Surface-modified Nafion (R) membrane by casting proton-conducting polyelectrolyte complexes for direct methanol fuel cells

Surface-modified Nafion (R) membrane was prepared by casting proton-conducting polyelectrolyte complexes on the surface of Nafion (R). The casting layer is homogeneous and its thickness is about 900 nm. The proton conductivity of modified Nafion (R) is slightly lower than that of plain Nafion (R); however, its methanol permeability is 41% lower than that of plain Nafion (R). The single cells with modified Nafion (R) exhibit higher open circuit voltage (OCV = 0.73 V) and maximal power density (P-max = 58 mW cm(-2)) than the single cells with plain Nafion (R) (OCV = 0.67 V, P x = 49 mW cm-2). It is a simple, efficient, cost-effective approach to modifying Nafion (R) by casting proton-conducting materials on the surface of Nafion (R).

Proton transfer across conducting polypyrrole membrane separated by two electrolyte solutions

Electrochemical behavior of the transfer of H+ across polypyrrole membrane (PPM) was studied. The transfer process was quasi-reversible and mainly diffusion-controlled. PPM electropolymerized in water solution has better reversibility than that in CH3CN solution for the transfer of H+. The transfer process of H+ across the two kinds of PPM indicated that the PPM electrochemically polymerized was of asymmetry.

Easy fabrication of dense ceramic membrane for oxygen separation

A combined EDTA-citrate complexing method was developed for the easy preparation of mixed oxygen-ionic and electronic conducting dense ceramic membrane for oxygen separation. The nea method takes the advantage of lower calcination temperature for phase formation. lower membrane sintering temperature and higher relative density over the standard ceramic method.

Synthesis and characterization of gallium-based perovskite-type dense membrane with oxygen semipermeability

La0.15Sr0.85Ga0.3Fe0.7O3-delta (LSGFO) and La0.15Sr0.85Co0.3Fe0.7O3-delta (LSCFO) mixed oxygen-ion and electron conducting oxides were synthesized by using a combined EDTA and citrate complexing method, and the corresponding dense membranes were fabricated. The properties of the oxide powders and membranes were characterized with combined SEM, XRD, H-2-TPR, O-2-TPD techniques, mechanical strength and oxygen permeation measurement. The results showed that LSGFO had much higher thermochemical stability than LSCFO due to the higher valence stability of Ga3+. After the temperature-programmed reduction by 5% H-2 in Ar from 20 degreesC to 1020 degreesC, the basic perovskite structure of LSGFO was successfully preserved. LSGFO also favors the oxygen vacancy formation better than LSCFO. Oxygen permeation measurement demonstrated that LSGFO had higher oxygen permeation flux than LSCFO, but they had similar activation energy for oxygen transportation, with a value of 110 and 117 kJ . mol(-1), respectively The difference in oxygen permeation fluxes was correlated with the difference in oxygen vacancy concentrations for the two materials.

Electrochemical performance of mixed ionic-electronic conducting oxides as anodes for solid oxide fuel cell

Mixed ionic-electronic conducting (MIEC) oxides, SrFeCo0.5Ox, SrCo0.8Fe0.2O3-delta and La0.6Sr0.4Fe0.8Co0.2O3-delta have been synthesized and prepared on yttria-stabilized zirconia as anodes for solid oxide fuel cells. Power output measurements show that the anodes composed of such kinds of oxides exhibit modest electrochemical activities to both H-2 and CH4 fuels, giving maximum power densities of around 0.1 W/cm(2) at 950 degrees C. Polarization and AC impedance measurements found that large activation overpotentials and ohmic resistance drops were the main causes for the relative inferior performance to the Ni-YSZ anode. While interlayered with an Ni-YSZ anode, a significant improvement in the electrochemical performance was observed. in particular, for the SrFeCo0.5Ox oxide interlayered Ni-YSZ anode, the maximum power output reaches 0.25 W/cm2 on CH,, exceeding those of both SrFeCo0.5Ox and the Ni-YSZ, as anodes alone. A synergetic effect of SrFeCo0.5Ox and the Ni-YSZ has been observed. Future work is needed to examine the long-term stability of MIEC oxide electrodes under a very reducing environment. (C) 1999 Elsevier Science B.V. All rights reserved.

Mixed reforming of heptane to syngas in the Ba0.5Sr0.5Co0.8Fe0.2O3 membrane reactor

Fuel cells are recognized as the most promising new power generation technology, but hydrogen supply is still a problem. In our previous work, we have developed a LiLaNiO/gamma-Al2O3 catalyst, which is excellent not only for partial oxidation of hydrocarbons, but also for steam reforming and autothermal reforming. However, the reaction needs pure oxygen or air as oxidant. We have developed a dense oxygen permeable membrane Ba0.5Sr0.5Co0.8Fe0.2O3 which has an oxygen permeation flux around 11.5 ml/cm(2) min at reaction conditions. Therefore, this work is to combine the oxygen permeable membrane with the catalyst LiLaNiO/gamma-Al2O3 in a membrane reactor for hydrogen production by mixed reforming of heptane. Under optimized reaction conditions, a heptane conversion of 100%, a CO selectivity of 91-93% and a H-2 selectivity of 95-97% have been achieved. (c) 2005 Elsevier B.V. All rights reserved.

Optimization of operational conditions in a submerged membrane bioreactor

In this study, optimization of operational conditions of a submerged membrane bioreactor treating municipal waste-water was studied. Mixed liquid suspended solid (MLSS), membrane flux (J(v)), aeration (Q), ratio of pumping, time to break time (t(p)/t(b)), and ratio of up flow area to down flow area (A Ad) were chosen as the easily manipulable parameters to study their effects on removal efficiency and membrane fouling. Totally, 16 different runs were designed to compare and select the best combination of the 5 parameters. The results showed that the optimal operational conditions were MLSS = 7g(.)L(-1), J(v) = 10L(.)m(-2.)h(-1), Q = 6 m(3.)h(-1), t(p)/t(b)= 4 min/1 min, and A(r)/A(d) = 1.7 m(2)/m(2). Under such conditions, the SMBR could achieve a double win of high removal efficiency and low membrane fouling.

Structure and oxygen permeability of a dual-phase membrane

The dual-phase membrane of La0.15Sr0.85Ga0.3Fe0.7O3-delta-Ba0.5Sr0.5Fe0.2Co0.8O3-delta (LSGF-BSCF) was prepared successfully. This membrane was characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM) and electron probe micro-analyzer (EPMA). This membrane has a dense dual-phase structure: LSGF being the dense body of this membrane and BSCF as another phase running along the LSGF body. This structure is favorable for the oxygen permeation through the membrane. The oxygen permeation test shows that the oxygen permeation flux of LSGF-BSCF membrane (Jo(2) = 0.45 ml/min cm(2), at 915 degreesC) is much higher than that of LSGF membrane (Jo(2) = 0.05 ml/min cm(2)). Thickness dependence of oxygen permeation indicates that the oxygen permeation is controlled by the bulk diffusion. Compared to pure BSCF the dual-phase membrane of LSGF-BSCF is stable in reducing atmosphere. (C) 2003 Elsevier B.V. All rights reserved.

Implantation of Nafion (R) ionomer into polyvinyl alcohol/chitosan composites to form novel proton-conducting membranes for direct methanol fuel cells

A series of cost-effective, proton-conducting composite membranes, comprising of Nafion (R) ionomer, chitosan (CS). and polyvinyl alcohol (PVA), is successfully prepared. By taking advantage of the strong electrostatic interactions between Nafion (R) ionomer and CS component, Nafion ionomer is effectively implanted into the PVA/CS composite membranes, and improves proton conductivity of the PVA/CS composite membranes. Furthermore, this effect dramatically depends on the composition ratio of PVA/CS, and the optimum conductivity is obtained at the PVA/CS ratio of 1:1. The developed composite membranes exhibit much lower methanol permeability compared with the widely used Nafion (R) membrane, indicating that these novel membranes have great potential for direct methanol fuel cells (DMFCs).

Preparation and evaluation of a proton exchange membrane based on oxidation and water stable sulfonated polyimides

A series of novel oxidation and water stable sulfonated polyimides (SPIs) were synthesized from 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BTDA), and wholly aromatic diamine 2,2'-bis(3-sulfobenzoyl) benzidine (2,2'-BSBB) for proton exchange membrane fuel cells. These polyimides could be cast into flexible and tough membranes from m-cresol solutions. The copolymer membranes exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendant groups. Moreover, all BTDA-based SPI membranes exhibited much better water stability than those based on the conventional 1,4,5,8-naphthalenecarboxylic dianhydride. The improved water stability of BTDA-based polyimides was attributed to its unique binaphthalimide structure. The SPI membranes with ion exchange capacity (IEC) of 1.36-1.90 mequiv g(-1) had proton conductivity in the range of 0.41 x 10(-1) to 1. 12 x 10(-1) S cm(-1) at 20 degrees C. The membrane with IEC value of 1.90 mequiv g(-1) displayed reasonably higher proton conductivity than Nafion((R)) 117 (0.9 x 10(-1) S cm(-1)) under the same test condition and the high conductivity of 0.184 S cm(-1) was obtained at 80 degrees C. Microscopic analyses revealed that well-dispersed hydrophilic domains contribute to better proton conducting properties. These results showed that the synthesized materials might have the potential to be applied as the proton exchange membranes for PEMFCs.

Loosely packed self-assembled monolayer of N-hexadecyl-3,6-di(p-mercaptophenylacetylene)carbazole on gold and its application in biomimetic membrane research

Dithiols of N-hexadecyl-3,6-di(p-mercaptophenylacetylene)carbazole (HDMC) have been synthesized and employed to form self-assembled monolayers (SAMs) on gold. One characteristic of the HDMC molecule is its peculiar molecular structure consisting of a large and rigid headgroup and a small and flexible alkyl-chain tail. HDMC adsorbates can attach to gold substrates by a strong Au-S bond with weak van der Waals interactions between the alkyl-chain tails, leading to a loosely packed hydrophobic SAM. In this way we can couple hybrid bilayer membranes (HBMs) to gold surfaces with more likeness to a cell bilayer than the conventional HBMs based on densely packed long-chain alkanethiol SAMs. The insulating properties and stability of the HDMC monolayer as well as the HDMC/lipid bilayer on gold have been investigated by electrochemical techniques including cyclic voltammetry and impedance spectroscopy. To test whether the quality of the bilayer is sufficiently high for biomimetic research, we incorporated the pore-forming protein a-hemolysin) and the horseradish peroxidase into the bilayers, respectively.

A room-temperature ionic-liquid-templated proton-conducting gelatinous electrolyte

Novel proton-conducting gelatinous electrolytes templated by room-temperature ionic liquid (RTIL) 1-butyl-3-methyl-imidazolium-tetrafluoroborate (BMImBF(4)) have been prepared in methylsisesquioxane backbone containing H3PO4, and the influences of the RTIL on the structure, morphology, thermal stability, and electrochemical properties of the gelatinous electrolytes have been examined. X-ray diffraction and scanning electron microscopy proved that BMImBF(4) acted as structure-directing template during the sol-gel process of methyl-trimethoxysilane. X-ray photoelectron spectra and infrared spectroscopy demonstrated that the hydrogen-bonding was formed between BMImBF(4) and H3PO4. The electrolytes had good thermal stability up to 300 degreesC and showed superior mechanical and electrochemical properties. A room-temperature conductivity of 1.2 x 10(-3) S cm(-1) was obtained for the electrolyte at the molar ratio of RTIL/Si/H3PO4 0.3/1/1, and its electrochemical window was up to 1.5 V.

Mixed ion transfer analysis in redox processes of electroactive thin films

Electrochemical quartz crystal microbalance (EQCM) technique was used to measure the ion transfer in redox processes in electroactive organic thin films, such as self-assembled monolayer (SAM) (4-pyridyl hydroquinone, abbr. 4PHQ), multilayer based on SAM and conducting polymer film (here poly-(3,4-ethylenedioxythiophene), abbr. PEDOT). A mechanism of mixed ion transfer is developed and presented. Analysis of mixed ion transfer during redox processes successfully elucidates the deviation of oscillation frequency of the quartz crystal from theoretical expectation.