Anodic Oxidation of Fuels at Low Temperatures

The anodic oxidation of fuels in low temperature cells, mainly on platinum metals, platinum metal alloys and alloys of platinum metals with other metals, is the subject of this chapter. Most oxidation studies were made on these metals because the efficiency of other electrocatalysts is too low. The mechanism for the oxidation of carbon monoxide, nlixtures of hydrogen and carbon monoxide, formic acid, methanol, higher alcohols, hydrocarbons, and hydrazine is discussed in separate sections. 

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A viable electrocatalyst operating with minimal polarization for the direct electrochemical oxidation of methanol at low temperature would strongly enhance the competitive position of fuel ceU systems for transportation appHcations. Fuel ceUs that directiy oxidize CH OH would eliminate the need for an external reformer in fuel ceU systems resulting in a less complex, more lightweight system occupying less volume and having lower cost. Improvement in the performance of PFFCs for transportation appHcations, which operate close to ambient temperatures and utilize steam-reformed CH OH, would be a more CO-tolerant anode electrocatalyst. Such an electrocatalyst would reduce the need to pretreat the steam-reformed CH OH to lower the CO content in the anode fuel gas. Platinum—mthenium alloys show encouraging performance for the direct oxidation of methanol. 

For these low-temperature fuel cells, the development of catalytic materials is essential to activate the electrochemical reactions involved. This concerns the electro-oxidation of the fuel (reformate hydrogen containing some traces of CO, which acts as a poisoning species for the anode catalyst methanol and ethanol, which have a relatively low reactivity at low temperatures) and the electroreduction of the oxidant (oxygen), which is still a source of high energy losses (up to 30-40%) due to the low reactivity of oxygen at the best platinum-based electrocatalysts. 

The high theoretical efficiency of a fuel cell is substantially reduced by the finite rate of dynamic processes at various locations in the cell. Substantial efficiency losses at typical operating temperatures occur already in the anodic and cathodic catalyst layers due to the low intrinsic reaction rates of the oxygen reduction and, in the case of the DMFC, of the methanol oxidation reaction. (The catalytic oxidation of hydrogen with platinum catalysts is very fast and thus does not limit PEFC performance.) In addition, at low temperatures, turnover may be limited by noble metal catalyst poisoning due to sulfur... 

The DMFC operates, as its name suggests, by direct, complete electrooxidation of methanol to CO2 at the cell anode. The methanol anode is coupled in the DMFC with an air cathode, completing a cell schematically shown in Fig. 50. In the majority of recent development efforts, the DMFC has been based on a protonconducting polymeric membrane. The uniqueness of this type of fuel cell is the direct anodic oxidation of a carbonaceous fuel. Such a direct electrochemical conversion process of liquid fuel and air to electric power at low temperatures can provide a basis for a very simple fuel-cell system. 

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