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(Si/Al=40) by blending method to demonstrate improved selectivity of zeolite-polymer composite membrane for DMFC application. The experiment shows that even tough addition of mordenite into PVA decrease methanol crossover, mordenite cannot conduct proton efficiently even though it contains sulfuric acid. However, its methanol selectivity increases more than proton conductivity reduction. The resulting PVA/mordenite membrane gives 20- fold selectivity compared with Nafion. Gribov et. al91 used supercritical CO2 pre-treatment and Fe-silicate-1 impregnation or in situ synthesis in Nafion. By using supercritical CO2, methanol crossover can be minimized. However, a significant decrease in proton conductivity is also inherent. Addition of Fe-silicate-1 to this membrane greatly reduce methanol crossover with only slight proton conductivity decrease. The best zeolite-Nafion membrane obtained prepared from immersion of Nafion membrane in zeolite colloid solution resulting in 19-fold selectivity of those obtained from pure Nafion. Not only as a membrane filler, zeolite is also applicable as electrodes as zeolite modified electrodes (ZME). ZMEs combine the advantages of ion exchange voltammetry with unique molecular sieving properties of the zeolites. Reactant small enough can diffuse freely within the zeolite framework and be distinguished from bulk reaction mixture. Moreover, ZMEs have the potential to be used in electrocatalysis.92 Zeolites offer selectivity based on the size and shape of the reactants thus can be very useful in this certain application.93-95 Mohan and Cindrella96 modify glassy carbon electrode with Fe-ZSM-5. Iron is present as both Fe (II) and Fe (III) that also undergo redox equilibrium alongside with methanol redox reaction. The presence of both state of iron enhances the efficiency of electrocatalytic activity for methanol oxidation. ZEOLITE MODIFICATION EFFECT ON FUEL CELL PERFORMANCE Polymer-zeolite performances made by several authors are shown in Table 2. Modification of polymer using zeolite is commonly prepared via blending-casting method. Zeolite is blended into polymer solution then cast into petri dish to obtain thin film composite membrane. Another method to incorporate zeolite to polymer matrix is immersion of polymer to zeolite solution.91 Zeolite particle will be trapped inside the polymer matrix. Wang et. al.84 investigate the effect different Si/Al ratio zeolite incorporation with chitosan on FC performance. Low Si/Al ratio zeolite (hydrophilic) offer weak hydrogen-bonding interaction between polymer and zeolite thus substantially increase free volume cavity. On the other hand, high Si/Al ratio zeolite (hydrophobic) gives strong hydrogen-bonding interactions with the polymer thus decreasing free volume cavity size. Hydrophobic zeolite also preferentially adsorbed methanol by London force, resulting in a decrease of water uptake, swelling, and methanol permeability. However, proton conductivity was slightly decreased with zeolite content when using hydrophobic membrane. The opposite trends are true for hydrophilic zeolite. Polymer Zeolite Nafion N/A Nafion Fe- Silicate-1 Modification Method N/A Immersion in zeolite solution Blending-Casting Blending-Casting Blending-Casting Blending-Casting Blending-Casting Immersion in zeolite solution Alcohol Permeability (cm2/s) 13.1 x 10-7 8.40 x 10-9 1 x 10-7 1.03 x 10-6 1 x 10-6 1.5 x 10-6 3.63 x 10-6 2.07 x 10-7 9.97 x 10-9 3.15 x 10-7 Proton Conductivity (mSm/cm) 95.6 3.8 100 Selectivity (s/cm3) Reference PVA MOR 7.3 x 104 97 4.50 x 105 91 105 27 Nafion 117 Chitosan ZSM-5 Chitosan LTA Nafion AFB Chitosan Beta PVA MOR SPEEK NaX 3.4 x 107 83 1.13 x 106 84 1.84 x 107 81 6.81 x 104 98 5 x 10 6 99 9.2 x104 97 TABLE 2. Zeolite-Modified Polymer Membrane Performance and their performance related to DAFC Blending-Casting LTA Blending-Casting 35 20 2x107 84 17 67 14.1 50.3 29.1 020030-7PDF Image | Zeolite modification for direct alcohol fuel cells DAFCs
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