Direct alcohol fuel cells formic acid

The main problems regarding the replacement of batteries by direct alcohol fuel cells are related to the largest volume required by the fuel cells, as compared to the batteries which have become highly compact (because DAFCs have not reached yet high efficiencies), elimination of residues of the methanol partial oxidation (generally mixtures of water with formic acid, methyl formate, and formaldehyde), and the high temperature which can reach the DAFC (up to around 85 °C for cells using Nafion membranes) [11, 12]. 

In direct alcohol fuels cells (DAFCs), some simple organic molecules such as methanol, ethanol, formic acid, and ethylene glycol are used as alternative fuels. Besides the slow kinetics of ORR in the cathode, the slow alcohol oxidation reaction on Pt is another major contribution to low DAFC performance. 

Other Fuel Cells Many other fuel cell systems exist, and new versions are constantly being developed. Many of these are simply existing fuel cell systems with a different fuel. For example, PEFCs based on a direct alcohol solution offer alternatives to DMFCs for portable power and include those based on formic acid [11], dimethyl ether [12], ethylene glycol, dimethyl oxalate, and other so-called direct alcohol fuel cells (DAFCs) [13, 14]. 

The conventional electrochemical reduction of carbon dioxide tends to give formic acid as the major product, which can be obtained with a 90% current efficiency using, for example, indium, tin, or mercury cathodes. Being able to convert CO2 initially to formates or formaldehyde is in itself significant. In our direct oxidation liquid feed fuel cell, varied oxygenates such as formaldehyde, formic acid and methyl formate, dimethoxymethane, trimethoxymethane, trioxane, and dimethyl carbonate are all useful fuels. At the same time, they can also be readily reduced further to methyl alcohol by varied chemical or enzymatic processes. 

Fuel cells using directly liquid fuels are advantageous in this aspect. Methanol, formaldehyde (water solution), formic acid (water solution) and hydrazine are among fuels relatively easy to oxidize electrochemically. Alcohol and hydrocarbon with larger molecular weight are much harder to oxidize completely to C02- Other qualifications to be considered are price, availability, safety, energy density and ease of handling. 

Chen W, Tang Y, Bao J, Gao Y, Liu C, Xing W, Lu T (2007) Study of cartxui-supported Au catalyst as the cathodic catalyst in a direct formic acid fuel cell prepared using a polyvinyl alcohol protectirai method. J Powct Sources 167 315—318... 

Chapter 1 discusses the current status of electrocatalysts development for methanol and ethanol oxidation. Chapter 2 presents a systematic study of electrocatalysis of methanol oxidation on pure and Pt or Pd overlayer-modified tungsten carbide, which has similar catalytic behavior to Pt. Chapters 3 and 4 outline the understanding of formic acid oxidation mechanisms on Pt and non-Pt catalysts and recent development of advanced electrocatalysts for this reaction. The faster kinetics of the alcohol oxidation reaction in alkaline compared to acidic medium opens up the possibility of using less expensive metal catalysts. Chapters 5 and 6 discuss the applications of Pt and non-Pt-based catalysts for direct alcohol alkaline fuel cells. 

Direct fuel cells are devices that directly convert the chemical energy stored in carbon-containing chemicals into electrical energy by oxidizing them at the anode of the fuel cell without prior conversion into hydrogen, as wiU be discussed in Section 15.6. Fuels suitable for direct conversion in low-temperature fuel cells typically contain oxygen atoms and include C1-C3 mono- and polyhydric alcohols and formic acid. 

Here, M represents the electronically conducting electrode material (e.g.. Ft) that is not involved in the overall reaction and plays the role of an electrocatalyst for the reaction. The last intermediate step occurs in two identical consecutive steps since electron transfer occurs by quantum mechanical tunneling, which involves only one electron transfer at a time. When multistep reactions take place, there is the possibility of parallel-intermediate steps. The parallel-step reactions could lead to the same final product or to different products. Direct electro-oxidation of organic fuels, such as hydrocarbons or alcohols, in a fuel cell exhibits this behavior. For instance, in the case of methanol, a six-electron transfer, complete oxidation to carbon dioxide can occur consecutively in six or more consecutive steps. In addition, partially oxidized reaction products could arise, producing formaldehyde and formic acid in parallel reactions. These, in turn, could then be oxidized to methanol. 

Other similar cases exist, such as direct electro-oxidation of alcohols such as methanol and formic acid in low-temperature fuel cells. In these cases, an alternative to the BV formulation that accounts for the limiting adsorption and charge transfer steps is appropriate. Two common models for a surface adsorption limited reaction are the Langmuir and Temkin kinetics. In the simpler Langmuir model, the surface adsorption rate constant is independent of surface coverage. In the Temkin model, the adsorption rate constant is modeled as a function of the surface coverage of adsorbed species. In both models, a two-step reaction mechanism is assumed [6] ... 

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