Fuel cell electrocatalysis electrochemical kinetics

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). 

Several important energy-related applications, including hydrogen production, fuel cells, and CO2 reduction, have thrust electrocatalysis into the forefront of catalysis research recently. Electrocatalysis involves several physiochemical environmental dfects, which poses substantial challenges for the theoreticians. First, there is the electric potential which can aifect the thermodynamics of the system and the kinetics of the electron transfer reactions. The electrolyte, which is usually aqueous, contains water and ions that can interact directly with a surface and charged/polar adsorbates, and indirectly with the charge in the electrode to form the electrochemical double layer, which sets up an electric field at the interface that further affects interfacial reactivity. 

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. 

The present chapter has presented a comprehensive review of electrode kinetic and catalytic aspects associated with methanol, ethanol, and formic acid oxidation. The prevalent point of view in selecting and organizing the vast amount of information in this area was that of practical applicability in order to advance the technology of direct fuel cells. Emphasis was placed on the catalytic system , starting with catalyst preparation methods and focusing on the interaction of catalyst/support/ionomer/chemical species. The development of catalytic systems was followed, from fundamental electrochemical and surface science studies to fuel cell experiments (whenever experimental data was available). Advances in both fundamental electrocatalysis and electrochemical engineering hold promise for the development of high-performance and cost-effective direct liquid fuel cells. 

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