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Energies 2010, 3 1504 Table 1. Electrochemical oxidation of various alcohols in alkaline medium. Fuel Methanol CH3OH Ethanol CH3CH2OH iso-Propanol CH3CHOHCH3 Ethylene glycol (CH2OH)2 Glycerol HOCH CHOHCH OH 2 2 2.2. Oxygen Reduction Anode Reactions CH3OH + 6OH−→CO2 + 5H2O + 6e− CH3CH2OH +2OH−→CH3CHO + 2H2O + 2e− CH3CH2OH + 4OH−→CH3COOH + 3H2O + 4e− CH3CH2OH + 12 OH−→2CO2 +9 H2O+12e− CH3CHOHCH3 + 2OH−→CH3COCH3 + 2H2O + 2e− CH3COCH3 + 16OH−→3CO2 + 11H2O + 16e− (CH2OH)2 + 14OH−→2CO32− + 10H2O + 10e− or (CH2OH)2 + 10OH−→(CO2)22− + 8H2O + 8e− HOCH2CHOHCH2OH+ 20OH−→3CO32− + 14H2O + 14e− or HOCH2CHOHCH2OH + 12OH−→(COO−- COH-COO−) + 10H2O + 10e− E° Energy (V/SHE) density (Wh/kg) −0.81 6100 −0.77 8030 −0.67 8600 −0.72 5200 −0.69 5000 The oxygen reduction reaction (ORR) has been studied extensively. Effects of different pH, electrolytes, temperature and pre-conditioning of electrodes on ORR have been investigated. The most accepted mechanism of ORR was first proposed by Damjanovic et al. [40,41]. They suggested that the ORR proceeds along two parallel reaction paths with comparable rates. One is the direct four-electron transfer reduction from oxygen to water; the other is the formation of hydrogen peroxide as an intermediate in a two-electron transfer reaction. The reaction scheme is shown as follows [42]: O2, b O2, a k1 k2 k3 H2O2, a H2O H2O2, b where a indicates an adsorbed state and b is the bulk solution. The reactions in alkaline media can be presented as: O2 + 2H2O + 4e−→4OH− and the path involving hydrogen peroxide suggested in [38] is: O2 + e− O2− O2− + H2O→HO2− + OH OH + e− OH− (8) (9) In the low current density region, the Tafel slope is −60 mV dec−1 and the reaction order is 0.5 with respect to pH in alkaline solutions. The fractional reaction order was interpreted in terms of the firstPDF Image | Aspects of Direct Alkaline Alcohol Fuel Cells
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