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pathways between two nodes, some of them can be neglected. Consequently, a clearer but still representative mechanism is obtained. Besides, the overall reaction rate (rOR) is easy to determine knowing the possible Reaction Routes. In analogy to Ohm’s law it is a function of the overall reaction resistance and affinity. r =AOR OR Such an approach seems to be an efficient one to simplify the complicated methanol oxidation mechanism and come up with a significant overall rate expression. However, Reaction Network Theory has been studied for surface reaction in gas phase. There are two challenges to face to adapt the method to methanol electro-oxidation in fuel cells. The mechanism contains some electrochemical steps. For these, activation energy is potential dependant. Consequently, a fundamental model should be found to express them. Besides, the unity bond index-quadratic exponential potential method (UBI-QEP) developed by Shustorovitch [23], valid in gas phase needs to be adapted to liquid phase or be replaced by another ab initio model. 2. Methanol oxidation mechanism The methanol oxidation overall reaction (OR) can be divided into two consecutive overall reactions. The first one is methanol decomposition into carbon monoxide. The second one is the water-gas shift reaction (WGSR). OR1: CH3OH + 4H2O CO + 4H3O+ + 4e- OR2: CO + 3H2O CO2 + 2H3O+ + 2e- CH3OH + 7H2O CO2 + 6H3O+ + 6e- In order to draw an overall of graph for methanol oxidation it seems easier to draw a graph for each of the consecutive reactions and then try to connect them together. - 85 - ROR (MeOH decomposition) (WGSR) (MeOH electro-oxidation)PDF Image | Direct Methanol Fuel Cell (DMFC) Performance
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