Active direct alcohol fuel cells

Bambagioni V, Bianchini C, Marchionni A, Filippi J, Vizza F, Teddy J, Serp P, Zhiani M (2009) Pd and Pt-Ru anode electrocatalysts supported on multi-walled carbon nanotubes and their use in passive and active direct alcohol fuel cells with an anion-exchange membrane (alcohol = methanol, ethanol, glycerol). J Power Sources 190(2) 241-251... 

Bambagioni, V, Bianchini, C., Marchionni, A., et al. (1990). Pd and Pt-Ru Anode Electrocatalysts Supported on Multi-waUed Carbon Nanotubes and their Use in Passive and Active Direct Alcohol Fuel Cells with an Anion-exchange Membrane (Alcohol = Methanol, Ethanol, Glycerol), J. Power Sources, 190, pp. 241-251. 

DMFCs and direct ethanol fuel cells (DEFCs) are based on the proton exchange membrane fuel cell (PEM FC), where hydrogen is replaced by the alcohol, so that both the principles of the PEMFC and the direct alcohol fuel cell (DAFC), in which the alcohol reacts directly at the fuel cell anode without any reforming process, will be discussed in this chapter. Then, because of the low operating temperatures of these fuel cells working in an acidic environment (due to the protonic membrane), the activation of the alcohol oxidation by convenient catalysts (usually containing platinum) is still a severe problem, which will be discussed in the context of electrocatalysis. One way to overcome this problem is to use an alkaline membrane (conducting, e.g., by the hydroxyl anion, OH ), in which medium the kinetics of the electrochemical reactions involved are faster than in an acidic medium, and then to develop the solid alkaline membrane fuel cell (SAMFC). 

In order to improve the fuel utilization in a Direct Alcohol Fuel Cell (DAFC) it is important to investigate the reaction mechanism and to develop active electrocatalysts able to activate each reaction path. The elncidation of the reaction mechanism, thus, needs to combine pnre electrochemical methods (cyclic voltammetry, rotating disc electrodes, etc.) with other physicochemical methods, such as in situ spectroscopic methods (infrared and UV-VIS" reflectance spectroscopy, or mass spectroscopy such as EQCM, DEMS " ), or radiochemical methods to monitor the adsorbed intermediates and on line chromatographic techniques"" to analyze qnantitatively the reaction products and by-products. 

Besides, it has been shown that palladium is promising for direct alcohol fuel cells applications as it is very active for ethanol electro-oxidation in basic media and that its electroactivity is even higher than that of platinum. Recently, Pd nanoballs and nanowires synthesized by radiolysis in hexagonal mesophases have shown an important elec-trocatalytic activity for ethanol electro-oxidation. ... 

Direct alcohol fuel cells (DAFC) are very attractive as power sources for mobile and portable applications. The alcohol is fed directly into the fuel cell without any previous chemical modification and is oxidized at the anode while oxygen is reduced at the cathode. Methanol has been considered the most promising fuel because it is more efficiently oxidized than other alcohols. Among different electrocatalysts tested in the methanol oxidation, PtRu-based electrocatalysts were the most active [1-3]. In Brazil ethanol is an attractive fuel as it is produced in large quantities from sugar cane and it is much less toxic than methanol. On the other hand, its complete oxidation to CO2 is more difficult than that of methanol due to the difficulty in C-C bond breaking and to the formation of CO-intermediates that poison the platinum anode catalysts. Thus, more active electrocatalysts are essential to enhance the ethanol electrooxidation [3],... 

Direct Alcohol Fuel Cell Active Systems... 

The Chapter by C. Bianchini provides a comprehensive and authoritative overview of recent advances on the use of Pd-based electrocatalysts in direct alcohol fuel cells. The Chapter shows lucidly how the dilution of Pd with non-noble metals in a smart catalytic architecture can lead to inexpensive and highly active anode electrodes which can knock down the main barriers for the commercialization of direct alcohol/fuel cells (DAFC). 

YE. (2008) Electrocatalytic activity and stability of Pt supported on Sb-doped Sn02 nanoparticles for direct alcohol fuel cells. / Catal., 258, 143-152. 

The same problem is encountered during electrosynthesis by the oxidation of a chemical compound. In an electrochemical reactor, the oxidation reaction has to be counterbalanced with a reduction reaction in order to close the electrical circuit. Under these conditions, it is better for industrial applications to use oxygen from air, which is free, as the oxidative agent. Such a system then becomes very close to a fuel cell system, apart from the oxidation reaction that has to be controlled here, whereas the complete oxidation of alcohol into CO2 is sought in direct alcohol fuel cells (DAFCs). For this reason, fuel cell systems will be considered in this chapter to illustrate the important problem of oxygen activation for electrochemical processes. 

Recently, Chu and Shul [128] have applied combinatorial chemistry to the screening of 66 PtRuSn-anode arrays for investigation of methanol, ethanol, and 2-propanol oxidation. The screening was performed by employing quinine as indicator of the catalytic activity, which allowed for selection of the optimum composition of electrocatalysts for DAFCs (Direct Alcohol Fuel Cells). PtRuSn (80 20 0), PtRuSn (50 0 50), and PtRuSn (50 30 20) furnished the lowest onset potential for methanol, ethanol, and 2-propanol electro-oxidation according to the CV results, respectively. The active area/composition for ethanol electro-oxidation is represented in Figure 15.8 as adapted from Ref. [128]. 

The same group, in a previous work, reported on the realization of a hybrid anode electrode [197]. An appreciable improvement in methanol oxidation activity was observed at the anode in direct methanol fuel cells containing Pt-Ru and Ti02 particles. Such an improvement was ascribed to a synergic effect of the two components (photocatalyst and metal catalyst). A similar behavior was also reported for a Pt-Ti02-based electrode [198]. Another recent study involved the electrolysis of aqueous solutions of alcohols performed on a Ti02 nanotube-based anode under solar irradiation [199]. 

Yet, the most interesting results for ORR on Fe-Pd/WC catalyst are those obtained in the presence of alcohol. The electrode response for Fe-Pd/WC system in oxygen saturated acid has not been affected even at high concentrations of methanol, whereas the ORR on conventional catalyst Pt/C was completely restrained since the dominant reaction was basically methanol oxidation rally. Such results suggested that Pd-Fe/WC/C could be an excellent candidate for direct methanol fuel cell (DMFC) cathode because of its inert activity toward methanol oxidation as seen in Fig. 23.3. The utilization of a completely inert catalyst to methanol oxidation is one of the important criteria for DMFCs to operate at higher power densities since the issue of methanol crossover is unavoidable and can cause dramatic loss in cell performance, especially with common catalysts that are active... 

In fuel cells working with a liquid fuel, usually an alcohol such as methanol (a direct methanol fuel cell - DMFC), ethanol (a direct ethanol fuel cell - DEFC), glycerol (a direct glycerol fuel cell - DGEC), etc., in addition to the necessity to activate the ORR at the cathode, the alcohol oxidation reaction at the anode also involves a high overpotential. This high overpotential is mainly due to the formation, after dissociative adsorption of the alcohol at the catalyst surface, of poisoning species which block the catalytic surface the main one adsorbed is carbon monoxide. ... 

Oxidation of hydrocarbons and alcohols If reasonably effective oxidation catalysts can be identified for aqueous electrolytes, hydrocarbon and alcohol oxidation processes would make possible promising fuel cells operating directly on quite practical fuels at moderate temperatures. The currently used platinum and platinum-family metals and alloys have substantial activity, but it is not sufficient for practical fuel cells with aqueous electrolytes. With the many electrons involved in the complete oxidation, the detailed mechanisms for the oxidation are likely to be quite complex. To avoid incomplete oxidation it is probably necessary to have the reactants remain adsorbed on the electrode surface through the complete oxidation to C02 and H20. Here again, new promising catalysts and new experimental approaches are needed. 

There are different kinds of DAFC operation conditions depending of the way the fuel and the oxidant (oxygen/air) are fed into the cell. In complete active fuel cells the liquid fuel (neat alcohol or aqueous solution) is pumped and gas is compressed, using auxiliary pumps and blowers, in order to improve mass transport and reduce concentration polarization losses in the system. On the other hand, in complete passive DAFC the alcohol reaches the anode catalyst layer by natural convection and the cathode breathes oxygen directly from the air. A number of intermediate options have been also studied and tested. 

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