Fuel cells anodic reaction

Fuel Cell Anode Reaction Cathode Reaction... 

Fuel processing is defined in this Handbook as the conversion of a commercially available gas, liquid, or solid fuel (raw fuel) to a fuel gas reformate suitable for the fuel cell anode reaction. Fuel processing encompasses the cleaning and removal of harmful species in the raw fuel, the conversion of the raw fuel to the fuel gas reformate, and downstream processing to alter the fuel gas reformate according to specific fuel cell requirements. Examples of these processes are ... 

The PtML/Ru electrocatalysts were inaugurated for fuel cell anode reactions, and the catalysts were synthesized by two methods. The first method facilitated the formation of submonolayer-to-multilayer Pt deposits on Ru surfaces via the electroless (spontaneous) deposition of Pt on Ru [103-107]. The coverage and morphology of the Pt deposit on Ru depended on the concentration of platinum ions and the time of deposition. The activity and selectivity of the electrocatalyst was fine-tuned by changing the coverage (the cluster size) of the Pt deposit, and the optimized PtRu2o/C (with atomic ratio of Pt Ru as 1 20) electrocatalyst demonstrated superior CO tolerance and stability compared to conventional Pt-Ru/C alloy catalyst [104]. 

In fuel processing, commercially available gas, liquid, or solid fuels are converted to a fuel gas reformate suitable for the fuel cell anode reaction. Fuel... 

Poisoning of platinum fuel cell catalysts by CO is undoubtedly one of the most severe problems in fuel cell anode catalysis. As shown in Fig. 6.1, CO is a strongly bonded intermediate in methanol (and ethanol) oxidation. It is also a side product in the reformation of hydrocarbons to hydrogen and carbon dioxide, and as such blocks platinum sites for hydrogen oxidation. Not surprisingly, CO electrooxidation is one of the most intensively smdied electrocatalytic reactions, and there is a continued search for CO-tolerant anode materials that are able to either bind CO weakly but still oxidize hydrogen, or that oxidize CO at significantly reduced overpotential. 

Finally, we have discussed the effect of incomplete Cj oxidation product formation for fuel cell applications and the implications of these processes for reaction modeling. While for standard DMFC applications, formaldehyde and formic acid formation will be negligible, they may become important for low temperature applications and for microstructured cells with high space velocities. For reaction modeling, we have particularly stressed the need for an improved kinetic data base, including kinetic data under defined reaction and transport conditions and kinetic measurements on the oxidation of Ci mixtures with defined amounts of formaldehyde and formic acid, for a better understanding of cross effects between the different reactants at an operating fuel cell anode. 

PAFC systems achieve about 37 to 42% electrical efficiency (based on the LHV of natural gas). This is at the low end of the efficiency goal for fuel cell power plants. PAFCs use high cost precious metal catalysts such as platinum. The fuel has to be reformed external to the cell, and CO has to be shifted by a water gas reaction to below 3 to 5 vol% at the inlet to the fuel cell anode or it will affect the catalyst. These limitations have prompted development of the alternate, higher temperature cells, MCFC, and SOFC. 

In general, reforming of the CH4 fuel with excess H2O outside the cell has been practiced both in molten carbonate and solid oxide fuel cell systems in order to produce H2, more reactive on a fuel cell anode, and to avoid the possible deposition of C. This reforming reaction... 

For every molecule of hydrogen (H2) that reacts within a fuel cell, two electrons are liberated at the fuel cell anode. This is most easily seen in the PAFC and PEFC because of the simplicity of the anode (fuel) reaction, although the rule of two electrons per diatomic hydrogen molecule (H2) holds true for all fuel cell types. The solution also requires knowledge of the definition of an ampere (A) and an equivalence of electrons. 

In a PEM fuel cell, the CDLs are where the electrochemical reactions occur for electric power generation. For example, for H2/air (O2) PEM fuel cells, the reactions occurring at the anode and cathode catalyst layers are as follows ... 

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). 

If mixture 1 is now considered, it can be seen that it contains 19% methane but only approximately 3% water. The methane and water are expected to react at the fuel cell anodes via the steam reforming reaction. The large excess of methane will result in almost complete depletion of the water content of the fuel gas. It is this depletion of the water content and not the hydrogen concentration that leads to an increase in the Nemst voltage and hence to improved performance of the fuel cells. 

A comparison of the E°s would lead us to predict that the reduction (it) would be favored over that of (i). This is certainly the case from a purely energetic standpoint, but as was mentioned in the section on fuel cells, electrode reactions involving 02 are notoriously slow (that is, they are kinetically hindered), so the anodic process here is under kinetic rather than thermodynamic control. The reduction of water (iv) is energetically favored over that of Na+ (iii), so the net result of the electrolysis of brine is the production of Cl2 and NaOH ( caustic ), both of which are of immense industrial importance ... 

A porous anode and cathode are attached to each surface of the membrane, forming a membrane-electrode assembly, similar to that employed in SPE fuel cells. Electrochemical reactions (electron transfer-l-hydrogenation) occur at the interfaces between the ion exchange membrane and electrochemically active layers of electrodes. Electrochemical reductive HDH occurred at the interfaces between the ion exchange membrane and the cathode catalyst layer when an electrical current is applied between the electrodes ... 

Setoguchi, T. et al., Effects of anode materials and fuel on anodic reaction of solid oxide fuel-cells,/. Electrochem. Soc., 139, 2875-2880 (1993). 

The high-cost of materials and efficiency limitations that chemical fuel cells currently have is a topic of primaiy concern. For a fuel cell to be effective, strong acidic or alkaline solutions, high temperatures and pressures are needed. Most fuel cells use platinum as catalyst, which is expensive, limited in availability, and easily poisoned by carbon monoxide (CO), a by-product of many hydrogen production reactions in the fuel cell anode chamber. In proton exchange membrane (PEM) fuel cells, the type of fuel used dictates the appropriate type of catalyst needed. Within this context, tolerance to CO is an important issue. It has been shown that the PEM fuel cell performance drops significantly with a CO con-... 

Some key adsorbates and reaction intermediates relevant to fuel-cell anodes are H2 as the fuel, CO and CO2 as poisons in hydrogen reformate feeds, and water as a co-adsorbate and potential oxidant. In the case of the cathode, oxygen is clearly the most important reactant. In the case of a number of these molecules, such as H2, O2, and H2O, not only is the molecular adsorption important on platinum (or promoted platinum catalysts), but the dissociative adsorption of the molecules is important as well. With this in mind, some details concerning the dynamics of adsorption of these molecules, the associated dissociation barriers, molecular degrees of freedom, and energy partition are important to the overall catalytic processes. In addition to the... 

MCFCs do not need external reforming of methane, as reforming takes place at the anode of the fuel cell. The reactions occurring at the anode are as follows (see Fig. 12) ... 

Fig. 12 Methane reforming reaction at the anode of a molten carbonate fuel cell. The reaction between fuel and water takes place in the outer part of the anode, the produced hydrogen reacts at the interface anode-electrolyte.

E25.17 Electrocatalysts are compounds that are capable of reducing the kinetic barrier for electrochemical reactions (barrier known as overpotential). While platinum is the most efficient electrocatalyst for accelerating oxygen reduction at the fuel cell cathode, it is expensive (recall Section 25.18 Electrocatalysis). Current research is focused on the efficiency of a platinum monolayer by placing it on a stable metal or alloy clusters your book mentions the use of the alloy PtsN. An example would be a platinum monolayer fuel-cell anode electrocatalyst, which consists of ruthenium nanoparticles with a sub-monolayer of platinum. Other areas of research include using tethered metalloporphyrin complexes for oxygen activation and subsequent reduction. 

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