuel cells.

    Liu, Jing Hua; Jeon, Min Ku; Lee, Ki Rak; Woo, Seong Ihl

    2010-12-14

    A combinatorial library of membrane-electrode-assemblies (MEAs) which consisted of 27 different compositions was fabricated to optimize the multilayer structure of direct methanol fuel cells. Each spot consisted of three layers of ink and a gradient was generated by employing different concentrations of the three components (Pt catalyst, Nafion® and polytetrafluoroethylene (PTFE)) of each layer. For quick evaluation of the library, a high-throughput optical screening technique was employed for methanol electro-oxidation reaction (MOR) activity. The screening results revealed that gradient layers could lead to higher MOR activity than uniform layers. It was found that the MOR activity was higher when the concentrations of Pt catalyst and Nafion ionomer decreased downward from the top layer to the bottom layer. On the other hand, higher MOR activity was observed when PTFE concentration increased downward from the top to the bottom layer.

  3. One-Pot and Facile Fabrication of Hierarchical Branched Pt-Cu Nanoparticles as Excellent Electrocatalysts for Direct Methanol Fuel Cells.

    Cao, Yanqin; Yang, Yong; Shan, Yufeng; Huang, Zhengren

    2016-03-09

    Hierarchical branched nanoparticles are one promising nanostructure with three-dimensional open porous structure composed of integrated branches for superior catalysis. We have successfully synthesized Pt-Cu hierarchical branched nanoparticles (HBNDs) with small size of about 30 nm and composed of integrated ultrathin branches by using a modified polyol process with introduction of poly(vinylpyrrolidone) and HCl. This strategy is expected to be a general strategy to prepare various metallic nanostructures for catalysis. Because of the special open porous structure, the as-prepared Pt-Cu HBNDs exhibit greatly enhanced specific activity toward the methanol oxidation reaction as much as 2.5 and 1.7 times compared with that of the commercial Pt-Ru and Pt-Ru/C catalysts, respectively. Therefore, they are potentially applicable as electrocatalysts for direct methanol fuel cells.

  4. An in-situ nano-scale swelling-filling strategy to improve overall performance of Nafion membrane for direct methanol fuel cell application

    Li, Jing; Fan, Kun; Cai, Weiwei; Ma, Liying; Xu, Guoxiao; Xu, Sen; Ma, Liang; Cheng, Hansong

    2016-11-01

    A novel in-situ nano-scale swelling-filling (SF) strategy is proposed to modify commercial Nafion membranes for performance enhancement of direct methanol fuel cells (DMFCs). A Nafion membrane was filled in-situ with proton conductive macromolecules (PCMs) in the swelling process of a Nafion membrane in a PCM solution. As a result, both proton conductivity and methanol-permeation resistivity of the SF-treated Naifion membrane was substantially improved with the selectivity nearly doubled compared to the original Nafion membrane. The mechanical strength of the optimal SF treated Nafion membrane was also enforced due to the strong interaction between the PCM fillers and the Nafion molecular chains. As a result, a DMFC equipped with the SF-treated membrane yielded a 33% higher maximum power density than that offered by the DMFC with the original Nafion membrane.

  5. Direct synthesis of bimetallic PtCo mesoporous nanospheres as efficient bifunctional electrocatalysts for both oxygen reduction reaction and methanol oxidation reaction

    Wang, Hongjing; Yu, Hongjie; Li, Yinghao; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

    2018-04-01

    The engineering of electrocatalysts with high performance for cathodic and/or anodic catalytic reactions is of great urgency for the development of direct methanol fuel cells. Pt-based bimetallic alloys have recently received considerable attention in the field of fuel cells because of their superior catalytic performance towards both fuel molecule electro-oxidation and oxygen reduction. In this work, bimetallic PtCo mesoporous nanospheres (PtCo MNs) with uniform size and morphology have been prepared by a one-step method with a high yield. The as-made PtCo MNs show superior catalytic activities for both oxygen reduction reaction and methanol oxidation reaction relative to Pt MNs and commercial Pt/C catalyst, attributed to their mesoporous structure and bimetallic composition.

  6. Phase transitions in liquids with directed intermolecular bonding

    Son, L.; Ryltcev, R.

    2005-01-01

    Liquids with quasi - chemical bonding between molecules are described in terms of vertex model. It is shown that this bonding results in liquid - liquid phase transition, which occurs between phases with different mean density of intermolecular bonds. The transition may be suggested to be a universal phenomena for those liquids.

  7. Methanol absorption characteristics for the removal of H2S (hydrogen sulfide), COS (carbonyl sulfide) and CO2 (carbon dioxide) in a pilot-scale biomass-to-liquid process

    Seo, Myung Won; Yun, Young Min; Cho, Won Chul; Ra, Ho Won; Yoon, Sang Jun; Lee, Jae Goo; Kim, Yong Ku; Kim, Jae Ho; Lee, See Hoon; Eom, Won Hyun; Lee, Uen Do; Lee, Sang Bong

    2014-01-01

    The BTL (biomass-to-liquid) process is an attractive process that produces liquid biofuels from biomass. The FT (Fisher–Tropsch) process is used to produce synfuels such as diesel and gasoline from gasified biomass. However, the H 2 S (hydrogen sulfide), COS (carbonyl sulfide) and CO 2 (carbon dioxide) in the syngas that are produced from the biomass gasifiers cause a decrease of the conversion efficiency and deactivates the catalyst that is used in the FT process. To remove the acid gases, a pilot-scale methanol absorption tower producing diesel at a rate of 1 BPD (barrel per day) was developed, and the removal characteristics of the acid gases were determined. A total operation time of 500 h was achieved after several campaigns. The average syngas flow rate at the inlet of methanol absorption tower ranged from 300 to 800 L/min. The methanol absorption tower efficiently removed H 2 S from 30 ppmV to less than 1 ppmV and COS from 2 ppmV to less than 1 ppmV with a removal of CO 2 from 20% to 5%. The outlet gas composition adhered to the guidelines for FT reactors. No remaining sulfurous components were found, and the tar component was analyzed in the spent methanol after long-term operations. - Highlights: • The gas cleaning system in a pilot-scale BTL (biomass-to-liquid) process is reported. • Although methanol absorption tower is conventional process, its application to BTL process is attempted. • The methanol absorption tower efficiently removed H 2 S, COS and CO 2 in the syngas. • The sulfurous and tar components in the methanol are analyzed

  8. Gas chromatography/isotope ratio mass spectrometry: analysis of methanol, ethanol and acetic acid by direct injection of aqueous alcoholic and acetic acid samples.

    Ai, Guomin; Sun, Tong; Dong, Xiuzhu

    2014-08-15

    Methanol, ethanol, and acetic acid are not easily extracted from aqueous samples and are susceptible to isotope fractionation in gas chromatography/isotope ratio mass spectrometry (GC/IRMS) analysis. Developing a direct dilution GC/IRMS method for aqueous samples, by adjusting the sample concentrations in common solvents to be similar to each other and using a fixed GC split ratio, is very convenient and important because any linearity effects caused by amount-dependent isotope fractionation can be avoided. The suitability of acetonitrile and acetone solvents for the GC/IRMS analysis of pure methanol, ethanol and acetic acid, and commercial liquor and vinegar samples was evaluated using n-hexane and water as control solvents. All the solvents including water were separated from the analyte on a HP-INNOWAX column and were diverted away from the combustion interface. The influence of liquor matrix on the ethanol GC/IRMS analyses was evaluated by adding pure ethanol to liquor samples. Acetonitrile and acetone gave similar δ(13) C values for pure ethanol and pure acetic acid to those obtained in water and n-hexane, and also gave similar δ(13) C values of ethanol in liquor and acetic acid in white vinegar to that obtained in water. For methanol analysis, acetonitrile and refined acetone gave similar δ(13) C values to that obtained in water, but n-hexane was not a suitable solvent. In addition, isotopic fractionation caused by solvent and solute interactions was observed. We recommend using acetonitrile for the GC/IRMS analysis of aqueous alcoholic samples, and acetone for the analysis of aqueous acetic acid samples. This direct dilution method can provide high accurate and precise GC/IRMS analysis of the relative changes in δ(13) C values of methanol, ethanol, and acetic acid. Copyright © 2014 John Wiley & Sons, Ltd.

  9. Direct hydrodeoxygenation of raw woody biomass into liquid alkanes.

    Xia, Qineng; Chen, Zongjia; Shao, Yi; Gong, Xueqing; Wang, Haifeng; Liu, Xiaohui; Parker, Stewart F; Han, Xue; Yang, Sihai; Wang, Yanqin

    2016-03-30

    Being the only sustainable source of organic carbon, biomass is playing an ever-increasingly important role in our energy landscape. The conversion of renewable lignocellulosic biomass into liquid fuels is particularly attractive but extremely challenging due to the inertness and complexity of lignocellulose. Here we describe the direct hydrodeoxygenation of raw woods into liquid alkanes with mass yields up to 28.1 wt% over a multifunctional Pt/NbOPO4 catalyst in cyclohexane. The superior performance of this catalyst allows simultaneous conversion of cellulose, hemicellulose and, more significantly, lignin fractions in the wood sawdust into hexane, pentane and alkylcyclohexanes, respectively. Investigation on the molecular mechanism reveals that a synergistic effect between Pt, NbOx species and acidic sites promotes this highly efficient hydrodeoxygenation of bulk lignocellulose. No chemical pretreatment of the raw woody biomass or separation is required for this one-pot process, which opens a general and energy-efficient route for converting raw lignocellulose into valuable alkanes.

  10. Direct patterning of nanoparticles and biomolecules by liquid nanodispensing.

    Fabié, Laure; Agostini, Pierre; Stopel, Martijn; Blum, Christian; Lassagne, Benjamin; Subramaniam, Vinod; Ondarçuhu, Thierry

    2015-03-14

    We report on the localized deposition of nanoparticles and proteins, nano-objects commonly used in many nanodevices, by the liquid nanodispensing (NADIS) technique which consists in depositing droplets of a solution through a nanochannel drilled at the apex of an AFM tip. We demonstrate that the size of spots can be adjusted from microns down to sub-50 nm by tuning the channel diameter, independently of the chemical nature of the solute. In the case of nanoparticles, we demonstrated the ultimate limit of the method and showed that large arrays of single (or pairs of) nanoparticles can be reproducibly deposited. We further explored the possibility to deposit different visible fluorescent proteins using NADIS without loss of protein function. The intrinsic fluorescence of these proteins is characteristic of their structural integrity; the retention of fluorescence after NADIS deposition demonstrates that the proteins are intact and functional. This study demonstrates that NADIS can be a viable alternative to other scanning probe lithography techniques since it combines high resolution direct writing of nanoparticles or biomolecules with the versatility of liquid lithography techniques.

  11. Thermophysical properties of binary mixtures of {l_brace}ionic liquid 2-hydroxy ethylammonium acetate + (water, methanol, or ethanol){r_brace}

    Alvarez, Victor H. [School of Chemical Engineering, State University of Campinas (UNICAMP), P.O. Box 6066, 13083-970 Campinas-SP (Brazil); Chemical Engineering Department, ETSE, University of Santiago de Compostela (USC), P.O. Box 15782, Santiago de Compostela (Spain); Mattedi, Silvana [Chemical Engineering Department, Polytechnic School, Federal University of Bahia (UFBA), 40210-630 Salvador-BA (Brazil); Martin-Pastor, Manuel [Unidade de Resonancia Magnetica, RIAIDT, edif. CACTUS, University of Santiago de Compostela (USC), P.O. Box 15706, Santiago de Compostela (Spain); Aznar, Martin [School of Chemical Engineering, State University of Campinas (UNICAMP), P.O. Box 6066, 13083-970 Campinas-SP (Brazil); Iglesias, Miguel, E-mail: miguel.iglesias@usc.es [Chemical Engineering Department, ETSE, University of Santiago de Compostela (USC), P.O. Box 15782, Santiago de Compostela (Spain)

    2011-07-15

    Research highlights: > This paper reports the density and speed of sound data of binary mixtures {l_brace}2-hydroxy ethylammonium acetate + (water, or methanol, or ethanol){r_brace} measured between the temperatures (298.15 and 313.15) K at atmospheric pressure. > The aggregation, dynamic behavior, and hydrogen-bond network were studied using thermo-acoustic, X-ray, and NMR techniques. > The Peng-Robinson equation of state, coupled with the Wong-Sandler mixing rule using the COSMO-SAC model predicted the density of the solutions with relative mean deviations below than 3.0%. - Abstract: In this work, density and speed of sound data of binary mixtures of an ionic liquid consisting of {l_brace}2-hydroxy ethylammonium acetate (2-HEAA) + (water, methanol, or ethanol){r_brace} have been measured throughout the entire concentration range, from the temperature of (288.15 to 323.15) K at atmospheric pressure. The excess molar volumes, variations of the isentropic compressibility, the apparent molar volume, isentropic apparent molar compressibility, and thermal expansion coefficient were calculated from the experimental data. The excess molar volumes were negative throughout the whole composition range. Compressibility data in combination with low angle X-ray scattering and NMR measurements proved that the presence of micelles formed due to ion pair interaction above a critical concentration of the ionic liquid in the mixtures. The Peng-Robinson equation of state coupled with the Wong-Sandler mixing rule and COSMO-SAC model was used to predict densities and the calculated deviations were lower than 3%, for binary mixtures in all composition range.

  12. Direct Partial Oxidation of Natural Gas to Liquid Chemicals

    Rasmussen, Christian Lund

    2007-01-01

    Direkte delvis oxidation af naturgas til flydende kemikalier er en attraktiv industriel proces, hvor naturgas omdannes til stoffer; primært methanol (CH3OH) som let kan transporteres over store afstande. Omdannelsen sker i en simpel et-trinsproces under højt tryk, lave forbrændingstemperaturer, s...

  13. Transient direct-contact condensation on liquid droplets

    Pasamehmetoglu, K.O.; Nelson, R.A.

    1987-01-01

    In this paper, direct-contact condensation on subcooled liquid droplets is studied in two parts. In the first part, simple design correlations for the condensation in a steady environment are developed based upon a conduction model. These correlations include the convective heat-transfer coefficient, condensation rate, total condensation, and the droplet-thermalization time. In the second part of the paper, the effect of a time-dependent saturation temperature on the condensation process is investigated. A rapid decrease in saturation temperature is typical of condensation environments in which the steam-supply rate is limited and condensation-induced depressurization becomes important. Design correlations are developed for condensation in an environment in which the saturation temperature decreases linearly with time. These correlations are graphically compared to the design correlations of the first part through a quasi-steady approach. The error associated with this approach is quantified as a function of the rate of change of the saturation temperature

  14. Renewable hydrogen utilisation for the production of methanol

    Galindo Cifre, P.; Badr, O.

    2007-01-01

    Electrolytic hydrogen production is an efficient way of storing renewable energy generated electricity and securing the contribution of renewables in the future electricity supply. The use of this hydrogen for the production of methanol results in a liquid fuel that can be utilised directly with minor changes in the existing infrastructure. To utilise the renewable generated hydrogen for production of renewable methanol, a sustainable carbon source is needed. This carbon can be provided by biomass or CO 2 in the flue gases of fossil fuel-fired power stations, cement factories, fermentation processes and water purification plants. Methanol production pathways via biomass gasification and CO 2 recovery from the flue gasses of a fossil fuel-fired power station have been reviewed in this study. The cost of methanol production from biomass was found to lie in the range of 300-400 EUR/tonne of methanol, and the production cost of CO 2 based methanol was between 500 and 600 EUR/tonne. Despite the higher production costs compared with methanol produced by conventional natural gas reforming (i.e. 100-200 EUR/tonne, aided by the low current price of natural gas), these new processes incorporate environmentally beneficial aspects that have to be taken into account. (author)

  15. First Principles Modeling of Structure and Transport in Solid Polymer Electrolytes, Ionic Liquids, and Methanol/Water Mixtures

    2016-02-10

    chemical calculations of the magnesium battery electrolytes we were able to make all vibrational frequency assignments (measured in the IR and Raman ...electrolytes for magnesium batteries incorporating chloro- or iodo- ionic liquids. Much of this work was done in collaboration with the experimental group... magnesium batteries incorporating chloro- or iodo- ionic liquids. Much of this work was done in collaboration with the experimental group of Prof. Vito Di

  16. Low Pt content of carbon supported Pt-Ni-TiO2 nanotube electrocatalysts for direct methanol fuel cell

    Jiang, Q.Z; Wu, X.; Ma, Z.F. [Shanghai Jiao Tong Univ., Shanghai, (China). Dept. of Chemical Engineering

    2008-07-01

    Interest in titanium oxide (TiO2) nanomaterial is growing due to their special characteristics for optics, catalysis, and photoelectricity conversion. In this study, the anatase/rutile crystalline of TiO2 nanoparticles was synthesized by co-deposition. TiO2 nanotubes were then obtained by microwave irradiations. This paper described the mechanism to fabricate TiO2 nanotubes. The conditions for preparing TiO2 nanotubes by microwave irradiation were optimized. Electrocatalysts were then prepared on the basis of the synthesized TiO2 nanotube. Their performances were investigated by the electro-oxidation of methanol. When Pt electrocatalysts were doped with a certain content of TiO2 nanotubes, they had more electrocatalytic activity for methanol electro-oxidation, particularly if the second transition metal, such as Ni, was added into the electrocatalyst. The electrocatalysts contained 5 and 10 wt per cent of Pt and Ni respectively. The 10 wt per cent TiO2 nanotubes showed better activities than any other catalysts for methanol electro-oxidation. According to XRD and TEM results, the size of nanoparticles of Pt became smaller after adding TiO2 nanotubes into the catalysts. It was concluded that here might be some interactions between Pt, Ni, and TiO2 nanotubes.

  17. Direct Synthesis of Methanol by Partial Oxidation of Methane with Oxygen over Cobalt Modified Mesoporous H-ZSM-5 Catalyst

    Yuni Krisyuningsih Krisnandi

    2015-11-01

    Full Text Available Partial oxidation of methane over mesoporous catalyst cobalt modified H-ZSM-5 has been carried out. Mesoporous Na-ZSM-5 (Si/Al = 35.4 was successfully synthesized using double template method which has high surface area (450 m2/g and average pore diameter distribution of 1.9 nm. The as-synthesized Na-ZSM-5 was converted to H-ZSM-5 through multi-exchange treatment with ammonium ion solution, causing decreased crystallinity and surface area, but increased porous diameter, due to dealumination during treatment process. Moreover, H-ZSM-5 was loaded with cobalt (Co = 2.5% w by the incipient impregnation method and calcined at 550 °C. Partial oxidation of methane was performed in the batch reactor with 0.75 bar methane and 2 bar of nitrogen (with impurities of 0.5% oxygen as the input at various reaction time (30, 60 and 120 min. The reaction results show that cobalt species in catalyst has an important role, because H-ZSM-5 cannot produce methanol in partial oxidation of methane. The presence of molecular oxygen increased the percentage of methanol yield. The reaction is time-dependent with the highest methanol yield (79% was acquired using Co/H-ZSM-5 catalyst for 60 min.

  18. Ionic Liquid Microemullsions, Templates for Directing Morphology of Cellulose Biopolymer Nanoparticles (Briefing Charts)

    2015-08-19

    Charts 3. DATES COVERED (From - To) July 2015-August 2015 4. TITLE AND SUBTITLE Ionic Liquid Microemullsions, Templates for Directing Morphology of...unlimited AFRL Public Affairs Clearance No. TBD Ionic Liquid Microemullsions, Templates for Directing Morphology of Cellulose Biopolymer...AFRL Public Affairs Clearance No. 15438 Outline • Background on Cellulose and Ionic Liquids • Materials and Methods • Results: Designing an IL

  19. Application of Mössbauer spectroscopy in industrial heterogeneous catalysis: effect of oxidant on FePO{sub 4} material phase transformations in direct methanol synthesis from methane

    Dasireddy, Venkata D. B. C., E-mail: dasireddy@ki.si [National Institute of Chemistry, Department of Catalysis and Chemical Reaction Engineering (Slovenia); Khan, Faiza B. [Energy Technology (South Africa); Hanzel, Darko [Jozef Stefan Institute (Slovenia); Bharuth-Ram, Krish [Durban University of Technology, Physics Department (South Africa); Likozar, Blaž [National Institute of Chemistry, Department of Catalysis and Chemical Reaction Engineering (Slovenia)

    2017-11-15

    The effect of the FePO{sub 4} material phase transformation in the direct selective oxidation of methane to methanol was studied using various oxidants, i.e. O{sub 2}, H{sub 2}O and N{sub 2}O. The phases of the heterogeneous catalyst applied, before and after the reactions, were characterized by M¨ossbauer spectroscopy. The main reaction products were methanol, carbon monoxide and carbon dioxide, whereas formaldehyde was produced in rather minute amounts. The Mössbauer spectra showed the change of the initial catalyst material, FePO{sub 4} (tridymite-like phase (tdm)), to the reduced metal form, iron(II) pyrophosphate, Fe{sub 2}P{sub 2}O{sub 7}, and thereafter, the material phase change was governed by the oxidation with individual oxidizing species.Mössbauer spectroscopy measurements applied along with X-ray diffraction (XRD) studies on fresh, reduced and spent catalytic materials demonstrated a transformation of the catalyst to a mixture of phases which depended on operating process conditions. Generally, activity was low and should be a subject of further material optimization and engineering, while the selectivity towards methanol at low temperatures applied was adequate. The proceeding redox mechanism should thus play a key role in catalytic material design, while the advantage of iron-based heterogeneous catalysts primarily lies in them being comparably inexpensive and comprising non-critical raw materials only.

  20. Highly effective and CO-tolerant PtRu electrocatalysts supported on poly(ethyleneimine) functionalized carbon nanotubes for direct methanol fuel cells

    Cheng, Yi; Jiang, San Ping

    2013-01-01

    A highly efficient and CO tolerant PtRu electrocatalysts supported on amino-rich, cationic poly(ethyleneimine) polyelectrolyte functionalized multi-walled carbon nanotubes (PtRu/PEI-MWCNTs) has been developed. The catalysts were characterized by thermogravimetric analysis, Raman spectroscopy, cyclic voltammograms, CO stripping, chronoamperometry, transmission electron microscopy (TEM) and X-ray diffraction (XRD). The PtRu particles with average size ∼2.5 nm are well dispersed on PEI-MWCNTs. The peak current for the methanol oxidation reaction on 40% PtRu/PEI-MWCNTs is 636mAmg Pt −1 , 5.7 times higher than 112mA mg Pt −1 measured on the 40% PtRu supported on acid treated MWCNTs (PtRu/AO-MWCNTs) under identical conditions. PtRu/PEI-MWCNTs catalysts exhibit a superior electrocatalytic activity and stability for the methanol oxidation reaction due to its high tolerance toward CO poisoning as compared with PtRu/AO-MWCNTs for direct methanol fuel cells

  1. Toxicological evaluation of liquids proposed for use in direct contact liquid--liquid heat exchangers for solar heated and cooled buildings

    Buchan, R.M.; Majestic, J.R.; Billau, R.

    1976-09-01

    This report contains the results of the toxicological evaluation part of the project entitled, ''Direct Contact Liquid-Liquid Heat Exchangers for Solar Heated and Cooled Buildings.'' Obviously any liquid otherwise suitable for use in such a device should be subjected to a toxicological evaluation. 34 liquids (24 denser than water, 10 less dense) have physical and chemical properties that would make them suitable for use in such a device. In addition to the complexity involved in selecting the most promising liquids from the standpoint of their chemical and physical properties is added the additional difficulty of also considering their toxicological properties. Some of the physical and chemical properties of these liquids are listed. The liquids are listed in alphabetical order within groups, the denser than water liquids are listed first followed by those liquids less dense than water.

  2. Vapor-liquid equilibrium data for five binary systems of methanol, tert-butylalcohol, tert-butylmethylether and water, and quaternary reactive system producing tert-butylmethylether from methanol and tert-butylalcohol; Metanoru, tert-buchiruarukoru, tert-buchirumechirueteru oyobi mizu wo kumiawaseta 5shu no niseibunkei to metanoru to tert-buchiruarukoru ni yoru eteruka hannokei no taikiatsuka ni okeru kieki heiko deta

    Komatsu, H.; Nakamura, M.; Yamashita, Y.; Hirai, C. [Toyohashi Univ. of Technology (Japan)

    1997-11-01

    At atmospheric pressure, vapor-liquid equilibrium relationships for five binary systems of methanol-tert-butylalcohol, methanol-tert-butylmethylether, tert-butylalcohol-tert-butylmethylether, water-tert-butylalcohol and water-tert-butylmethylether are observed. The Wilson parameters for the binary systems have been obtained. Comparisons between the Wilson method, The ASOG method and the UNIFAC method are made. Vapor-liquid equilibrium relationships of the quaternary reactive system producing tert-butylmethylether by use of methanol and tert-butylalcohol are also observed, and it is confirmed that the Wilson parameters resulting from the data of binary systems can be used to estimate the vapor-liquid equilibrium data for the quaternary reactive system of methanol-tert-butylalcohol-tert-butylmethylether-water. 6 refs., 7 figs., 5 tabs.

  3. Isothermal (vapour + liquid) equilibrium for binary mixtures of polyethylene glycol mono-4-nonylphenyl ether (PEGNPE) with methanol, ethanol, or 2-propanol

    Khoiroh, Ianatul; Lee, Ming-Jer

    2011-01-01

    Highlights: → An autoclave apparatus was used for binary (vapour + liquid) equilibrium data measurement. → The studied systems are polyethylene glycol mono-4-nonylphenyl ether with alcohols. → The saturated pressure data were fitted accurately to the Antoine equation. → The NRTL model correlated well the phase equilibrium data. → The solvent activities have been calculated. - Abstract: Saturated pressures of three binary systems of oligomeric polyethylene glycol mono-4-nonylphenyl ether (PEGNPE) with methanol, ethanol, and 2-propanol have been measured by using an autoclave (vapour + liquid) equilibrium (VLE) apparatus at temperatures ranging from (340 to 455) K and the oligomer content ranging from 0.100 to 0.400 in mole fraction. With a given feed composition, equilibrium pressures were measured at various temperatures to obtain VLE data. The experimental data were fitted to the Antoine equation and also correlated with activity coefficient models, the NRTL and the UNIQUAC. The correlation results showed good agreement between the calculated values and the experimental data. In general, the NRTL model yielded better results. Additionally, the solvent activities were evaluated from the experimental results and were compared with those from the NRTL and the UNIQUAC models.

  4. Preparation of Pt Ru/C electrocatalysts using gamma radiation for application as anode in direct methanol fuel cell

    Spinace, Estevam V.; Silva, Dionisio F. da; Cruz, Victor A. da; Oliveira Neto, Almir; Machado, Luci D.B.; Pino, Eddy S.; Linardi, Marcelo

    2005-01-01

    PtRu nanoparticles supported on carbon (PtRu/C electrocatalysts) were prepared submitting a water/2-propanol mixture containing the metal ions and the carbon support to gamma radiation. The water/2-propanol (v/v) and the total dose (kGy) were studied. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The methanol electro-oxidation was studied by cyclic voltammetry using the thin porous coating. In the studied conditions, the electrocatalytic activity of the prepared electrocatalysts depend on the water/2-propanol ratio used in the reaction medium. (author)

  5. Ion conductivity and mass spectrometry of methanol diffusion and electroosmotic drag on proton-conducting membranes for the Direct Methanol Fuel Cell (DMFC); Ionische Leitfaehigkeit und massenspektrometrische Bestimmung der Methanol-Diffusion und des 'Electroosmotic Drag' an protonenleitenden Membranen fuer die Direkt-Methanol-Brennstoffzelle (DMFC)

    Oeztuerk, N.

    2001-07-01

    The methanol permeability of the nafion membrane is one reason why the DMFC is not marketable as yet. As a result of diffusion, permeation and electroosmotic drag, methanol is transferred to the kation side where it will reduce the fuel cell performance. Research is going on world-wide to develop new materials that will prevent methanol crossover. The report describes the development of a measuring cell that will provide the necessary information on diffusion, permeation, electroosmotic drag and conductivity. [German] Ein wesentlicher Grund, der die Einfuehrung der DMFC noch verhindert, ist die Methanoldurchlaessigkeit der Nafion-Membran. Durch Diffusion und Permeation und durch den Electroosmotic Drag gelangt Methanol auf die Kathodenseite und fuehrt dann zu einem Leistungsabfall der Brennstoffzelle. Daher werden weltweit neue Materialien entwickelt, die bei guter lonenleitfaehigkeit den Methanol-crossover unterdruecken. Zur Beurteilung und Weiterentwicklung der neuen Materialien werden Informationen zur Diffusion, Permeation, zum Electroosmotic Drag und zur Leitfaehigkeit benoetigt. Um diese Parameter schnell und einfach zu bestimmen, wurde im Rahmen der vorliegenden Arbeit eine Messzelle weiter entwickelt. Diese Messzelle erlaubt die schnelle Bestimmung aller vier wichtigen Parameter. (orig.)

  6. New catalysts for miniaturized methanol fuel cells

    Pedersen, Christoffer Mølleskov

    The methanol fuel cell is an interesting energy technology, capable of converting the chemical energy of methanol directly into electricity. The technology is specifically attractive for small mobile applications such as laptops, smartphones, tablets etc. since it offers almost instantaneously...

  7. Direct numerical simulation of stratified gas-liquid flow

    Lombardi, P.; De Angelis, V.; Banerjee, S.

    1996-01-01

    Interactions through an interface between two turbulent flows play an important role in many environmental and industrial problems, e.g. in determining the coupling fluxes of heat mass and momentum, between the ocean and atmosphere, and in the design of gas-liquid contractors for the chemical industry, as well as in determining interactions between phases in nuclear transients that are accompanied by system voiding e.g. LOCAs. Here, the Direct Numerical Simulation (DNS) of the interaction of two turbulent fluids through a flat interface has been simulated. The flow and the temperature fields are computed using a pseudospectral method. This study shows that shear stress at the interface correlates well with the heat flux. Extensive analysis of the near interface turbulence structure has been performed using quadrant analysis. From this it is clear that gas-side sweeps dominate over the high shear stress regions. This suggests that simple parameterizations based on sweep frequency may be adequate for predictions of scalar transport rates

  8. Fabrication and Characterization of New Composite Tio2 Carbon Nanofiber Anodic Catalyst Support for Direct Methanol Fuel Cell via Electrospinning Method

    Abdullah, N.; Kamarudin, S. K.; Shyuan, L. K.; Karim, N. A.

    2017-12-01

    Platinum (Pt) is the common catalyst used in a direct methanol fuel cell (DMFC). However, Pt can lead towards catalyst poisoning by carbonaceous species, thus reduces the performance of DMFC. Thus, this study focuses on the fabrication of a new composite TiO2 carbon nanofiber anodic catalyst support for direct methanol fuel cells (DMFCs) via electrospinning technique. The distance between the tip and the collector (DTC) and the flow rate were examined as influencing parameters in the electrospinning technique. To ensure that the best catalytic material is fabricated, the nanofiber underwent several characterizations and electrochemical tests, including FTIR, XRD, FESEM, TEM, and cyclic voltammetry. The results show that D18, fabricated with a flow rate of 0.1 mLhr-1 and DTC of 18 cm, is an ultrafine nanofiber with the smallest average diameter, 136.73 ± 39.56 nm. It presented the highest catalyst activity and electrochemical active surface area value as 274.72 mAmg-1 and 226.75m2 g-1 PtRu, respectively, compared with the other samples.

  9. Fabrication of Highly Stable and Efficient PtCu Alloy Nanoparticles on Highly Porous Carbon for Direct Methanol Fuel Cells.

    Khan, Inayat Ali; Qian, Yuhong; Badshah, Amin; Zhao, Dan; Nadeem, Muhammad Arif

    2016-08-17

    Boosting the durability of Pt nanoparticles by controlling the composition and morphology is extremely important for fuel cells commercialization. We deposit the Pt-Cu alloy nanoparticles over high surface area carbon in different metallic molar ratios and optimize the conditions to achieve desired material. The novel bimetallic electro-catalyst {Pt-Cu/PC-950 (15:15%)} offers exceptional electrocatalytic activity when tested for both oxygen reduction reaction and methanol oxidation reactions. A high mass activity of 0.043 mA/μgPt (based on Pt mass) is recorded for ORR. An outstanding longevity of this electro-catalyst is noticed when compared to 20 wt % Pt loaded either on PC-950 or commercial carbon. The high surface area carbon support offers enhanced activity and prevents the nanoparticles from agglomeration, migration, and dissolution as evident by TEM analysis.

  10. Research Progress on the Indirect Hydrogenation of Carbon Dioxide to Methanol.

    Du, Xian-Long; Jiang, Zheng; Su, Dang Sheng; Wang, Jian-Qiang

    2016-02-19

    Methanol is a sustainable source of liquid fuels and one of the most useful organic chemicals. To date, most of the work in this area has focused on the direct hydrogenation of CO2 to methanol. However, this process requires high operating temperatures (200-250 °C), which limits the theoretical yield of methanol. Thus, it is desirable to find a new strategy for the efficient conversion of CO2 to methanol at relatively low reaction temperatures. This Minireview seeks to outline the recent advances on the indirect hydrogenation of CO2 to methanol. Much emphasis is placed on discussing specific systems, including hydrogenation of CO2 derivatives (organic carbonates, carbamates, formates, cyclic carbonates, etc.) and cascade reactions, with the aim of critically highlighting both the achievements and remaining challenges associated with this field. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Proton conducting membranes prepared by incorporation of organophosphorus acids into alcohol barrier polymers for direct methanol fuel cells

    Jiang, Zhongyi; Zheng, Xiaohong; Wu, Hong; Pan, Fusheng

    A novel type of DMFC membrane was developed via incorporation of organophosphorus acids (OPAs) into alcohol barrier materials (polyvinyl alcohol/chitosan, PVA/CS) to simultaneously acquire high proton conductivity and low methanol permeability. Three kinds of OPAs including amino trimethylene phosphonic acid (ATMP), ethylene diamine tetra(methylene phosphonic acid) (EDTMP) and hexamethylene diamine tetra(methylene phosphonic acid) (HDTMP), with different molecular structure and phosphonic acid groups content were added into PVA/CS blends and served the dual functions as proton conductor as well as crosslinker. The as-prepared OPA-doped PVA/CS membranes exhibited remarkably enhanced proton conducting ability, 2-4 times higher than that of the pristine PVA/CS membrane, comparable with that for Nafion ®117 membrane (5.04 × 10 -2 S cm -1). The highest proton conductivities 3.58 × 10 -2, 3.51 × 10 -2 and 2.61 × 10 -2 S cm -1 for ATMP-, EDTMP- and HDTMP-doped membranes, respectively were all achieved at highest initial OPA doping content (23.1 wt.%) at room temperature. The EDTMP-doped PVA/CS membrane with an acid content of 13.9 wt.% showed the lowest methanol permeability of 2.32 × 10 -7 cm 2 s -1 which was 16 times lower than that of Nafion ®117 membrane. In addition, the thermal stability and oxidative durability were both significantly improved by the incorporation of OPAs in comparison with pristine PVA/CS membranes.

  12. Proton conducting membranes prepared by incorporation of organophosphorus acids into alcohol barrier polymers for direct methanol fuel cells

    Jiang, Zhongyi; Zheng, Xiaohong; Wu, Hong; Pan, Fusheng [Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China)

    2008-10-15

    A novel type of DMFC membrane was developed via incorporation of organophosphorus acids (OPAs) into alcohol barrier materials (polyvinyl alcohol/chitosan, PVA/CS) to simultaneously acquire high proton conductivity and low methanol permeability. Three kinds of OPAs including amino trimethylene phosphonic acid (ATMP), ethylene diamine tetra(methylene phosphonic acid) (EDTMP) and hexamethylene diamine tetra(methylene phosphonic acid) (HDTMP), with different molecular structure and phosphonic acid groups content were added into PVA/CS blends and served the dual functions as proton conductor as well as crosslinker. The as-prepared OPA-doped PVA/CS membranes exhibited remarkably enhanced proton conducting ability, 2-4 times higher than that of the pristine PVA/CS membrane, comparable with that for Nafion {sup registered} 117 membrane (5.04 x 10{sup -2} S cm{sup -1}). The highest proton conductivities 3.58 x 10{sup -2}, 3.51 x 10{sup -2} and 2.61 x 10{sup -2} S cm{sup -1} for ATMP-, EDTMP- and HDTMP-doped membranes, respectively were all achieved at highest initial OPA doping content (23.1 wt.%) at room temperature. The EDTMP-doped PVA/CS membrane with an acid content of 13.9 wt.% showed the lowest methanol permeability of 2.32 x 10{sup -7} cm{sup 2} s{sup -1} which was 16 times lower than that of Nafion {sup registered} 117 membrane. In addition, the thermal stability and oxidative durability were both significantly improved by the incorporation of OPAs in comparison with pristine PVA/CS membranes. (author)

  13. Continuous gas/liquid–liquid/liquid flow synthesis of 4-fluoropyrazole derivatives by selective direct fluorination

    Jessica R. Breen

    2011-08-01

    Full Text Available 4-Fluoropyrazole systems may be prepared by a single, sequential telescoped two-step continuous gas/liquid–liquid/liquid flow process from diketone, fluorine gas and hydrazine starting materials.

  14. Enhanced Proton Conductivity of Sulfonated Hybrid Poly(arylene ether ketone) Membranes by Incorporating an Amino-Sulfo Bifunctionalized Metal-Organic Framework for Direct Methanol Fuel Cells.

    Ru, Chunyu; Li, Zhenhua; Zhao, Chengji; Duan, Yuting; Zhuang, Zhuang; Bu, Fanzhe; Na, Hui

    2018-03-07

    Novel side-chain-type sulfonated poly(arylene ether ketone) (SNF-PAEK) containing naphthalene and fluorine moieties on the main chain was prepared in this work, and a new amino-sulfo-bifunctionalized metal-organic framework (MNS, short for MIL-101-NH 2 -SO 3 H) was synthesized via a hydrothermal technology and postmodification. Then, MNS was incorporated into a SNF-PAEK matrix as an inorganic nanofiller to prepare a series of organic-inorganic hybrid membranes (MNS@SNF-PAEK-XX). The mechanical property, methanol resistance, electrochemistry, and other properties of MNS@SNF-PAEK-XX hybrid membranes were characterized in detail. We found that the mechanical strength and methanol resistances of these hybrid membranes were improved by the formation of an ionic cross-linking structure between -NH 2 of MNS and -SO 3 H on the side chain of SNF-PAEK. Particularly, the proton conductivity of these hybrid membranes increased obviously after the addition of MNS. MNS@SNF-PAEK-3% exhibited the proton conductivity of 0.192 S·cm -1 , which was much higher than those of the pristine membrane (0.145 S·cm -1 ) and recast Nafion (0.134 S·cm -1 ) at 80 °C. This result indicated that bifunctionalized MNS rearranged the microstructure of hybrid membranes, which could accelerate the transfer of protons. The hybrid membrane (MNS@SNF-PAEK-3%) showed a better direct methanol fuel cell performance with a higher peak power density of 125.7 mW/cm 2 at 80 °C and a higher open-circuit voltage (0.839 V) than the pristine membrane.

  15. Small-sized and contacting Pt-WC nanostructures on graphene as highly efficient anode catalysts for direct methanol fuel cells.

    Wang, Ruihong; Xie, Ying; Shi, Keying; Wang, Jianqiang; Tian, Chungui; Shen, Peikang; Fu, Honggang

    2012-06-11

    The synergistic effect between Pt and WC is beneficial for methanol electro-oxidation, and makes Pt-WC catalyst a promising anode candidate for the direct methanol fuel cell. This paper reports on the design and synthesis of small-sized and contacting Pt-WC nanostructures on graphene that bring the synergistic effect into full play. Firstly, DFT calculations show the existence of a strong covalent interaction between WC and graphene, which suggests great potential for anchoring WC on graphene with formation of small-sized, well-dispersed WC particles. The calculations also reveal that, when Pt attaches to the pre-existing WC/graphene hybrid, Pt particles preferentially grow on WC rather than graphene. Our experiments confirmed that highly disperse WC nanoparticles (ca. 5 nm) can indeed be anchored on graphene. Also, Pt particles 2-3 nm in size are well dispersed on WC/graphene hybrid and preferentially grow on WC grains, forming contacting Pt-WC nanostructures. These results are consistent with the theoretical findings. X-ray absorption fine structure spectroscopy further confirms the intimate contact between Pt and WC, and demonstrates that the presence of WC can facilitate the crystallinity of Pt particles. This new Pt-WC/graphene catalyst exhibits a high catalytic efficiency toward methanol oxidation, with a mass activity 1.98 and 4.52 times those of commercial PtRu/C and Pt/C catalysts, respectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Direct methanol fuel cell with extended reaction zone anode: PtRu and PtRuMo supported on graphite felt

    Bauer, Alex; Gyenge, Elod L.; Oloman, Colin W. [Department of Chemical and Biological Engineering, The University of British Columbia, 2360 East Mall, Vancouver, BC (Canada)

    2007-05-15

    Pressed graphite felt (thickness {proportional_to}350 {mu}m) with electrodeposited PtRu (43 g m{sup -2}, 1.4:1 atomic ratio) or PtRuMo (52 g m{sup -2}, 1:1:0.3 atomic ratio) nanoparticle catalysts was investigated as an anode for direct methanol fuel cells. At temperatures above 333 K the fuel cell performance of the PtRuMo catalyst was superior compared to PtRu. The power density was 2200 W m{sup -2} with PtRuMo at 5500 A m{sup -2} and 353 K while under the same conditions PtRu yielded 1925 W m{sup -2}. However, the degradation rate of the Mo containing catalyst formulation was higher. Compared to conventional gas diffusion electrodes with comparable PtRu catalyst composition and load, the graphite felt anodes gave higher power densities mainly due to the extended reaction zone for methanol oxidation. (author)

  17. Effect of heat treatment on stability of gold particle modified carbon supported Pt-Ru anode catalysts for a direct methanol fuel cell

    Li Xiaowei; Liu Juanying; Huang Qinghong; Vogel, Walter; Akins, Daniel L.; Yang Hui

    2010-01-01

    Carbon supported Au-PtRu (Au-PtRu/C) catalysts were prepared as the anodic catalysts for the direct methanol fuel cell (DMFC). The procedure involved simple deposition of Au particles on a commercial Pt-Ru/C catalyst, followed by heat treatment of the resultant composite catalyst at 125, 175 and 200 o C in a N 2 atmosphere. High-resolution transmission electron microscopy (HR-TEM) measurements indicated that the Au nanoparticles were attached to the surface of the Pt-Ru nanoparticles. We found that the electrocatalytic activity and stability of the Au-PtRu/C catalysts for methanol oxidation is better than that of the PtRu/C catalyst. An enhanced stability of the electrocatalyst is observed and attributable to the promotion of CO oxidation by the Au nanoparticles adsorbed onto the Pt-Ru particles, by weakening the adsorption of CO, which can strongly adsorb to and poison Pt catalyst. XPS results show that Au-PtRu/C catalysts with heat treatment lead to surface segregation of Pt metal and an increase in the oxidation state of Ru, which militates against the dissolution of Ru. We additionally find that Au-PtRu/C catalysts heat-treated at 175 o C exhibit the highest electrocatalytic stability among the catalysts prepared by heat treatment: this observation is explained as due to the attainment of the highest relative concentration of gold and the highest oxidation state of Ru oxides for the catalyst pretreated at this temperature.

  18. Ru-decorated Pt nanoparticles on N-doped multi-walled carbon nanotubes by atomic layer deposition for direct methanol fuel cells

    Johansson, Anne-Charlotte Elisabeth Birgitta; Yang, R.B.; Haugshøj, K.B.

    2013-01-01

    We present atomic layer deposition (ALD) as a new method for the preparation of highly dispersed Ru-decorated Pt nanoparticles for use as catalyst in direct methanol fuel cells (DMFCs). The nanoparticles were deposited onto N-doped multi-walled carbon nanotubes (MWCNTs) at 250 °C using trimethyl......(methylcyclopentadienyl)platinum MeCpPtMe3, bis(ethylcyclopentadienyl)ruthenium Ru(EtCp)2 and O2 as the precursors. Catalysts with 5, 10 and 20 ALD Ru cycles grown onto the CNT-supported ALD Pt nanoparticles (150 cycles) were prepared and tested towards the electro-oxidation of CO and methanol, using cyclic voltammetry...... and chronoamperometry in a three-electrode electrochemical set-up. The catalyst decorated with 5 ALD Ru cycles was of highest activity in both reactions, followed by the ones with 10 and 20 ALD Ru cycles. It is demonstrated that ALD is a promising technique in the field of catalysis as highly dispersed nanoparticles...

  19. High performance anode based on a partially fluorinated sulfonated polyether for direct methanol fuel cells operating at 130 °C

    Mack, Florian; Gogel, Viktor; Jörissen, Ludwig; Kerres, Jochen

    2014-06-01

    Due to the disadvantages of the Nafion polymer for the application in the direct methanol fuel cell (DMFC) especial at temperatures above 100 °C several polymers of the hydrocarbon type have already been investigated as membranes and ionomers in the DMFC. Among them were nonfluorinated and partially fluorinated arylene main-chain hydrocarbon polymers. In previous work, sulfonated polysulfone (sPSU) has been applied as the proton-conductive binder in the anode of a DMFC, ending up in good and stable performance. In continuation of this work, in the study presented here a polymer was prepared by polycondensation of decafluorobiphenyl and bisphenol AF. The formed polymer was sulfonated after polycondensation by oleum and the obtained partially fluorinated sulfonated polyether (SFS) was used as the binder and proton conductor in a DMFC anode operating at a temperature of 130 °C. The SFS based anode with 5% as ionomer showed comparable performance for the methanol oxidation to Nafion based anodes and significant reduced performance degradation versus Nafion and sPSU based anodes on the Nafion 115 membrane. Membrane electrode assemblies (MEAs) with the SFS based anode showed drastically improved performance compared to MEAs with Nafion based anodes during operation with lower air pressure at the cathode.

  20. Considerations of the Effects of Naphthalene Moieties on the Design of Proton-Conductive Poly(arylene ether ketone) Membranes for Direct Methanol Fuel Cells.

    Wang, Baolong; Hong, Lihua; Li, Yunfeng; Zhao, Liang; Wei, Yuxue; Zhao, Chengji; Na, Hui

    2016-09-14

    Novel sulfonated poly(arylene ether ketones) (SDN-PAEK-x), consisting of dual naphthalene and flexible sulfoalkyl groups, were prepared via polycondensation, demethylation, and sulfobutylation grafting reaction. Among them, SDN-PAEK-1.94 membrane with the highest ion exchange capacity (IEC = 2.46 mequiv·g(-1)) exhibited the highest proton conductivity, which was 0.147 S· cm(-1) at 25 °C and 0.271 S·cm(-1) at 80 °C, respectively. The introduction of dual naphthalene moieties is expected to achieve much enhanced properties compared to those of sulfonated poly(arylene ether ketones) (SNPAEK-x), consisting of single naphthalene and flexible sulfoalkyl groups. Compared with SNPAEK-1.60 with a similar IEC, SDN-PAEK-1.74 membrane showed higher proton conductivity, higher IEC normalized conductivity, and higher effective proton mobility, although it had lower analytical acid concentration. The SDN-PAEK-x membranes with IECs higher than 1.96 mequiv·g(-1) also exhibited higher proton conductivity than that of recast Nafion membrane. Furthermore, SDN-PAEK-1.94 displayed a better single cell performance with a maximum power density of 60 mW·cm(-2) at 80 °C. Considering its high proton conductivity, excellent single cell performance, good mechanical stabilities, low membrane swelling, and methanol permeability, SDN-PAEK-x membranes are promising candidates as alternative polymer electrolyte membranes to Nafion for direct methanol fuel cell applications.

  1. Performance comparison of portable direct methanol fuel cell mini-stacks based on a low-cost fluorine-free polymer electrolyte and Nafion membrane

    Baglio, V.; Stassi, A.; Modica, E.; Antonucci, V.; Arico, A.S.; Caracino, P.; Ballabio, O.; Colombo, M.; Kopnin, E.

    2010-01-01

    A low-cost fluorine-free proton conducting polymer electrolyte was investigated for application in direct methanol fuel cell (DMFC) mini-stacks. The membrane consisted of a sulfonated polystyrene grafted onto a polyethylene backbone. DMFC operating conditions specifically addressing portable applications, i.e. passive mode, air breathing, high methanol concentration, room temperature, were selected. The device consisted of a passive DMFC monopolar three-cell stack. Two designs for flow-fields/current collectors based on open-flow or grid-like geometry were investigated. An optimization of the mini-stack structure was necessary to improve utilization of the fluorine-free membrane. Titanium-grid current collectors with proper mechanical stiffness allowed a significant increase of the performance by reducing contact resistance even in the case of significant swelling. A single cell maximum power density of about 18 mW cm -2 was achieved with the fluorine-free membrane at room temperature under passive mode. As a comparison, the performance obtained with Nafion 117 membrane and Ti grids was 31 mW cm -2 . Despite the lower performance, the fluorine-free membrane showed good characteristics for application in portable DMFCs especially with regard to the perspectives of significant cost reduction.

  2. A feasibility study on direct methanol fuel cells for laptop computers based on a cost comparison with lithium-ion batteries

    Wee, Jung-Ho

    2007-01-01

    This paper compares the total cost of direct methanol fuel cell (DMFC) and lithium (Li)-ion battery systems when applied as the power supply for laptop computers in the Korean environment. The average power output and operational time of the laptop computers were assumed to be 20 W and 3000 h, respectively. Considering the status of their technologies and with certain conditions assumed, the total costs were calculated to be US$140 for the Li-ion battery and US$362 for DMFC. The manufacturing costs of the DMFC and Li-ion battery systems were calculated to be $16.65 W -1 and $0.77 W h -1 , and the energy consumption costs to be $0.00051 W h -1 and $0.00032 W h -1 , respectively. The higher fuel consumption cost of the DMFC system was due to the methanol (MeOH) crossover loss. Therefore, the requirements for DMFCs to be able to compete with Li-ion batteries in terms of energy cost include reducing the crossover level to at an order magnitude of -9 and the MeOH price to under $0.5 kg -1 . Under these conditions, if the DMFC manufacturing cost could be reduced to $6.30 W -1 , then the DMFC system would become at least as competitive as the Li-ion battery system for powering laptop computers in Korea. (author)

  3. Graphitized nanodiamond supporting PtNi alloy as stable anodic and cathodic electrocatalysts for direct methanol fuel cell

    Wang, Yongjiao; Zang, Jianbing; Dong, Liang; Pan, Hong; Yuan, Yungang; Wang, Yanhui

    2013-01-01

    Highlights: • The graphitized nanodiamond (GND) showed a higher oxidation-resistance than XC-72. • The PtNi/GND electrocatalytic exhibited greater stability than PtNi/XC-72. • The PtNi/GND had a better catalytic activity for MOR and ORR than Pt/GND. -- Abstract: Surface graphitized nanodiamond (GND) with a diamond core covered by a graphitic carbon shell was prepared by annealing ND at the temperature of 1300 °C in a vacuum of 10 −3 Pa. PtNi electrocatalysts were prepared by a microwave heating polyol method using the prepared GND as a support. The composition and morphology of the PtNi electrocatalysts supported on GND (PtNi/GND) were characterized by X-ray diffraction, transmission electron microscopy and energy dispersion spectra. The results showed that nano-scaled PtNi alloy particles with an atomic ratio of approximately 1:1 were uniformly deposited on the GND through co-reduction process. The electrocatalytic activities of the PtNi/GND electrocatalysts for methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) were investigated by cyclic voltammetry, chronoamperometry and linear sweep voltammetry. The PtNi/GND exhibited better electrocatalytic activities than the Pt/GND either for MOR and ORR. In comparison with traditional carbon support Vulcan XC-72, GND showed higher oxidation-resistance, and consequently led to greater stability for the PtNi/GND than PtNi/XC-72

  4. Investigation of sulfonated polysulfone membranes as electrolyte in a passive-mode direct methanol fuel cell mini-stack

    Lufrano, F.; Baglio, V.; Staiti, P.; Stassi, A.; Arico, A.S.; Antonucci, V. [CNR - ITAE, Istituto di Tecnologie Avanzate per l' Energia ' ' Nicola Giordano' ' , Via Salita S. Lucia sopra Contesse n. 5 - 98126 S. Lucia - Messina (Italy)

    2010-12-01

    This paper reports on the development of polymer electrolyte membranes (PEMs) based on sulfonated polysulfone for application in a DMFC mini-stack operating at room temperature in passive mode. The sulfonated polysulfone (SPSf) with two degrees of sulfonation (57 and 66%) was synthesized by a well-known sulfonation process. SPSf membranes with different thicknesses were prepared and investigated. These membranes were characterized in terms of methanol/water uptake, proton conductivity, and fuel cell performance in a DMFC single cell and mini-stack operating at room temperature. The study addressed (a) control of the synthesis of sulfonated polysulfone, (b) optimization of the assembling procedure, (c) a short lifetime investigation and (d) a comparison of DMFC performance in active-mode operation vs. passive-mode operation. The best passive DMFC performance was 220 mW (average cell power density of about 19 mW cm{sup -2}), obtained with a thin SPSf membrane (70 {mu}m) at room temperature, whereas the performance of the same membrane-based DMFC in active mode was 38 mW cm{sup -2}. The conductivity of this membrane, SPSf (IEC = 1.34 mequiv. g{sup -1}) was 2.8 x 10{sup -2} S cm{sup -1}. A preliminary short-term test (200 min) showed good stability during chrono-amperometry measurements. (author)

  5. High utilization platinum deposition on single-walled carbon nanotubes as catalysts for direct methanol fuel cell

    Wang, J.J.; Yin, G.P.; Zhang, J.; Wang, Z.B.; Gao, Y.Z.

    2007-01-01

    This research aims to enhance the activity of Pt catalysts, thus to lower the loading of Pt metal in fuel cell. Highly dispersed platinum supported on single-walled carbon nanotubes (SWNTs) as catalyst was prepared by ion exchange method. The homemade Pt/SWNTs underwent a repetition of ion exchange and reduction process in order to achieve an increase of the metal loading. For comparison, the similar loading of Pt catalyst supported on carbon nanotubes was prepared by borohydride reduction method. The catalysts were characterized by using energy dispersive analysis of X-ray (EDAX), transmission electron micrograph (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectrum (XPS). Compared with the Pt/SWNTs catalyst prepared by borohydride method, higher Pt utilization was achieved on the SWNTs by ion exchange method. Furthermore, in comparison to the E-TEK 20 wt.% Pt/C catalyst with the support of carbon black, the results from electrochemical measurement indicated that the Pt/SWNTs prepared by ion exchange method displayed a higher catalytic activity for methanol oxidation and higher Pt utilization, while no significant increasing in the catalytic activity of the Pt/SWNTs catalyst obtained by borohydride method

  6. Binary vapour—liquid equilibria of methanol with sulfolane. Tetraethylene glycol dimethyl ether and 18-crown-6 = Phasengleichgewichte in binären systemen von Methanol mit Sulfolan, Tetraethylenglycoldimethylether und 18-krone-6 Kronenether

    Kuczynski, M.; 't Hart, W.; Westerterp, K.R.

    1986-01-01

    The activity coefficients of methanol in sulfolane, tetraethylene glycol dimethyl ether (TEGDME) and 18-crown-6 under conditions of equilibrium have been determined in the temperature range 423–503 K and in the pressure range 0.28–3.5 MPa. A minimum in the activity coefficient was found for the

  7. Direct Analysis of Organic Compounds in Liquid Using a Miniature Photoionization Ion Trap Mass Spectrometer with Pulsed Carrier-Gas Capillary Inlet.

    Lu, Xinqiong; Yu, Quan; Zhang, Qian; Ni, Kai; Qian, Xiang; Tang, Fei; Wang, Xiaohao

    2017-08-01

    A miniature ion trap mass spectrometer with capillary direct sampling and vacuum ultraviolet photoionization source was developed to conduct trace analysis of organic compounds in liquids. Self-aspiration sampling is available where the samples are drawn into the vacuum chamber through a capillary with an extremely low flow rate (less than 1 μL/min), which minimizes sample consumption in each analysis to tens of micrograms. A pulsed gas-assisted inlet was designed and optimized to promote sample transmission in the tube and facilitate the cooling of ions, thereby improving instrument sensitivity. A limit of detection of 2 ppb could be achieved for 2,4-dimethylaniline in a methanol solution. The sampling system described in the present study is specifically suitable for a miniature photoionization ion trap mass spectrometer that can perform rapid and online analysis for liquid samples. Graphical Abstract ᅟ.

  8. Design and fabrication of light weight current collectors for direct methanol fuel cells using the micro-electro mechanical system technique

    Sung, Min-Feng; Kuan, Yean-Der; Chen, Bing-Xian; Lee, Shi-Min

    The direct methanol fuel cell (DMFC) is suitable for portable applications. Therefore, a light weight and small size is desirable. The main objective of this paper is to design and fabricate a light weight current collector for DMFC usage. The light weight current collector mainly consists of a substrate with two thin film metal layers. The substrate of the current collector is an FR4 epoxy plate. The thin film metal layers are accomplished by the thermo coater technique to coat metal powders onto the substrate surfaces. The developed light weight current collectors are further assembled to a single cell DMFC test fixture to measure the cell performance. The results show that the proposed current collectors could even be applied to DMFCs because they are light, thin and low cost and have potential for mass production.

  9. Direct patterning of nanoparticles and biomolecules by liquid nanodispensing

    Fabie, Laure; Agostini, Pierre; Stopel, M.H.W.; Blum, Christian; Lassagne, Benjamin; Subramaniam, Vinod; Ondarcuhua, Thierry

    2015-01-01

    We report on the localized deposition of nanoparticles and proteins, nano-objects commonly used in many nanodevices, by the liquid nanodispensing (NADIS) technique which consists in depositing droplets of a solution through a nanochannel drilled at the apex of an AFM tip. We demonstrate that the

  10. Methanol as an energy carrier

    Biedermann, P.; Grube, T.; Hoehlein, B. (eds.)

    2006-07-01

    For the future, a strongly growing energy demand is expected in the transport sector worldwide. Economically efficient oil production will run through a maximum in the next decade. Higher fuel prices and an environmentally desirable reduction of emissions will increase the pressure for reducing fuel consumption and emissions in road traffic. These criteria show the urgent necessity of structural changes in the fuel market. Due to its advantages concerning industrial-scale production, storage and global availability, methanol has the short- to medium-term potential for gaining increased significance as a substitution product in the energy market. Methanol can be produced both from fossil energy sources and from biomass or waste materials through the process steps of synthesis gas generation with subsequent methanol synthesis. Methanol has the potential to be used in an environmentally friendly manner in gasoline/methanol mixtures for flexible fuel vehicles with internal combustion engines and in diesel engines with pure methanol. Furthermore, it can be used in fuel cell vehicles with on-board hydrogen production in direct methanol fuel cell drives, and in stationary systems for electricity and heat generation as well as for hydrogen production. Finally, in portable applications it serves as an energy carrier for electric power generation. In this book, the processes for the production and use of methanol are presented and evaluated, markets and future options are discussed and issues of safety and environmental impacts are addressed by a team of well-known authors. (orig.)

  11. Vitrification of human pronuclear oocytes by direct plunging into cooling agent: Non sterile liquid nitrogen vs. sterile liquid air.

    Isachenko, Vladimir; Todorov, Plamen; Seisenbayeva, Akerke; Toishibekov, Yerzhan; Isachenko, Evgenia; Rahimi, Gohar; Mallmann, Peter; Foth, Dolores; Merzenich, Markus

    2018-02-01

    In fact, a full sterilization of commercially-produced liquid nitrogen contaminated with different pathogens is not possible. The aim of this study was to compare the viability of human pronuclear oocytes subjected to cooling by direct submerging of open carrier in liquid nitrogen versus submerging in clean liquid air (aseptic system). One- and three-pronuclei stage embryos (n = 444) were cryopreserved by direct plunging into liquid nitrogen (vitrified) in ethylene glycol (15%), dimethylsulphoxide (15%) and 0.2M sucrose. Oocytes were exposed in 20, 33, 50 and 100% vitrification solution for 2, 1 and 1 min, and 30-50 s, respectively at room temperature. Then first part of oocytes (n = 225) were directly plunged into liquid nitrogen, and second part of oocytes (n = 219) into liquid air. Oocytes were thawed rapidly at a speed of 20,000 °C/min and then subsequently were placed into a graded series of sucrose solutions (0.5, 0.25, 0.12 and 0.06M) at 2.5 min intervals and cultured in vitro for 3 days. In both groups, the rate of high-quality embryos (Grade 6A: 6 blastomeres, no fragmentation; Grade 8A: 8 blastomeres, no fragmentation; Grade 8A compacting: 8 blastomeres, beginning of compacting) was noted. The rates of high-quality embryos developed from one-pronuclear oocytes vitrified by cooling in liquid nitrogen and liquid air were: 39.4% ± 0.6 and 38.7% ± 0.8, respectively (P > 0.1). These rates for three-pronuclear oocytes were: 45.8 ± 0.8% and 52.0 ± 0.7%, respectively (P liquid air (aseptic system) is a good alternative for using of not sterile liquid nitrogen. Copyright © 2017. Published by Elsevier Inc.

  12. Structure and reactivity of C7H7+ ions from the decay of tritiated toluenes. Part 1. Reactions of free tolyl ions with methanol in the gas and liquid phases

    Cacace, F.; Ciranni, G.; Sparapani, C.; Speranza, M.

    1984-01-01

    Labeled tolyl cations from the decay of ring-multitritiated toluene have been allowed to react with methanol in the liquid and the gas phases, at pressures ranging from 6 to 100 torr, yielding methyl tolyl ethers as the major products, without appreciable formation of benzyl methyl ether. The isomeric composition of the products from the gaseous systems depends on the pressure, the percentage of o-tolyl ether increasing at the expense of the para isomer as the methanol pressure is reduced. The results show that the three tolyl ions exist as distinct species in the dilute gas state. When formed in a sufficiently excited state, as from the β decay of a 3 H atom in toluene, they undergo appreciable interconversion, without detectable isomerization to the benzyl cation, at least within the pressure range accessible to the decay technique. 50 references, 1 table

  13. Sample introduction systems for reversed phase LC-ICP-MS of selenium using large amounts of methanol - comparison of systems based on membrane desolvation, a spray chamber and direct injection

    Bendahl, L.; Gammelgaard, Bente

    2005-01-01

    nebuliser (MCN) in combination with a membrane desolvator ( MD), a MCN in combination with a cyclonic spray chamber ( CS) and a direct injection nebuliser ( DIN), respectively. Thirteen selenium standards diluted in 50% methanol were introduced in each system at a flow rate of 50 mu l min(-1). Except...

  14. Thermodynamics and structure of liquid surfaces investigated directly with surface analytical tools

    Andersson, Gunther [Flinders Univ., Adelaide, SA (Australia). Centre for NanoScale Science and Technology; Morgner, Harald [Leipzig Univ. (Germany). Wilhelm Ostwald Inst. for Physical and Theoretical Chemistry

    2017-06-15

    Measuring directly the composition, the distribution of constituents as function of the depth and the orientation of molecules at liquid surfaces is essential for determining physicochemical properties of liquid surfaces. While the experimental tools that have been developed for analyzing solid surfaces can in principal be applied to liquid surfaces, it turned out that they had to be adjusted to the particular challenges imposed by liquid samples, e.g. by the unavoidable vapor pressure and by the mobility of the constituting atoms/molecules. In the present work it is shown, how electron spectroscopy and ion scattering spectroscopy have been used for analyzing liquid surfaces. The emphasis of this review is on using the structural information gained for determining the physicochemical properties of liquid surfaces. (copyright 2017 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. 1995 world methanol conference

    Anon.

    1995-01-01

    The 20 papers contained in this volume deal with the global markets for methanol, the production of MTBE, integrating methanol production into a coal-to-SNG complex, production of methanol from natural gas, catalysts for methanol production from various synthesis gases, combined cycle power plants using methanol as fuel, and economics of the methanol industry. All papers have been processed for inclusion on the data base

  16. Review of the direct thermochemical conversion of lignocellulosic biomass for liquid fuels

    Jianchun JIANG,Junming XU,Zhanqian SONG

    2015-03-01

    Full Text Available Increased demand for liquid transportation fuels, environmental concerns and depletion of petroleum resources requires the development of efficient conversion technologies for production of second-generation biofuels from non-food resources. Thermochemical approaches hold great potential for conversion of lignocellulosic biomass into liquid fuels. Direct thermochemical processes convert biomass into liquid fuels in one step using heat and catalysts and have many advantages over indirect and biological processes, such as greater feedstock flexibility, integrated conversion of whole biomass, and lower operation costs. Several direct thermochemical processes are employed in the production of liquid biofuels depending on the nature of the feedstock properties: such as fast pyrolysis/liquefaction of lignocellulosic biomass for bio-oil, including upgrading methods, such as catalytic cracking and hydrogenation. Owing to the substantial amount of liquid fuels consumed by vehicular transport, converting biomass into drop-in liquid fuels may reduce the dependence of the fuel market on petroleum-based fuel products. In this review, we also summarize recent progress in technologies for large-scale equipment for direct thermochemical conversion. We focus on the technical aspects critical to commercialization of the technologies for production of liquid fuels from biomass, including feedstock type, cracking catalysts, catalytic cracking mechanisms, catalytic reactors, and biofuel properties. We also discuss future prospects for direct thermochemical conversion in biorefineries for the production of high grade biofuels.

  17. Desenvolvimento de conjunto membrana-eletrodos para célula a combustível de metanol direto passiva Development of membrane electrode assembly for passive direct methanol fuel cell

    Eli Carlos Lisboa Ferreira

    2010-01-01

    Full Text Available Direct methanol fuel cells (DMFCs without external pumps or other ancillary devices for fuel and oxidant supply are known as passive DMFCs and are potential candidates to replace lithium-ion batteries in powering portable electronic devices. This paper presents the results obtained from a membrane electrode assembly (MEA specifically designed for passive DMFCs. Appropriated electrocatalysts were prepared and the effect of their loadings was investigated. Two types of gas diffusion layers (GDL were also tested. The influence of the methanol concentration was analyzed in each case. The best MEA performance presented a maximum power density of 11.94 mW cm-2.

  18. Direct current dielectrophoretic manipulation of the ionic liquid droplets in water.

    Zhao, Kai; Li, Dongqing

    2018-07-13

    The ionic liquids (ILs) as the environmentally benign solvents show great potentials in microemulsion carrier systems and have been widely used in the biochemical and pharmaceutical fields. In the work, the ionic liquid-in-water microemulsions were fabricated by using two kinds of hydrophobic ionic liquid, 1-Butyl-3-methylimidazolium hexafluorophosphate [Bmim][PF 6 ] and 1-Hexyl-3-methylimidazolium hexafluorophosphate [Hmim][PF 6 ] with Tween 20. The ionic liquid droplets in water experience the dielectrophoretic (DEP) forces induced by applying electrical field via a nano-orifice and a micron orifice on the opposite channel walls of a microchannel. The dielectrophoretic behaviors of the ionic liquid-in-water emulsion droplets were investigated under direct current (DC) electric field. The positive and negative DEP behaviors of the ionic liquid-in-water droplets varying with the electrical conductivity of the suspending medium were investigated and two kinds of the ionic liquid droplets of similar sizes were separated by their different DEP behaviors. In addition, the separation of the ionic liquid-in-water droplets by size was conducted. This paper, for the first time to our knowledge, presents the DC-DEP manipulation of the ionic liquid-in-water emulsion droplets by size and by type. This method provides a platform to manipulate the ionic liquid droplets individually. Copyright © 2018 Elsevier B.V. All rights reserved.

  19. Methanol commercial aviation fuel

    Price, R.O.

    1992-01-01

    Southern California's heavy reliance on petroleum-fueled transportation has resulted in significant air pollution problems within the south Coast Air Basin (Basin) which stem directly from this near total dependence on fossil fuels. To deal with this pressing issue, recently enacted state legislation has proposed mandatory introduction of clean alternative fuels into ground transportation fleets operating within this area. The commercial air transportation sector, however, also exerts a significant impact on regional air quality which may exceed emission gains achieved in the ground transportation sector. This paper addresses the potential, through the implementation of methanol as a commercial aviation fuel, to improve regional air quality within the Basin and the need to flight test and demonstrate methanol as an environmentally preferable fuel in aircraft turbine engines

  20. Fuel options for the fuel cell vehicle: hydrogen, methanol or gasoline?

    Thomas, C.E.; James, B.D.; Lomax, F.D. Jr.; Kuhn, I.F. Jr.

    2000-01-01

    Fuel cell vehicles can be powered directly by hydrogen or, with an onboard chemical processor, other liquid fuels such as gasoline or methanol. Most analysts agree that hydrogen is the preferred fuel in terms of reducing vehicle complexity, but one common perception is that the cost of a hydrogen infrastructure would be excessive. According to this conventional wisdom, the automobile industry must therefore develop complex onboard fuel processors to convert methanol, ethanol or gasoline to hydrogen. We show here, however, that the total fuel infrastructure cost to society including onboard fuel processors may be less for hydrogen than for either gasoline or methanol, the primary initial candidates currently under consideration for fuel cell vehicles. We also present the local air pollution and greenhouse gas advantages of hydrogen fuel cell vehicles compared to those powered by gasoline or methanol. (Author)

  1. Ionic liquids as silica deactivating agents in gas chromatography for direct analysis of primary amines in water.

    Krzyżaniak, Agnieszka; Weggemans, Wilko; Schuur, Boelo; de Haan, André B

    2011-12-16

    Analysis of primary amines in aqueous samples remains a challenging analytical issue. The preferred approach by gas chromatography is hampered by interactions of free silanol groups with the highly reactive amine groups, resulting in inconsistent measurements. Here, we report a method for direct analysis of aliphatic amines and diamines in aqueous samples by gas chromatography (GC) with silanol deactivation using ionic liquids (ILs). ILs including trihexyl(tetradecyl)phosphonium bis 2,4,4-(trimethylpentyl)phosphinate (Cyphos IL-104), 1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide [pmim][Tf(2)N] and N″-ethyl-N,N,N',N'-tetramethylguanidinium tris(pentafluoroethyl)trifluorophosphate [etmg][FAP] were tested as deactivating media for the GC liner. Solutions of these ILs in methanol were injected in the system prior to the analysis of primary amines. Butane-1,4-diamine (putrescine, BDA) was used as a reference amine. The best results were obtained using the imidazolium IL [pmim][Tf(2)N]. With this deactivator, excellent reproducibility of the analysis was achieved, and the detection limit of BDA was as low as 1mM. The applicability of the method was proven for the analysis of two different primary amines (C4-C5) and pentane-1,5-diamine. Copyright © 2011 Elsevier B.V. All rights reserved.

  2. Direct numerical simulations of gas-liquid multiphase flows

    Tryggvason, Grétar; Zaleski, Stéphane

    2011-01-01

    Accurately predicting the behaviour of multiphase flows is a problem of immense industrial and scientific interest. Modern computers can now study the dynamics in great detail and these simulations yield unprecedented insight. This book provides a comprehensive introduction to direct numerical simulations of multiphase flows for researchers and graduate students. After a brief overview of the context and history the authors review the governing equations. A particular emphasis is placed on the 'one-fluid' formulation where a single set of equations is used to describe the entire flow field and

  3. Direct observation of ionic structure at solid-liquid interfaces

    Siretanu, Igor; Ebeling, Daniel; Andersson, Martin Peter

    2014-01-01

    The distribution of ions and charge at solid-water interfaces plays an essential role in a wide range of processes in biology, geology and technology. While theoretical models of the solid-electrolyte interface date back to the early 20th century, a detailed picture of the structure of the electric...... double layer has remained elusive, largely because of experimental techniques have not allowed direct observation of the behaviour of ions, i.e. with subnanometer resolution. We have made use of recent advances in high-resolution Atomic Force Microscopy to reveal, with atomic level precision, the ordered...

  4. Nano-composite of PtRu alloy electrocatalyst and electronically conducting polymer for use as the anode in a direct methanol fuel cell

    Jongho Choi; Kyungwon Park; Hyekyung Lee; Youngmin Kim; Jaesuk Lee; Yungeun Sung [Kwangju Inst. of Science and Technology, Dept. of Materials Science and Engineering, Gwangju (Korea)

    2003-08-15

    Nano-composites comprised of PtRu alloy nanoparticles and an electronically conducting polymer for the anode electrode in direct methanol fuel cell (DMFC) were prepared. Two conducting polymers of poly(N-vinyl carbazole) and poly(9-(4-vinyl-phenyl)carbazole) were used for the nano-composite electrodes. Structural analyses were carried out using Fourier transform nuclear magnetic resonance spectroscopy, AC impedance spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM). Electrocatalytic activities were investigated by voltammetry and chronoamperometry in a 2 M CH{sub 3}OH/{sub 0.5} M H{sub 2}SO{sub 4} solution and the data compared with a carbon-supported PtRu electrode. XRD patterns indicated good alloy formation and nano-composite formation was confirmed by TEM. Electrochemical measurements and DMFC unit-cell tests indicate that the nano-composites could be useful in a DMFC, but its performance would be slightly lower than that of a carbon-supported electrode. The interfacial property between the PtRu-polymer nano-composite anode and the polymer electrolyte was good, as evidenced by scanning electron microscopy. For better performance in a DMFC, a higher electric conductivity of the polymer and a lower catalyst loss are needed in nano-composite electrodes. (Author)

  5. Enhance performance of micro direct methanol fuel cell by in situ CO2 removal using novel anode flow field with superhydrophobic degassing channels

    Liang, Junsheng; Luo, Ying; Zheng, Sheng; Wang, Dazhi

    2017-05-01

    Capillary blocking caused by CO2 bubbles in anode flow field (AFF) is one of the bottlenecks for performance improvement of a micro direct methanol fuel cell (μDMFC). In this work, we present a novel AFF structure with nested layout of hydrophilic fuel channels and superhydrophobic degassing channels which can remove most of CO2 from AFF before it is released to the fuel channels. The new AFFs are fabricated on Ti substrates by using micro photochemical etching combined with anodization and fluorination treatments. Performance of the μDMFCs with and without superhydrophobic degassing channels in their AFF is comparatively studied. Results show that the superhydrophobic degassing channels can significantly speed up the exhaust of CO2 from the AFF. CO2 clogging is not observed in the new AFFs even when their comparison AFFs have been seriously blocked by CO2 slugs under the same operating conditions. 55% and 60% of total CO2 produced in μDMFCs with N-serpentine and N-spiral AFF can be respectively removed by the superhydrophobic degassing channels. The power densities of the μDMFCs equipped with new serpentine and spiral AFFs are respectively improved by 30% and 90% compared with those using conventional AFFs. This means that the new AFFs developed in this work can effectively prevent CO2-induced capillary blocking in the fuel channels, and finally significantly improve the performance of the μDMFCs.

  6. Effect of the nanosized TiO2 particles in Pd/C catalysts as cathode materials in direct methanol fuel cells.

    Choi, Mahnsoo; Han, Choonsoo; Kim, In-Tae; Lee, Ji-Jung; Lee, Hong-Ki; Shim, Joongpyo

    2011-07-01

    Pd-TiO2/C catalysts were prepared by impregnating titanium dioxide (TiO2) on carbon-supported Pd (Pd/C) for use as the catalyst for the oxygen reduction reaction (ORR) in direct methanol fuel cells (DMFCs). Transmission electron microscope (TEM), scanning electron microscope (SEM) and X-ray diffraction (XRD) analyses were carried to confirm the distribution, morphology and structure of Pd and TiO2 on the carbon support. In fuel cell test, we confirmed that the addition of TiO2 nanoparticles make the improved catalytic activity of oxygen reduction. The electrochemical characterization of the Pd-TiO2/C catalyst for the ORR was carried out by cyclic voltammetry (CV) in the voltage window of 0.04 V to 1.2 V with scan rate of 25 mV/s. With the increase in the crystallite size of TiO2, the peak potential for OH(ads) desorption on the surface of Pd particle shifted to higher potential. This implies that TiO2 might affect the adsorption and desorption of oxygen molecules on Pd catalyst. The performance of Pd-TiO2/C as a cathode material was found to be similar to or better performance than that of Pt/C.

  7. Thermodynamic analysis of carbon formation in solid oxide fuel cells with a direct internal reformer fueled by ethanol, methanol, and methane

    Laosiripojana, N.; Assabumrungrat, S.; Pavarajarn, V.; Sangtongkitcharoen, W.; Tangjitmatee, A.; Praserthdam, P.

    2004-01-01

    'Full text:' This paper concerns a detailed thermodynamic analysis of carbon formation for a Direct Internal Reformer (DIR) Solid Oxide Fuel Cells (SOFC). The modeling of DIR-SOFC fueled by ethanol, methanol, and methane were compared. Two types of fuel cell electrolytes, i.e. oxygen-conducting and hydrogen-conducting, are considered. Equilibrium calculations were performed to find the ranges of inlet steam/fuel ratio where carbon formation is thermodynamically unfavorable in the temperature range of 500-1200 K. It was found that the key parameters determining the boundary of carbon formation are temperature, type of solid electrolyte and extent of the electrochemical reaction of hydrogen. The minimum requirements of H2O/fuel ratio for each type of fuel in which the carbon formation is thermodynamically unfavored were compared. At the same operating conditions, DIR-SOFC fueled by ethanol required the lowest inlet H2O/fuel ratio in which the carbon formation is thermodynamically unfavored. The requirement decreased with increasing temperature for all three fuels. Comparison between two types of the electrolytes reveals that the hydrogen-conducting electrolyte is impractical for use, regarding to the tendency of carbon formation. This is due mainly to the water formed by the electrochemical reaction at the electrodes. (author)

  8. Metabolism of methanol in acetogenic bacteria

    Ivey, D.K.W.

    1987-01-01

    Acetogens can grown on methanol in the presence of a cosubstrate that is more oxidized than methanol. Three mol of acetate is formed from 4 mol methanol and 2 mol CO 2 . One mol of methanol is oxidized to CO 2 . The levels of the tetrahydrofolate enzymes, carbon monoxide dehydrogenase, and corrinoids indicate the presence of the acetyl CoA pathway when growing on methanol. The acetyl-CoA pathway of acetate synthesis as presently understood does not include methanol as a substrate. It is demonstrated that methanol is oxidized to formaldehyde and then to formate by a methanol dehydrogenase. It is also possible that the methyl group of methanol is transferred directly to either a corrinoid-type enzyme, or tetrahydrofolate. When cells of C. thermoautotrophicum are grown on 14 CO 2 , acetate becomes labeled in both carbons with a ratio 14 CH 3 / 14 COOH of 0.7. In addition, methanol gets labeled. When cells are grown on 14 CH 3 OH, label appears in both acetate carbons with a ratio of 3.3, and also appears in CO 2 . Thus methanol is preferentially incorporated into the methyl group of acetate, whereas CO 2 is the preferred source of the carboxyl carbon

  9. Triboluminescence and associated decomposition of solid methanol

    Trout, G.J.; Moore, D.E.; Hawke, J.G.

    1975-01-01

    The decomposition is initiated by the cooling of solid methanol through the β → α transiRon at 157.8K, producing the gases hydrogen, carbon monoxide, and methane. The passage through this lambda transition causes the breakup of large crystals of β-methanol into crystallites of α-methanol and is accompanied by light emission as well as decomposition. This triboluminescence is accompanied by, and apparently produced by, electrical discharges through methanol vapor in the vicinity of the solid. The potential differences needed to produce the electrical breakdown of the methanol vapor apparently arise from the disruption of the long hydrogen bonded chains of methanol molecules present in crystalline methanol. Charge separation following crystal deformation is a characteristic of substances which exhibit gas discharge triboluminescence; solid methanol has been found to emit such luminescence when mechanically deformed in the absence of the β → α transition The decomposition products are not produced directly by the breaking up of the solid methanol but from the vapor phase methanol by the electrical discharges. That gas phase decomposition does occur was confirmed by observing that the vapors of C 2 H 5 OH, CH 3 OD, and CD 3 OD decompose on being admitted to a vessel containing methanol undergoing the β → α phase transition. (U.S.)

  10. Reduction of FFA in jatropha curcas oil via sequential direct-ultrasonic irradiation and dosage of methanol/sulfuric acid catalyst mixture on esterification process

    Andrade-Tacca, Cesar Augusto; Chang, Chia-Chi; Chen, Yi-Hung; Ji, Dar-Ren; Wang, Yi-Yu; Yen, Yue-Quen; Chang, Ching-Yuan

    2014-01-01

    Highlights: • Ultrasonic irradiation (UI) can auto-induce temperature rise. • Esterification at higher temperature (T) by UI offers greater reduction of acid value. • Sequential UI and catalyst dosing enhance esterification conversion efficiency (η). • UR of jatropha oil at higher T results in less water content on ester as product. • A 99.35% of η is achievable via sequential UI and dosing of 5 mL per dose. - Abstract: Production of jatropha-ester (JO-ester) from jatropha oil (JO) under sequential direct-ultrasonic irradiation (UI) with auto-induced temperature rise followed by adding a mixture of methanol/sulfuric-acid catalyst (M/C) dose between high temperature intervals was studied. Comparisons with various doses of 5, 10, 16.6 and 25 mL at different temperature intervals of 108.9–120 °C, 100–120 °C, 85–120 °C and 75–120 °C respectively were performed. System parameters examined include: esterification times (t E ) for UI, settling time (t S ) after esterification and temperature (T). Properties of acid value (AV), iodine value (IV), kinematic viscosity (kV), density (ρ LO ) and water content (m w ) of JO and JO-ester product were measured. The esterification conversion efficiencies (η) were determined and assessed. An η of 99.35% was obtained at temperature interval of 108.9–120 °C with 5 mL per dose for 20 doses and t E of 167.39 min (denoted as Process U 120-5 ), which is slightly higher than η of 98.87% at temperature interval of 75–120 °C with 25 mL per dose for 4 doses and t E of 108.79 min (noted as Process U 120-25 ). The JO-ester obtained via sequential UI with adding doses of 5 mL possess AV of 0.24 mg KOH/g, IV of 124.77 g I 2 /100 g, kV of 9.89 mm 2 /s, ρ LO of 901.73 kg/m 3 and m w of 0.3 wt.% showing that sequential UI and dose at higher temperature interval can give higher reduction of AV compared with 36.56 mg KOH/g of original oil. The effects of t S and t E on AV are of minor and moderate importance

  11. Property Enhancement Effects of Side-Chain-Type Naphthalene-Based Sulfonated Poly(arylene ether ketone) on Nafion Composite Membranes for Direct Methanol Fuel Cells.

    Wang, Baolong; Hong, Lihua; Li, Yunfeng; Zhao, Liang; Zhao, Chengji; Na, Hui

    2017-09-20

    Nafion/SNPAEK-x composite membranes were prepared by blending raw Nafion and synthesized side-chain-type naphthalene-based sulfonated poly(arylene ether ketone) with a sulfonation degree of 1.35 (SNPAEK-1.35). The incorporation of SNPAEK-1.35 polymer with ion exchange capacity (IEC) of 2.01 mequiv·g -1 into a Nafion matrix has the property enhancement effects, such as increasing IECs, improving proton conductivity, enhancing mechanical properties, reducing methanol crossover, and improving single cell performance of Nafion. Morphology studies show that Nafion/SNPAEK-x composite membranes exhibit a well-defined microphase separation structure depending on the contents of SNPAEK-1.35 polymer. Among them, Nafion/SNPAEK-7.5% with a bicontinuous morphology exhibits the best comprehensive properties. For example, it shows the highest proton conductivities of 0.092 S cm -1 at 25 °C and 0.163 S cm -1 at 80 °C, which are higher than those of recast Nafion with 0.073 S cm -1 at 25 °C and 0.133 S cm -1 at 80 °C, respectively. Nafion/SNPAEK-5.0% and Nafion/SNPAEK-7.5% membranes display an open circuit voltage of 0.77 V and a maximum power density of 47 mW cm -2 at 80 °C, which are much higher than those of recast Nafion of 0.63 V and 24 mW cm -2 under the same conditions. Nafion/SNPAEK-5.0% membrane also has comparable tensile strength (12.7 MPa) to recast Nafion (13.7 MPa), and higher Young's modulus (330 MPa) than that of recast Nafion (240 MPa). By combining their high proton conductivities, comparable mechanical properties, and good single cell performance, Nafion/SNPAEK-x composite membranes have the potential to be polymer electrolyte materials for direct methanol fuel cell applications.

  12. Cu₂O template synthesis of high-performance PtCu alloy yolk-shell cube catalysts for direct methanol fuel cells.

    Ye, Sheng-Hua; He, Xu-Jun; Ding, Liang-Xin; Pan, Zheng-Wei; Tong, Ye-Xiang; Wu, Mingmei; Li, Gao-Ren

    2014-10-21

    Novel PtCu alloy yolk-shell cubes were fabricated via the disproportionation and displacement reactions in Cu2O yolk-shell cubes, and they exhibit significantly improved catalytic activity and durability for methanol electrooxidation.

  13. Direct numerical simulation of 3D particle motion in an evaporating liquid film

    Hwang, Ho Chan; Son, Gi Hun

    2016-01-01

    A direct numerical simulation method is developed for 3D particle motion in liquid film evaporation. The liquid-gas and fluid-solid interfaces are tracked by a sharp-interface Level-set (LS) method, which includes the effects of evaporation, contact line and solid particles. The LS method is validated through simulation of the interaction between two particles falling in a single-phase fluid. The LS based DNS method is applied to computation of the particle motion in liquid film evaporation to investigate the particle-interface and particle-particle interactions

  14. Activity coefficients, interfacial tensions and retention in reversed-phase liquid chormatography on LiChrosorb RP-18 with methanol-water mixtures

    Hammers, W.E.; Meurs, G.J.; Ligny, C.L. de

    1982-01-01

    Literature data on activity coefficients of various solutes in water, of some tetraalkyl compounds in methanol-water mixture and of water in organic solvents have been correlated with the product of the molecular surface area of the solute and the solute-solvent interfacial tension at ambient

  15. Development of an Efficient Methanol Production Process for Direct CO2 Hydrogenation over a Cu/ZnO/Al2O3 Catalyst

    Fereshteh Samimi

    2017-11-01

    Full Text Available Carbon capture and utilization as a raw material for methanol production are options for addressing energy problems and global warming. However, the commercial methanol synthesis catalyst offers a poor efficiency in CO2 feedstock because of a low conversion of CO2 and its deactivation resulting from high water production during the process. To overcome these barriers, an efficient process consisting of three stage heat exchanger reactors was proposed for CO2 hydrogenation. The catalyst volume in the conventional methanol reactor (CR is divided into three sections to load reactors. The product stream of each reactor is conveyed to a flash drum to remove methanol and water from the unreacted gases (H2, CO and CO2. Then, the gaseous stream enters the top of the next reactor as the inlet feed. This novel configuration increases CO2 conversion almost twice compared to one stage reactor. Also to reduce water production, a water permselective membrane was assisted in each reactor to remove water from the reaction side. The proposed process was compared with one stage reactor and CR from coal and natural gas. Methanol is produced 288, 305, 586 and 569 ton/day in CR, one-stage, three-stage and three-stage membrane reactors (MR, respectively. Although methanol production rate in three-stage MR is a bit lower than three stage reactors, the produced water, as the cause of catalyst poisoning, is notably reduced in this configuration. Results show that the proposed process is a strongly feasible way to produce methanol that can competitive with a traditional synthesis process.

  16. CeO2/rGO/Pt sandwich nanostructure: rGO-enhanced electron transmission between metal oxide and metal nanoparticles for anodic methanol oxidation of direct methanol fuel cells.

    Yu, Xue; Kuai, Long; Geng, Baoyou

    2012-09-21

    Pt-based nanocomposites have been of great research interest. In this paper, we design an efficient MO/rGO/Pt sandwich nanostructure as an anodic electrocatalyst for DMFCs with combination of the merits of rigid structure of metallic oxides (MOs) and excellent electronic conductivity of reduced oxidized graphene (rGO) as well as overcoming their shortcomings. In this case, the CeO(2)/rGO/Pt sandwich nanostructure is successfully fabricated through a facile hydrothermal approach in the presence of graphene oxide and CeO(2) nanoparticles. This structure has a unique building architecture where rGO wraps up the CeO(2) nanoparticles and Pt nanoparticles are homogeneously dispersed on the surface of rGO. This novel structure endows this material with great electrocatalytic performance in methanol oxidation: it reduces the overpotential of methanol oxidation significantly and its electrocatalytic activity and stability are much enhanced compared with Pt/rGO, CeO(2)/Pt and Pt/C catalysts. This work supplies a unique MO/rGO/Pt sandwich nanostructure as an efficient way to improve the electrocatalytic performance, which will surely shed some light on the exploration of some novel structures of electrocatalyst for DMFCs.

  17. Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

    Shan, Junjun; Li, Mengwei; Allard, Lawrence F.; Lee, Sungsik; Flytzani-Stephanopoulos, Maria

    2017-11-01

    An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. We find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolite-supported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. We anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful

  18. Thermophysical properties of biodiesel and related systems. Part I. Vapour–liquid equilibrium at low pressures of binary and ternary systems involving methanol, ethanol, glycerol, water and NaCl

    Veneral, Josamaique G.; Benazzi, Tassio; Mazutti, Marcio A.; Voll, Fernando A.P.; Cardozo-Filho, Lúcio; Corazza, Marcos L.; Guirardello, Reginaldo; Vladimir Oliveira, J.

    2013-01-01

    Highlights: ► Experimental vapour–liquid equilibrium data of multicomponent mixtures of biodiesel-related systems. ► Othmer-type ebulliometer in the pressure range of 6.7 to 66.7 kPa. ► Experimental data satisfactorily represented by the UNIQUAC model. -- Abstract: Experimental vapour–liquid equilibrium data of several binary mixtures (methanol + glycerol), (ethanol + glycerol) and (glycerol + water) and ternary (methanol + glycerol + water), (ethanol + glycerol + water) and (water + glycerol + NaCl) were obtained over the pressure range of 6.7 kPa to 66.7 kPa through an Othmer-type ebulliometer, allowing the construction of temperature – mass fraction and pressure – temperature diagrams. It is shown that the systems without NaCl were satisfactorily represented by the UNIQUAC model with good agreement between theory and experimental results. It was observed that alcohol concentrations lower than 10 wt% increase the phase transition temperature. The systems investigated show positive deviations in relation to Raoult’s law. Results presented in this work may be relevant in process design towards efficient recovering of components in the biodiesel down-stream processes

  19. Three dimensional PtRh alloy porous nanostructures: tuning the atomic composition and controlling the morphology for the application of direct methanol fuel cells

    Zhang, Yuan [Department of Chemistry, Shanghai University, Shanghai 200444 (China); Department of Chemical Engineering, Case Western Reserve University, Cleveland, OH 44106 (United States); Janyasupab, Metini; Liu, Chung-Chiun [Department of Chemical Engineering, Case Western Reserve University, Cleveland, OH 44106 (United States); Liu, Chen-Wei [Institute of Material Sciences and Engineering, National Central University, Chung-Li 320 (China); Li, Xinxin [State Key Laboratory of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China); Xu, Jiaqiang [Department of Chemistry, Shanghai University, Shanghai 200444 (China)

    2012-09-11

    A strategy for the synthesis of PtRh alloy 3D porous nanostructures by controlled aggregation of nanoparticles in oleylamine is presented. The atomic ratio between the two components (Pt and Rh) is tuned by varying the concentration of precursor salts accommodating the oxidation of methanol. The morphology of PtRh alloy nanostructure is controlled by elevating the temperature of the reaction system to 240 C. The prepared 3D porous nanostructures provide a high degree of electrochemical activity and good durability toward the methanol oxidation reaction compared to those of the commercial Pt/C (E-TEK) and PtRh nanoparticles. Therefore, the 3D alloy porous nanostructures provide a good opportunity to explore their catalytic properties for methanol oxidation. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Stability studies of oxytetracycline in methanol solution

    Wang, Wei; Wu, Nan; Yang, Jinghui; Zeng, Ming; Xu, Chenshan; Li, Lun; Zhang, Meng; Li, Liting

    2018-02-01

    As one kind of typical tetracycline antibiotics, antibiotic residues of oxytetracycline have been frequently detected in many environmental media. In this study, the stability of oxytetracycline in methanol solution was investigated by high-performance liquid chromatography combined with UV-vis (HPLC-UV). The results show that the stability of oxytetracycline in methanol solution is highly related to its initial concentration and the preserved temperature. Under low temperature condition, the solution was more stable than under room temperature preservation. Under the same temperature preservation condition, high concentrations of stock solutions are more stable than low concentrations. The study provides a foundation for preserving the oxytetracycline-methanol solution.

  1. Volumetric and viscosity properties of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid in methanol%[Bmim]BF4离子液体在甲醇中的体积和黏度性质

    李诗琴; 周贤丰; 许映杰

    2013-01-01

    在298.15 K和常压下,测定了1-丁基-3-甲基咪唑四氟硼酸([Bmim] BF4)离子液体+甲醇体系的密度和黏度.由密度计算了体系的表观摩尔体积,并采用Redlich-Mayer方程关联了体系的表观摩尔体积与组成的关系,得到了[Bmim]BF4在甲醇中的标准偏摩尔体积.由Jones-Dole方程对体系的黏度随组成的变化进行了拟合,获得了[Bmim] BF4在甲醇中的黏度B系数.结果表明:[Bmim] BF4+甲醇体系的表观摩尔体积和黏度均随[Bmim] BF4浓度的增加而增加,[Bmim] BF4在甲醇中的标准偏摩尔体积和黏度B系数分别为155.72×10-6m3/mol和0.282 9.%Densities and viscosities of l-butyl-3-methylimi-dazolium tetrafluoroborate ionic liquid ( [ Bmim ] BF4 ) with methanol were measured at 298. 15 K and atmospheric pressure. Apparent molar volumes, Vf of the above-mentioned mixture were determined from the experimental densities. Standard partial molar volume , Vo/f of [ Bmim] BF4 in methanol was estimated by the Redlich-Mayer equation. The achieved viscosities were used to calculate the viscosity B-coefficient of [ Bmim ] BF4 in methanol through Jones-Dole equation. The results indicate that the apparent molar volumes and viscosities increase with increasing of ionic liquid concentration. Standard partial molar volume and viscosity B-coefficient of [Bmim] BF4 in methanol is 155.72 ?10-6 m3 穖ol-1 and 0.282 9,respectively.

  2. DIRECT FORMATION OF TETRAHYDROPYRANOLS VIA CATALYSIS IN IONIC LIQUID. (R828129)

    Utilizing a simple homoallyl alcohol and an aldehyde in the presence of a catalytic amount of cerium triflate, the direct stereoselective formation of tetrahydropyranol derivatives in ionic liquid is reported.

    Bifunctional catalysts for the direct production of liquid fuels from syngas

    Sartipi, S.

    2014-01-01

    Design and development of catalyst formulations that maximize the direct production of liquid fuels by combining Fischer-Tropsch synthesis (FTS), hydrocarbon cracking, and isomerization into one single catalyst particle (bifunctional FTS catalyst) have been investigated in this thesis. To achieve

  3. Direct conversion of glucose to 5-(hydroxymethyl)furfural in ionic liquids with lanthanide catalysts

    Ståhlberg, Tim; Sørensen, Mathilde Grau; Riisager, Anders

    2010-01-01

    The direct conversion of glucose to 5-(hydroxymethyl)furfural (HMF) in ionic liquids with lanthanide catalysts was examined in search of a possibly more environmentally feasible process not involving chromium. The highest HMF yield was obtained with ytterbium chloride or triflate together...

  4. Study liquid length penetration results obtained with a direct acting piezo electric injector

    Payri, Raul; Gimeno, Jaime; Bardi, Michele; Plazas, Alejandro H.

    2013-01-01

    Highlights: ► A direct acting injector capable of controlling needle lift has been used to determine liquid phase penetration. ► The influence of injection pressure, chamber density and chamber temperature have been measured. ► When needle lift is reduced the stabilized liquid length is shortened. ► The relationship between needle lift and liquid length makes needle lift as a new way to control the injection event. - Abstract: A state of the art prototype common rail injector featuring direct control of the needle by means of a piezo stack (direct acting) has been tested. Liquid phase penetration of the sprays in diesel engine-like conditions has been studied via imaging technique in a novel continuous flow test chamber that allows an accurate control on a wide range of thermodynamic conditions (up to 1000 K and 15 MPa). This state of the art injector fitted with a 7-hole nozzle, allows a fully flexible control on the nozzle needle movement, enabling various fuel injection rate typologies. The temporal evolution of the seven sprays has been studied recording movies of the injection event in evaporative conditions via Mie scattering imaging technique and using a high speed camera. The results showed a strong influence of needle position on the stabilized liquid length while the effect of the injection pressure is negligible: the decrease of the needle lift causes a pressure drop in the needle seat and thus a reduction in the effective pressure upstream of the orifices (in the nozzle sac). According to known literature the stabilized liquid-length depends mainly on effective diameter, spray cone-angle and fuel/air properties and does not depend on fuel velocity at the orifice outlet. Therefore, due to small change in the spray cone-angle, higher injection pressures give slightly lower liquid length. However, partial needle lifts has an opposite effect: when needle is partially lifted a dramatic increase of the spray cone-angle and a consequent reduction of

  5. A vapor feed methanol microfluidic fuel cell with high fuel and energy efficiency

    Wang, Yifei; Leung, Dennis Y.C.; Xuan, Jin; Wang, Huizhi

    2015-01-01

    Highlights: • A microfluidic fuel cell with a vapor feed anode is investigated. • Its advantages include simpler design, direct usage of methanol and better performance. • The prototype achieves a peak power density of 55.4 mW cm −2 under room temperature. • The energy efficiency of 9.4% is much higher than its liquid feed counterpart. - Abstract: In this paper, a prototype of methanol microfluidic fuel cell with vapor feed anode configuration is proposed to improve the fuel and energy efficiency of the conventional liquid feed methanol microfluidic fuel cells. Peak power density of 55.4 mW cm −2 can be achieved with this prototype under room temperature, which is 30% higher than its conventional liquid feed counterpart. Moreover, an energy efficiency of 9.4% is achieved, which is 27.5 times higher than its liquid feed counterpart. This superiority on both cell performance and energy efficiency is directly benefitted from its vapor feed anode configuration, which alleviates the fuel crossover, eliminates the fuel depletion boundary layer, and avoids the bulk anolyte wastage. The tradeoff between cell performance and fuel utilization for conventional liquid feed microfluidic fuel cells is also evaded

  6. Process for obtaining methanol. Verfahren zur Gewinnung von Methanol

    Link, H; Watson, A

    1983-12-08

    Synthetic gas is generated and converted to methanol in a reactor. After the separation of the crude methanol, there is a multi-stage methanol distillation. Condensate occurring during distillation is at least partly fed back before the methanol synthesis.

  7. Determination of piroxicam in pharmaceutical preparations by ultraviolet direct spectrophotometry, ultraviolet difference spectrophotometry and high performance liquid chromatography

    Hackmann, E.R.M.; Santos Gianotto, E.A. dos; Miritello Santoro, M.I.R. (Universidade de Sao Paulo (Brazil))

    1993-02-01

    Piroxicam in pharmaceutical preparations (capsules (C), tablets (T), oral drops (OD), suppositories (S) and simulated sample (SS)) was determined by UV direct spectrophotometry (UVS) at 333 nm, by UV difference spectrophotometry (UVDS) at 327 nm, and in C and T, by high performance liquid chromatography (HPLC). For UVS, Beer's law was obeyed in the range 3.0-8.5 [mu]g/mL. The coefficient of correlation (CC), absolute precision (AP) and relative precision (RP) were 0.9999, 0.02 and 0.33%, respectively. The coefficient of variation (CV) for C, T, OD, S and SS were 0.48%, 0.35%, 0.48% and 0.19%, respectively. The recovery average (RA) was 100.22%. For UVDS, Beer's law was obeyed in the range 5.0-15.0 [mu]g/mL. The CC, AP and RP were respectively 0.9999, 0.05 and 0.47%. The CV for C, T, OD, S and SS were 0.64%, 0.84%, 0.62%, 0.54% and 0.15%, respectively. The RA was 99.02%. In HPLC determination, a LiChrospher[reg sign] 100 RP-18 (5 [mu]m) in LiChroCART[reg sign] 125-4 column at ambient temperature with a mobile phase consisting of methanol: (buffer solution citric acid-dibasic sodium phosphate pH 3.0) (55:45) and UV detection at 254 nm enabled the determination of piroxicam in C and T. The response peak area versus concentration presented linearity in the range 10.0-100.0 [mu]g/mL. The CC, AP and RP were 0.9997, 0.45 and 0.90%, respectively. The CV was 0.51%-0.82% and the RA, 97.13%. 14 refs., 1 fig., 5 tabs.

  8. Ultrasonic pumping of liquids in the two directions of a vertical tube by a vibrating surface

    Santillan, Arturo Orozco; Cutanda Henriquez, Vicente

    2010-01-01

    of the oscillations of the vibrating horizontal surface determine the direction in which the liquid is pumped. In addition, the size of the gap is also a relevant factor, which has to be significantly small. The carried out numerical simulations show that the Lagrangian excess pressure and the density of linear......It has been reported that it is possible to pump a liquid into the interior of a vertical pipe when its lower end is facing a vibrating plane surface immersed in the liquid. The column of liquid pumped in a thin pipe can be higher than 2 m if the gap between the pipe end and the vibrating...... horizontal surface is very small, around 0.01 mm. In this paper we present experimental results showing that, with a similar set up as the one mentioned above, it is also possible to pump liquids in the opposite direction, from the interior of the pipe through the gap. The general objective of the work has...

  9. Direct analysis of formate in human plasma, serum and whole blood by in-line coupling of microdialysis to capillary electrophoresis for rapid diagnosis of methanol poisoning

    Kubáň, Pavel; Boček, Petr

    2013-01-01

    Roč. 768, 21 JAN (2013), s. 82-89 ISSN 0003-2670 R&D Projects: GA ČR GAP206/10/1219 Institutional support: RVO:68081715 Keywords : capillary electrophoresis * in-line microdialysis * methanol intoxication Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 4.517, year: 2013

  10. A facile approach to the synthesis of highly electroactive Pt nanoparticles on graphene as an anode catalyst for direct methanol fuel cells.

    Zhou, Yi-Ge; Chen, Jing-Jing; Wang, Feng-bin; Sheng, Zhen-Huan; Xia, Xing-Hua

    2010-08-28

    A one-step electrochemical approach to the synthesis of highly dispersed Pt nanoparticles on graphene has been proposed. The resultant Pt NPs@G nanocomposite shows higher electrocatalytic activity and long-term stability towards methanol electrooxidation than the Pt NPs@Vulcan.

  11. Modelling (vapour + liquid) and (vapour + liquid + liquid) equilibria of {water (H2O) + methanol (MeOH) + dimethyl ether (DME) + carbon dioxide (CO2)} quaternary system using the Peng-Robinson EoS with Wong-Sandler mixing rule

    Ye Kongmeng; Freund, Hannsjoerg; Sundmacher, Kai

    2011-01-01

    Highlights: → Phase behaviour modelling of H 2 O-MeOH-DME under pressurized CO 2 (anti-solvent) using PRWS. → PRWS-UNIFAC-PSRK has better performance than PRWS-UNIFAC-Lby in general. → Reliable to extend the VLE and VLLE phase behaviour from binary to multicomponent systems. → Successful prediction of the VLE and VLLE of binary, ternary, and quaternary systems. → Potential to apply the model for designing new DME separation process. - Abstract: The (vapour + liquid) equilibria (VLE) and (vapour + liquid + liquid) equilibria (VLLE) binary data from literature were correlated using the Peng-Robinson (PR) equation of state (EoS) with the Wong-Sandler mixing rule (WS). Two group contribution activity models were used in the PRWS: UNIFAC-PSRK and UNIFAC-Lby. The systems were successfully extrapolated from the binary systems to ternary and quaternary systems. Results indicate that the PRWS-UNIFAC-PSRK generally displays a better performance than the PRWS-UNIFAC-Lby.

  12. Methanol Fuel Cell

    Voecks, G. E.

    1985-01-01

    In proposed fuel-cell system, methanol converted to hydrogen in two places. External fuel processor converts only part of methanol. Remaining methanol converted in fuel cell itself, in reaction at anode. As result, size of fuel processor reduced, system efficiency increased, and cost lowered.

  13. Nuclear recoil energy scale in liquid xenon with application to the direct detection of dark matter

    Sorensen, Peter; Dahl, Carl Eric

    2011-01-01

    We show for the first time that the quenching of electronic excitation from nuclear recoils in liquid xenon is well-described by Lindhard theory, if the nuclear recoil energy is reconstructed using the combined (scintillation and ionization) energy scale proposed by Shutt et al. We argue for the adoption of this perspective in favor of the existing preference for reconstructing nuclear recoil energy solely from primary scintillation. We show that signal partitioning into scintillation and ionization is well described by the Thomas-Imel box model. We discuss the implications for liquid xenon detectors aimed at the direct detection of dark matter.

  14. Liquid Chromatography with Post-Column Reagent Addition of Ammonia in Methanol Coupled to Negative Ion Electrospray Ionization Tandem Mass Spectrometry for Determination of Phenoxyacid Herbicides and their Degradation Products in Surface Water

    Michele L. Etter

    2010-02-01

    Full Text Available A new liquid chromatography (LC-negative ion electrospray ionization (ESI–tandem mass spectrometry (MS/MS method with post-column addition of ammonia in methanol has been developed for the analysis of acid herbicides: 2,4-dichlorophenoxy ace- tic acid, 4-chloro-o-tolyloxyacetic acid, 2-(2-methyl-4-chlorophenoxybutyric acid, mecoprop, dichlorprop, 4-(2,4-dichlorophenoxy butyric acid, 2,4,5-trichlorophenoxy propionic acid, dicamba and bromoxynil, along with their degradation products: 4-chloro-2- methylphenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol and 3,5-dibromo-4-hydroxybenzoic acid. The samples were extracted from the surface water matrix using solid-phase extraction (SPE with a polymeric sorbent and analyzed with LC ESI- with selected reaction monitoring (SRM using a three-point confirmation approach. Chromatography was performed on a Zorbax Eclipse XDB-C18 (50 × 4.6 mm i.d., 1.8 µm with a gradient elution using water-methanol with 2 mM ammonium acetate mobile phase at a flow rate of 0.15 mL/min. Ammonia in methanol (0.8 M was added post-column at a flow rate of 0.05 mL/min to enhance ionization of the deg- radation products in the MS source. One SRM transition was used for quantitative analysis while the second SRM along with the ratio of SRM1/SRM2 within the relative standard deviation determined by standards for each individual pesticide and retention time match were used for confirmation. The standard deviation of ratio of SRM1/SRM2 obtained from standards run on the day of analysis for different phenoxyacid herbicides ranged from 3.9 to 18.5%. Limits of detection (LOD were between 1 and 15 ng L-1 and method detection limits (MDL with strict criteria requiring

  15. Development of vanadium-phosphate catalysts for methanol production by selective oxidation of methane

    McCormick, R.L. [Colorado School of Mines, Golden, CO (United States)

    1995-12-31

    The United States has vast natural gas reserves which could contribute significantly to our energy security if economical technologies for conversion to liquid fuels and chemicals were developed. Many of these reserves are small scale or in remote locations and of little value unless they can be transported to consumers. Transportation is economically performed via pipeline, but this route is usually unavailable in remote locations. Another option is to convert the methane in the gas to liquid hydrocarbons, such as methanol, which can easily and economically be transported by truck. Therefore, the conversion of methane to liquid hydrocarbons has the potential to decrease our dependence upon oil imports by opening new markets for natural gas and increasing its use in the transportation and chemical sectors of the economy. In this project, we are attempting to develop, and explore new catalysts capable of direct oxidation of methane to methanol. The specific objectives of this work are discussed.

  16. A simple multi-residue method for the determination of pesticides in fruits and vegetables using a methanolic extraction and ultra-high-performance liquid chromatography-tandem mass spectrometry: optimization and extension of scope.

    Hanot, V; Goscinny, S; Deridder, M

    2015-03-06

    In 2004, a new multi-residue pesticides method had been published using methanol as extraction solvent. Our goal for this study was to optimize the analytical scheme while extending the compound scope from 19 to 200 pesticides. The main changes from the original method take place at the sample extraction and processing with a special attention to make the overall method fit for routine analysis with minimal cost. Hence, after a quick Ultra-Turrax homogenization with a methanolic solution, the sample is simply diluted before the separation and detection by ultra-high-performance liquid chromatography and MS/MS detection for quantitative and confirmatory purposes. The performance of the method including limits of quantification (LOQs), linearity, matrix effect, precision was evaluated during validation in accordance with the European Union SANCO/12571/2013 regulatory guidelines. Two representative matrices, lettuce and orange, were selected and fortified at two concentration levels for these experiments. At the LOQ and ten times the LOQ, recoveries of the analytes were mostly within 70-120%, with coefficients of variation lower than 25% in intra-day repeatability conditions. In addition to being simple and fast, these results demonstrate the suitability of the optimized method for the analysis of large scope pesticides in routine laboratories. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Synthesis of silicon containing materials using liquid hydrosilane compositions through direct injection

    Srinivasan, Guruvenket; Sailer, Robert A.; Hoey, Justin

    2018-03-13

    An apparatus and a non-vapor-pressure dependent method of chemical vapor deposition of Si based materials using direct injection of liquid hydrosilane(s) are presented. Liquid silane precursor solutions may also include metal, non-metal or metalloid dopants, nanomaterials and solvents. An illustrative apparatus has a precursor solution and carrier gas system, atomizer and deposit head with interior chamber and a hot plate supporting the substrate. Atomized liquid silane precursor solutions and carrier gas moves through a confined reaction zone that may be heated and the aerosol and vapor are deposited on a substrate to form a thin film. The substrate may be heated prior to deposition. The deposited film may be processed further with thermal or laser processing.

  18. Liquid direct correlation function, singlet densities and the theory of freezing

    March, N.H.; Tosi, M.P.

    1981-04-01

    We have examined the solutions for the singlet density rho(r) in the hierarchical equation connecting rho(r) with the liquid direct correlation function c(r). In addition to the homogeneous solution rho(r)=rhosub(liquid), we exhibit a periodic solution which can co-exist with the liquid solution. If the defining equation for this is linearized, we recover the bifurcation condition of Lovett and Buff. We stress the difference between the two treatments as that between first and second-order transitions. It turns out that the treatment presented here leads to the same periodic density as that derived, using the hypernetted chain approximation, by Ramakrishnan and Yussouff in their theory of freezing. Invoking that approximation is shown thereby to be inessential. (author)

  19. Polymer-Derived In- Situ Metal Matrix Composites Created by Direct Injection of a Liquid Polymer into Molten Magnesium

    Sudarshan; Terauds, Kalvis; Anilchandra, A. R.; Raj, Rishi

    2014-02-01

    We show that a liquid organic precursor can be injected directly into molten magnesium to produce nanoscale ceramic dispersions within the melt. The castings made in this way possess good resistance to tensile deformation at 673 K (400 °C), confirming the non-coarsening nature of these dispersions. Direct liquid injection into molten metals is a significant step toward inserting different chemistries of liquid precursors to generate a variety of polymer-derived metal matrix composites.

  1. Effect of the solvent in the catalyst ink preparation on the properties and performance of unsupported PtRu catalyst layers in direct methanol fuel cells

    Alcaide, Francisco; Álvarez, Garbiñe; Cabot, Pere L.; Genova-Koleva, Radostina; Grande, Hans-Jürgen; Miguel, Oscar

    2017-01-01

    The effect of the organic solvent polarity on the properties of unsupported PtRu catalyst inks and on the performance of the catalyst layers prepared with them for the methanol electrooxidation, has been studied. The light scattering results indicate that the PtRu-Nafion ® aggregates in the inks prepared with n-butyl acetate (NBA) are larger than those prepared with 2-propanol (IPA). The lower polarity of the former favours the aggregation of Nafion ® and nanoparticles. The electron microscopy images and porosimetry measurements of the catalyst layers show that the secondary pore volume between the agglomerates is larger for NBA. The linear sweep voltammetry and eis results for the methanol electrooxidation in the three-electrode cell denote the higher active surface area for NBA and comparable specific oxidation rates of the intermediates in both catalysts layers. The current densities for PtRu anode catalyst layers in single DMFC are higher when the solvent is NBA, the mass transport limitations being much more apparent with IPA. The adapted transmission line equivalent circuit to interpret the impedance results in single DMFC indicates that the proton resistance for NBA is significantly lower than for IPA, thus suggesting that the greater number of accessible active sites for methanol oxidation in the former are well connected to the Nafion ® ionomers and easier transported to the membrane.

  2. Study on fuel supplying method and methanol concentration sensor for the high efficient operation of methanol fuel cells. Methanol nenryo denchi no unten ni okeru nenryo kyokyu hoho no kento to methanol nodo sensor no kaihatsu

    Tsukui, Tsutomu; Doi, Ryota; Yasukawa, Saburo; Kuroda, Osamu [Hirachi, Ltd., Tokyo, (Japan)

    1990-01-20

    A fuel supplying method was studied and demonstrated, essential to the high efficient operation of methanol fuel cells. Methanol and water were supplied independently from each tank to an anordic electrolyte tank in a circulating system, detecting a methanol concentration and liquid level of anordic electrolyte by each sensor, respectively. A methanol sensor was also developed to detect accurately the concentration based on electrochemical reaction under a constant voltage. A detection control circuit was insulated from a constant-voltage power supply to prevent external noises. The methanol sensor output was compensated for temperature, and a new level sensing method was adopted to send out a command comparing different responses to electrolyte shortage. As the methanol fuel cell was operated with this fuel supplying system, the stable characteristics of the cell were obtained within the variation of {plus minus} 0.1mol/l from the specified methanol concentration. 6 refs., 17 figs., 1 tab.

  3. Compact Fuel-Cell System Would Consume Neat Methanol

    Narayanan, Sekharipuram; Kindler, Andrew; Valdez, Thomas

    2007-01-01

    In a proposed direct methanol fuel-cell electric-power-generating system, the fuel cells would consume neat methanol, in contradistinction to the dilute aqueous methanol solutions consumed in prior direct methanol fuel-cell systems. The design concept of the proposed fuel-cell system takes advantage of (1) electro-osmotic drag and diffusion processes to manage the flows of hydrogen and water between the anode and the cathode and (2) evaporative cooling for regulating temperature. The design concept provides for supplying enough water to the anodes to enable the use of neat methanol while ensuring conservation of water for the whole fuel-cell system.

  4. Recycling of greenhouse gases via methanol

    Bill, A [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Eliasson, B; Kogelschatz, U [ABB Corporate Research Center, Baden-Daettwil (Switzerland)

    1997-06-01

    Greenhouse gas emissions to the atmosphere can be mitigated by using direct control technologies (capture, disposal or chemical recycling). We report on carbon dioxide and methane recycling with other chemicals, especially with hydrogen and oxygen, to methanol. Methanol synthesis from CO{sub 2} is investigated on various catalysts at moderate pressures ({<=}30 bar) and temperatures ({<=}300{sup o}C). The catalysts show good methanol activities and selectivities. The conversion of CO{sub 2} and CH{sub 4} to methanol is also studied in a silent electrical discharge at pressures of 1 to 4 bar and temperatures close to room temperature. Methanol yields are given for mixtures of CO{sub 2}/H{sub 2}, CH{sub 4}/O{sub 2} and also for CH{sub 4} and air mixtures. (author) 2 figs., 5 refs.

  5. Fabrication of MEA based on optimum amount of Co in PdxCo/C alloy nanoparticles as a new cathode for oxygen reduction reaction in passive direct methanol fuel cells

    Gharibi, Hussein; Golmohammadi, Farhad; Kheirmand, Mehdi

    2013-01-01

    Highlights: ► The optimal amount of Pd/Co in the catalyst layer reduces the polarization resistance in comparison with Pd alone. ► The Pd/Co in catalyst layer increases the Pd utilization in the ORR. ► The DMFC test results indicate that the MEA prepared from Pd 3 Co/C cathode exhibits best performance. -- Abstract: Carbon supported Pd and Pd x Co alloy electrocatalysts of different Pd x Co atomic ratios (x = 1, 2, 3 and 10) were prepared by the impregnation synthesis method at room temperature without heat treatment by ethylene glycol (EG) reduction. As prepared Pd x Co bimetallic nanoparticles show a single-phase face-centered-cubic (fcc) disordered structure. The performance of these electrodes in the ORR was measured with cyclic voltammetry (CV), linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), chronoamperometry (CA), inductive coupled plasma (ICP), X-ray diffraction (XRD); scanning electron microscopy coupled to energy dispersive X-ray (SEM–EDX) and transmission electron microscope (TEM). For synthesized Pd x Co/C electrocatalysts, the highest catalytic activity for the ORR, was found for a Pd:Co atomic ratio of 3:1 in acid media at the presence and absence of methanol with optimal Pd–Pd bond distance (0.2729 nm). Since the Pd x Co/C alloy electrocatalysts are inactive for the adsorption and oxidation of methanol, it can act as a methanol-tolerant ORR catalyst in a direct methanol fuel cell (DMFC). A membrane-electrode assembly (MEA) has been prepared by employing of the Pd 3 Co/C as a cathode for passive direct methanol fuel cell and characterized by polarization curves and impedance diagrams. The DMFC test results indicate that the MEA prepared from Pd 3 Co/C cathode exhibits better performance compared to the MEA prepared from Pt/C (Electrochem) and an in-house Pd/C catalyst synthesized, in terms of maximum power density and minimum charge transfer resistance

  6. Thermal properties of phosphoric acid-doped polybenzimidazole membranes in water and methanol-water mixtures

    Nores-Pondal, Federico J.; Corti, Horacio R. [Grupo de Pilas de Combustible, Departamento de Fisica de la Materia Condensada, Centro Atomico Constituyentes, Comision Nacional de Energia Atomica (CNEA), Av. General Paz 1499, B1650KNA San Martin, Buenos Aires (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (Argentina); Buera, M. Pilar [Consejo Nacional de Investigaciones Cientificas y Tecnicas (Argentina); Departamento de Industrias, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Av. Cantilo s/n, Ciudad Universitaria (1428) Buenos Aires (Argentina)

    2010-10-01

    The thermal properties of phosphoric acid-doped poly[2-2'-(m-phenylene)-5-5' bi-benzimidazole] (PBI) and poly[2,5-benzimidazole] (ABPBI) membranes, ionomeric materials with promising properties to be used as electrolytes in direct methanol and in high temperature polymer electrolyte membrane (PEM) fuel cells, were studied by means of differential scanning calorimetry (DSC) technique in the temperature range from -145 C to 200 C. The DSC scans of samples equilibrated in water at different relative humidities (RH) and in liquid water-methanol mixtures were analyzed in relation to glass transition, water crystallization/melting and solvent desorption in different temperature regions. The thermal relaxation observed in the very low temperature region could be ascribed to the glass transition of the H{sub 3}PO{sub 4}-H{sub 2}O mixture confined in the polymeric matrix. After cooling the samples up to -145 C, frozen water was detected in PBI and ABPBI at different RH, although at 100% RH less amount of water had crystallized than that observed in Nafion membranes under the same conditions. Even more important is the fact that the freezing degree of water is much lower in ABPBI membranes equilibrated in liquid water-methanol mixtures than that observed for PBI and, in a previous study, for Nafion. Thus, apart from other well known properties, acid-doped ABPBI emerges as an excellent ionomer for applications in direct methanol fuel cells working in cold environments. (author)

  7. Studies of catalyst material for the electro-oxidation of methanol, ethanol, formaldehyde and formic acid

    Bajwa, S.Z.; Ahmed, R.

    2007-01-01

    Fuel cell is an electrochemical device that converts the chemical energy of reaction directly into the electrical energy. It is highly efficient and environment friendly device. Normally used fuel in fuel cells is hydrogen, but due to the convenience in handling some other liquid fuels are also used and now direct methanol fuel cells are available in the market. Rapid electro-oxidation of the fuel at the fuel cell electrode is necessary for its optimum use. In addition to the methanol, other liquid fuels can also be used in the fuel cell. In this work, cyclic voltammetric studies have been done for the electro-oxidation of the methanol, ethanol, formic acid and formaldehyde on fuel cell catalyst. Platinum electrode is characterized by the measurement of active surface area and roughness factor. Classical electrochemical equations have been employed to find out rate constants for electro-oxidation of methanol fuel and calculations have been carried out to find out thermodynamic parameters. Exchange current density has been evaluated with reference to catalyst by drawing polarization curves. (author)

  8. Effect of nitrogen source on methanol oxidation and genetic diversity of methylotrophic mixed cultures enriched from pulp and paper mill biofilms.

    Babbitt, Callie W; Lindner, Angela S

    2011-04-01

    Methanol-oxidizing bacteria may play an important role in the development and use of biological treatment systems for the removal of methanol from industrial effluents. Optimization of methanol degradation potential in such systems is contingent on availability of nutrients, such as nitrogen, in the most favorable form and concentration. To that end, this study examined the variation in growth, methanol degradation, and bacterial diversity of two mixed methylotrophic cultures that were provided nitrogen either as ammonium or nitrate and in three different concentrations. Methanol-degrading cultures were enriched from biofilms sampled at a pulp and paper mill and grown in liquid batch culture with methanol as the only carbon source and either ammonium or nitrate as the only added nitrogen source. Results indicate that growth and methanol removal of the mixed cultures increase directly with increased nitrogen, added in either form. However, methanol removal and bacterial diversity, as observed by polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) methods, were higher when using nitrate as the nitrogen source for enrichment and growth, rather than ammonium. Based on results described here, nitrate may potentially be a better nitrogen source when enriching or working with mixed methylotrophic cultures, and possibly more effective when used as a nutrient addition to biofilters.

  9. Directional Transport of a Liquid Drop between Parallel-Nonparallel Combinative Plates.

    Huang, Yao; Hu, Liang; Chen, Wenyu; Fu, Xin; Ruan, Xiaodong; Xie, Haibo

    2018-04-17

    Liquids confined between two parallel plates can perform the function of transmission, support, or lubrication in many practical applications, due to which to maintain liquids stable within their working area is very important. However, instabilities may lead to the formation of leaking drops outside the bulk liquid, thus it is necessary to transport the detached drops back without overstepping the working area and causing destructive leakage to the system. In this study, we report a novel and facile method to solve this problem by introducing the wedgelike geometry into the parallel gap to form a parallel-nonparallel combinative construction. Transport performances of this structure were investigated. The criterion for self-propelled motion was established, which seemed more difficult to meet than that in the nonparallel gap. Then, we performed a more detailed investigation into the drop dynamics under squeezing and relaxing modes because the drops can surely return in hydrophilic combinative gaps, whereas uncertainties arose in gaps with a weak hydrophobic character. Therefore, through exploration of the transition mechanism of the drop motion state, a crucial factor named turning point was discovered and supposed to be directly related to the final state of the drops. On the basis of the theoretical model of turning point, the criterion to identify whether a liquid drop returns to the parallel part under squeezing and relaxing modes was achieved. These criteria can provide guidance on parameter selection and structural optimization for the combinative gap, so that the destructive leakage in practical productions can be avoided.

  10. Radiolytical Preparation of a Poly(Vinylbenzyl Sulfonic Acid)-Grafted FEP Membrane and Characterization as Polymer Electrolytes for Direct Methanol Fuel Cells

    Nho, Y -C; Shin, J; Sohn, J -Y; Fei, G [Radiation Research Division for Industry and Environment, Korea Atomic Energy Research Institute, 1266 Sinjeong-dong, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of)

    2012-09-15

    In this study, a novel polymer electrolyte membrane, poly(vinylbenzyl sulfonic acid)-grafted poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP-g-PVBSA), has been successfully prepared by simultaneous irradiation grafting of vinylbenzyl chloride(VBC) monomer onto a FEP film and taking subsequent chemical modification steps to modify the benzyl chloride moiety to the benzyl sulfonic acid moiety. The chemical reactions for the sulfonation were carried out via the formation of thiouronium salt with thiourea, base-catalyzed hydrolysis for the formation of thiol, and oxidation with hydrogen peroxide. Each chemical conversion process was confirmed by FTIR, elemental analysis, and SEM-EDX. A chemical stability study performed with Fenton's reagent (3% H{sub 2}O{sub 2} solution containing 4 ppm of Fe{sup 2+}) at 70 deg. C revealed that FEP-g-PVBSA has a higher chemical stability than the poly(styrene sulfonic acid)-grafted membranes (FEP-g-PSSA). An EDX analysis was also used to observe the cross-sectional distribution behaviors of the hydrophilic sulfonic acid groups and hydrophobic fluorine groups. The characteristics of an ion-exchange capacity (IEC), water and methanol uptake, methanol permeability, and proton conductivity as a function of the degree of grafting were also studied. The IECs and water uptakes of membranes with different degrees of grafting (36-102%) were measured to be in the range of 0.8-1.62 meq/g, and 10-30%, respectively. When the degree of grafting reached 60% the proton conductivity was higher than that of a Nafion (registered) 212 membrane (6.1E-02 S/cm). The methanol permeability and uptake of the FEP-g-PVBSA membrane was significantly lower than that of the Nafion (registered) 212 membrane, and even the degree of grafting reached 102%. (author)

  11. Dynamic signature of molecular association in methanol

    Bertrand, C. E.; Copley, J. R. D.; Faraone, A.; Self, J. L.

    2016-01-01

    Quasielastic neutron scattering measurements and molecular dynamics simulations were combined to investigate the collective dynamics of deuterated methanol, CD 3 OD. In the experimentally determined dynamic structure factor, a slow, non-Fickian mode was observed in addition to the standard density-fluctuation heat mode. The simulation results indicate that the slow dynamical process originates from the hydrogen bonding of methanol molecules. The qualitative behavior of this mode is similar to the previously observed α-relaxation in supercooled water [M. C. Bellissent-Funel et al., Phys. Rev. Lett. 85, 3644 (2000)] which also originates from the formation and dissolution of hydrogen-bonded associates (supramolecular clusters). In methanol, however, this mode is distinguishable well above the freezing transition. This finding indicates that an emergent slow mode is not unique to supercooled water, but may instead be a general feature of hydrogen-bonding liquids and associating molecular liquids.

  12. Applications Ni59Nb40Pt(1-x) Xx (X= Sn,Sby and Ru) amorphous alloy as anodes for direct methanol (DMFC) fuel cells

    Rodriguez Pierna, A

    2005-01-01

    The search of new anode materials of amorphous nature for methanol fuel cells is one of the aims of this work.The main problem that fuel cells present is related to the catalytic material and its distribution in a suitable matrix.Amorphous alloys are particularly attractive materials as catalyst supports because of their high conductivity, high corrosion resistance in sulphuric acid, as well as the possibility of a good distribution of the electrocatalytic particles, mainly platinum and platinum-tin, on a conducting matrix.The electrooxidation of methanol, in percloric acid medium, has been used as probe to evaluate the performance of metallic amorphous electrodes, with compositions Ni 5 9Nb 4 0Pt 1 , Ni 5 9Nb 4 0Pt 0 .6Sn0.4, Ni 5 9Nb 4 0Pt 0 .6Sb 0 .4 and Ni 5 9Nb 4 0Pt 0 .6Ru 0 .4.The electrocatalytic activity of the alloyed ribbons of compositions (x = 0.6, 1% at. in platinum) is improved considerably, so much for the change in their composition, as for the roughness degree that the catalytic surfaces present. The increase of the tolerance to adsorbed species, and better resistance to the poisoning of their catalytic centers, can be observed by means of voltammetric experiments at different activation times with HF 48%. The electrooxidation of methanol in the amorphous alloy of composition Ni 5 9Nb 4 0Pt 1 , is influenced by the nature of the used electrolyte, presenting smaller values of current density in solutions 1M H 2 SO 4 than in 1M of HClO 4 .This behavior is not observed in the alloy Ni 5 9Nb 4 0Pt 0 .6Sn 0 .4, Ni 5 9Nb 4 0Pt 0 .6Sb 0 .4 and Ni 5 9Nb 4 0Pt 0 .6Ru 0 .4which does not present a poisoning of the catalytic centers depending on the used electrolyte.Adding tin to the alloys showed the existence of a synergetic effect in the methanol electrooxidation process, attaining to a descent of 20 mV vs Ag/AgCl in the onset potential, and about 200 mV in the maximun peak potential

  13. Structure-directing effects of ionic liquids in the ionothermal synthesis of metal-organic frameworks.

    Vaid, Thomas P; Kelley, Steven P; Rogers, Robin D

    2017-07-01

    Traditional synthesis of metal-organic frameworks (MOFs) involves the reaction of a metal-containing precursor with an organic linker in an organic solvent at an elevated temperature, in what is termed a 'solvothermal' reaction. More recently, many examples have been reported of MOF synthesis in ionic liquids (ILs), rather than an organic solvent, in 'ionothermal' reactions. The high concentration of both cations and anions in an ionic liquid allows for the formation of new MOF structures in which the IL cation or anion or both are incorporated into the MOF. Most commonly, the IL cation is included in the open cavities of the MOF, countering the anionic charge of the MOF framework itself and acting as a template around which the MOF structure forms. Ionic liquids can also serve other structure-directing roles, for example, when an IL containing a single enantiomer of a chiral anion leads to a homochiral MOF, even though the IL anion is not itself incorporated into the MOF. A comprehensive review of ionothermal syntheses of MOFs, and the structure-directing effects of the ILs, is given.

  14. Structure-directing effects of ionic liquids in the ionothermal synthesis of metal–organic frameworks

    Thomas P. Vaid

    2017-07-01

    Full Text Available Traditional synthesis of metal–organic frameworks (MOFs involves the reaction of a metal-containing precursor with an organic linker in an organic solvent at an elevated temperature, in what is termed a `solvothermal' reaction. More recently, many examples have been reported of MOF synthesis in ionic liquids (ILs, rather than an organic solvent, in `ionothermal' reactions. The high concentration of both cations and anions in an ionic liquid allows for the formation of new MOF structures in which the IL cation or anion or both are incorporated into the MOF. Most commonly, the IL cation is included in the open cavities of the MOF, countering the anionic charge of the MOF framework itself and acting as a template around which the MOF structure forms. Ionic liquids can also serve other structure-directing roles, for example, when an IL containing a single enantiomer of a chiral anion leads to a homochiral MOF, even though the IL anion is not itself incorporated into the MOF. A comprehensive review of ionothermal syntheses of MOFs, and the structure-directing effects of the ILs, is given.

  15. Ionic Liquid Directed Mesoporous Carbon Nanoflakes as an Effiencient Electrode material

    Kong, Lirong; Chen, Wei

    2015-12-01

    Supercapacitors are considered to be the most promising approach to meet the pressing requirements for energy storage devices. The electrode materials for supercapacitors have close relationship with their electrochemical properties and thus become the key point to improve their energy storage efficiency. Herein, by using poly (vinylidene fluoride-co-hexafluoropropylene) and ionic liquid as the dual templates, polyacrylonitrile as the carbon precursor, a flake-like carbon material was prepared by a direct carbonization method. In this method, poly (vinylidene fluoride-co-hexafluoropropylene) worked as the separator for the formation of isolated carbon flakes while aggregated ionic liquid worked as the pore template. The obtained carbon flakes exhibited a specific capacitance of 170 F/g at 0.1 A/g, a high energy density of 12.2 Wh/kg and a high power density of 5 kW/kg at the current of 10 A/g. It also maintained a high capacitance retention capability with almost no declination after 500 charge-discharge cycles. The ionic liquid directed method developed here also provided a new idea for the preparation of hierarchically porous carbon nanomaterials.

  16. Highly tilted liquid crystalline materials possessing a direct phase transition from antiferroelectric to isotropic phase

    Milewska, K.; Drzewiński, W. [Institute of Chemistry, Military University of Technology, 00-908 Warsaw (Poland); Czerwiński, M., E-mail: mczerwinski@wat.edu.pl [Institute of Chemistry, Military University of Technology, 00-908 Warsaw (Poland); Dąbrowski, R. [Institute of Chemistry, Military University of Technology, 00-908 Warsaw (Poland); Piecek, W. [Institute of Applied Physics, Military University of Technology, 00-908 Warsaw (Poland)

    2016-03-01

    Pure compounds and multicomponent mixtures with a broad temperature range of high tilted liquid crystalline antiferroelectric phase and a direct phase transition from antiferroelectric to isotropic phase, were obtained. X-ray diffraction analysis confirms these kinds of materials form a high tilted anticlinic phase, with a fixed layer spacing and very weak dependency upon temperature, after the transition from the isotropic phase. Due to this, not only pure orthoconic antiferroelectric liquid crystals but also those with a moderate tilt should generate a good dark state. Furthermore, due to the increased potential for forming anticlinic forces, such materials could minimize a commonly observed asymmetry of a rise and fall switching times at a surface stabilized geometry. - Highlights: • The new class of liquid crystalline materials with the direct SmC{sub A}*. • Iso phase transition were obtained. • Materials possess the layer spacing fixed and very weak dependent upon temperature. • Smectic layers without shrinkage are observed. • A good dark state can be generate in SSAFLC.

  17. Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst

    Gao, Peng; Li, Shenggang; Bu, Xianni; Dang, Shanshan; Liu, Ziyu; Wang, Hui; Zhong, Liangshu; Qiu, Minghuang; Yang, Chengguang; Cai, Jun; Wei, Wei; Sun, Yuhan

    2017-10-01

    Although considerable progress has been made in carbon dioxide (CO2) hydrogenation to various C1 chemicals, it is still a great challenge to synthesize value-added products with two or more carbons, such as gasoline, directly from CO2 because of the extreme inertness of CO2 and a high C-C coupling barrier. Here we present a bifunctional catalyst composed of reducible indium oxides (In2O3) and zeolites that yields a high selectivity to gasoline-range hydrocarbons (78.6%) with a very low methane selectivity (1%). The oxygen vacancies on the In2O3 surfaces activate CO2 and hydrogen to form methanol, and C-C coupling subsequently occurs inside zeolite pores to produce gasoline-range hydrocarbons with a high octane number. The proximity of these two components plays a crucial role in suppressing the undesired reverse water gas shift reaction and giving a high selectivity for gasoline-range hydrocarbons. Moreover, the pellet catalyst exhibits a much better performance during an industry-relevant test, which suggests promising prospects for industrial applications.

  18. Direct writing of flexible electronics through room temperature liquid metal ink.

    Yunxia Gao

    Full Text Available BACKGROUND: Conventional approaches of making a flexible circuit are generally complex, environment unfriendly, time and energy consuming, and thus expensive. Here, we describe for the first time the method of using high-performance GaIn(10-based electrical ink, a significantly neglected room temperature liquid metal, as both electrical conductors and interconnects, for directly writing flexible electronics via a rather easy going and cost effective way. METHODS: The new generation electric ink was made and its wettability with various materials was modified to be easily written on a group of either soft or rigid substrates such as epoxy resin board, glass, plastic, silica gel, paper, cotton, textiles, cloth and fiber etc. Conceptual experiments were performed to demonstrate and evaluate the capability of directly writing the electrical circuits via the invented metal ink. Mechanisms involved were interpreted through a series of fundamental measurements. RESULTS: The electrical resistivity of the fluid like GaIn(10-based material was measured as 34.5 µΩ·cm at 297 K by four point probe method and increased with addition of the oxygen quantity, which indicates it as an excellent metal ink. The conductive line can be written with features that are approximately 10 µm thick. Several functional devices such as a light emitting diode (LED array showing designed lighting patterns and electrical fan were made to work by directly writing the liquid metal on the specific flexible substrates. And satisfactory performances were obtained. CONCLUSIONS: The present method opens the way to directly and quickly writing flexible electronics which can be as simple as signing a name or drawing a picture on the paper. The unique merit of the GaIn(10-based liquid metal ink lies in its low melting temperature, well controlled wettability, high electrical conductivity and good biocompability. The new electronics writing strategy and basic principle has generalized

  19. Direct writing of flexible electronics through room temperature liquid metal ink.

    Gao, Yunxia; Li, Haiyan; Liu, Jing

    2012-01-01

    Conventional approaches of making a flexible circuit are generally complex, environment unfriendly, time and energy consuming, and thus expensive. Here, we describe for the first time the method of using high-performance GaIn(10)-based electrical ink, a significantly neglected room temperature liquid metal, as both electrical conductors and interconnects, for directly writing flexible electronics via a rather easy going and cost effective way. The new generation electric ink was made and its wettability with various materials was modified to be easily written on a group of either soft or rigid substrates such as epoxy resin board, glass, plastic, silica gel, paper, cotton, textiles, cloth and fiber etc. Conceptual experiments were performed to demonstrate and evaluate the capability of directly writing the electrical circuits via the invented metal ink. Mechanisms involved were interpreted through a series of fundamental measurements. The electrical resistivity of the fluid like GaIn(10)-based material was measured as 34.5 µΩ·cm at 297 K by four point probe method and increased with addition of the oxygen quantity, which indicates it as an excellent metal ink. The conductive line can be written with features that are approximately 10 µm thick. Several functional devices such as a light emitting diode (LED) array showing designed lighting patterns and electrical fan were made to work by directly writing the liquid metal on the specific flexible substrates. And satisfactory performances were obtained. The present method opens the way to directly and quickly writing flexible electronics which can be as simple as signing a name or drawing a picture on the paper. The unique merit of the GaIn(10)-based liquid metal ink lies in its low melting temperature, well controlled wettability, high electrical conductivity and good biocompability. The new electronics writing strategy and basic principle has generalized purpose and can be extended to more industrial areas, even

  20. Evidence for CO formation in irradiated methanol and acetone: contribution of low-energy electron-energy-loss spectroscopy to γ-radiolysis

    Jay-Gerin, J.-P.; Fraser, M.-J.; Michaud, M.; Sanche, L.; Swiderek, P.; Ferradini, C.

    1997-01-01

    Energy-loss spectra for low-energy electrons incident on acetone condensed on a multilayer film of argon, and on a methanol film deposited on a metallic substrate, are reported. In both cases, the formation of carbon monoxide has been detected. These results are directly related to those obtained in the liquid-phase γ-radiolysis of the two compounds. (author)