Cathode electrocatalysis reduction

V. Electrocatalysis of Cathodic Oxygen Reduction and Anodic Hydrogen Oxidation in Fuel Cells... 

Also for cathodic oxygen reduction in low-temperature fuel cells, platinum is indispensible as a catalyst whereas the cathodic electrocatalysts in MCFCs and SOFCs are lithiated nickel oxide and lanthanum-manganese per-ovskite, respectively. Appleby and Foulkes in the Fuel Cell Handbook (101) reviewed the fundamental work as well as the technologically important publications covering electrocatalysis in fuel cells till 1989. 

K. Wiesener and D. Ohms, "Electrochemical Hydrogen Technologies Cap. 3 - Electrocatalysis of the Cathodic Oxygen Reduction", Ed. H. Wendt, Elsevier, Amsterdam, 1990 63-103. 

The cathodic oxygen reduction (ORR) electrocatalysis on chalcogenides is discussed in an authoritative Chapter by N. Alonso-Vante. Several new finding are discussed related to the design, genesis and ORR mechanism on these materials which are promising catalysts for Pt replacement in the future. 

Research in electrocatalysis was strongly stimulated in the early 1960s by efforts toward the development of various types of fuel cells. Studies were initiated on the various factors influencing the rates not only of hydrogen evolution but also of other reactions, particularly cathodic oxygen reduction and the complete oxidation of simple organic substances ( fuels ) to carbon dioxide. The... 

Electrocatalysis Again by definition, an electrocatalyst is a solid, in fact an electrode, which can accelerate a process involving a net charge transfer, such as e.g. the anodic oxidation of H2 or the cathodic reduction of 02 in solid electrolyte cells utilizing YSZ ... 

ELECTROCATALYSIS OF OXYGEN REDUCTION IN THE FUEL CELL CATHODE NEW INSIGHTS AND NEW OUESTIONS... 

ELECTROCATALYSIS OE OXYGEN REDUCTION IN THE EUEL CELL CATHODE... 

The electrode reaction of an organic substance that does not occur through electrocatalysis begins with the acceptance of a single electron (for reduction) or the loss of an electron (for oxidation). However, the substance need not react in the form predominating in solution, but, for example, in a protonated form. The radical formed can further accept or lose another electron or can react with the solvent, with the base electrolyte (this term is used here rather than the term indifferent electrolyte) or with another molecule of the electroactive substance or a radical product. These processes include substitution, addition, elimination, or dimerization reactions. In the reactions of the intermediates in an anodic process, the reaction partner is usually nucleophilic in nature, while the intermediate in a cathodic process reacts with an electrophilic partner. 

Figure 6.7 illustrates the voltammetric response of the third-generation SOD-based 02 biosensors with Cu, Zn-SOD confined onto cystein-modified Au electrode as an example. The presence of 02" in solution essentially increases both the cathodic and anodic peak currents of the SOD compared with its absence [150], Such a redox response was not observed at the bare Au or cysteine-modified Au electrodes in the presence of 02". The observed increase in the anodic and cathodic current response of the Cu, Zn-SOD/cysteine-modified Au electrode in the presence of 02 can be considered to result from the oxidation and reduction of 02, respectively, which are effectively mediated by the SOD confined on the electrode as shown in Scheme 3. Such a bi-directional electromediation (electrocatalysis) by the SOD/cysteine-modified Au electrode is essentially based on the inherent specificity of SOD for the dismutation of 02", i.e. SOD catalyzes both the reduction of 02 to H202 and the oxidation to 02 via a redox cycle of its Cu (II/I) complex moiety as well as the direct electron transfer of SOD realized at the cysteine-modified Au electrode. Thus, this coupling between the electrode and enzyme reactions of SOD could facilitate the development of the third-generation biosensor for 02". ...

Moreover, despite the many advances in electrochemical measurement and modeling, our understanding of SOFC cathode mechanisms remains largely circumstantial today. Our understanding often relies on having limited explanations for an observed phenomenon (e.g., chemical capacitance as evidence for bulk transport) rather than direct independent measures of the mechanism (e.g., spectroscopic evidence of oxidation/reduction of the electrode material). At various points in this review we saw that high-vacuum techniques commonly employed in electrocatalysis can be used in some limited cases for SOFC materials and conditions (PEEM, for example). New in-situ analytical techniques are needed, particularly which can be applied at ambient pressures, that can probe what is happening in an electrode as a function of temperature, P02, polarization, local position, and time. 

Electrocatalysis in fuel cells requires as well substances capable of catalyzing the anodic oxidation of fuels as catalysts for the cathodic reduction of oxygen. Several dyestuffs that catalyze oxygen reduction are known, but up to now only one has been described as active in anodic reactions. All these dyestuffs are N4-chelates. 

The chemistry of electrochemical reaction mechanisms is the most hampered and therefore most in need of catalytic acceleration. Therefore, we understand that electrochemical catalysis does not, in principle, differ much fundamentally and mechanistically from chemical catalysis. In addition, apart from the fact that charge-transfer rates and electrosorption equilibria do depend exponentially on electrode potential—a fact that has no comparable counterpart in chemical heterogeneous catalysis—in many cases electrocatalysis and catalysis of electrochemical and chemical oxidation or reduction processes follow very similar if not the same pathways. For instance as electrochemical hydrogen oxidation and generation is coupled to the chemical splitting of the H2 molecule or its formation from adsorbed hydrogen atoms, respectively, electrocatalysts for cathodic hydrogen evolution—... 

The Electrocatalysis of Oxygen Reduction at Fuel Cell Cathodes... 

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