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Energies 2010, 3 1503 The rate-determining step is step 4, in which the adsorbed ethoxy intermediate is removed by adsorbed hydroxyl ions to form acetate. Fang et al. studied the mechanism of ethanol electrooxidation on a palladium electrode in alkaline solution with various concentrations of NaOH (0.01 to 5 M) [35]. Cyclic voltammetry and in situ Fourier Transform Infrared (FTIR) spectroelectrochemistry were used to investigate oxidation products at different pH values. They found that the ethanol oxidation activity on Pd was largely affected by pH. The highest activity was obtained in 1 M NaOH. This was supported by their previous study [36], which was attributed to OHads species on Pd. The density functional theory (DFT) calculations show that in acidic media continued dehydrogenation of ethanol is difficult due to the lack of OH species to instantly remove hydrogen, while in alkaline media, ethanol and sufficient OH can be adsorbed on Pd leading to continuous oxidation. The main oxidation product was sodium acetate with NaOH concentrations higher than 0.5 M. No CO formation was detected by FTIR suggesting low poisoning effect with ethanol oxidation on Pd in alkaline media. The mechanism for electrochemical oxidation of ethylene glycol in alkaline media was proposed by Matsuoka et al. [37]. They stated that ethylene glycol can be oxidised to oxalate (COO--COO-) via a non-poisoning path, and to formate via a poisoning path (Figure 2). Further oxidation of formate will produce CO poisoning species, while oxalate is very stable in alkaline medium and cannot be further oxidised, and as a result, no CO poisoning species are produced. In this case, the poisoning effect on the platinum is less significant compared to methanol. Glycerol has attracted interest in its use as fuel for DAFCs recently. It is produced in large quantities as a byproduct of biodiesel production. DAFCs provide the possibility of generating energy from the waste. The mechanism of electrochemical oxidation of glycerol in alkaline solution was investigated by Roquet et al. and Schell et al. [38,39]. Glyceraldehyde was found to be the main reaction product, but formic, glycolic, tartronic and glyceric acids were also detected [38]. Figure 2. Reaction pathways of ethylene glycol electrochemical oxidation in alkaline media [37]. CH2OH CH2OH Ethylene Glycol CH2OH(CHO) Glycol aldehyde In Table 1, the electrochemical oxidation of various alcohols studied in alkaline media has been summarised. Poisoning path Non poisoning path CO32- (COO-) (COO-) Oxalate (CHO) (CHO) Glyoxal CHO(COO-) Glyoxylate CH2OH(COO-) Glycolate HCOO- Formate COPDF Image | Aspects of Direct Alkaline Alcohol Fuel Cells
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