Electrocatalytic kinetics

Part I presents the state of the art of the theory of catalysis and electrocatalysis at clusters and nanoparticles. This section provides the current frame of modeling of the interaction of clusters with substrates as well as catalytic and electrocatalytic kinetics on clusters and nanoparticles, including ab initio quantum mechanical calculations, and epitomizes recent advances in understanding the relation between electronic structure and catalytic/electrocatalytic activity. 

The relevance and the need to addreess electrocatalytic kinetics is closely associated with the recent developments of fuel cells. The process for fuels cells, with hydrogen as fuel can be represented in a simple way... 

S.3.3 Electrocatalytic Modified Electrodes Often the desired redox reaction at the bare electrode involves slow electron-transfer kinetics and therefore occurs at an appreciable rate only at potentials substantially higher than its thermodynamic redox potential. Such reactions can be catalyzed by attaching to the surface a suitable electron transfer mediator (45,46). Knowledge of homogeneous solution kinetics is often used to select the surface-bound catalyst. The function of the mediator is to facilitate the charge transfer between the analyte and the electrode. In most cases the mediated reaction sequence (e.g., for a reduction process) can be described by... 

With the exception of H20 electrolysis51,59 it is likely that, for all other electrocatalytic reactions listed on Table 3.2, catalytic phenomena taking place on the gas-exposed electrode surface or also on the solid electrolyte surface, had a certain role in the observed kinetic behaviour. However, this role cannot be quantified, since the measured increase in reaction rate was, similarly to the case of the reactions listed on Table 3.1, limited by Faraday s law, i.e. ... 

The electrocatalytic oxidation of methanol has been thoroughly investigated during the past three decades (see reviews in Refs. 21-27), particularly in regard to the possible development of DMFCs. The oxidation of methanol, the electrocatalytic reaction, consists of several steps, which also include adsorbed species. The determination of the mechanism of this reaction needs two kinds of information (1) the electrode kinetics of the formation of partially oxidized and completely oxidized products (main and side products) and (2) the nature and the distribution of intermediates adsorbed at the electrode surface. 

The model assumes a well-mixed gas phase composition in the recycle loop, a well justified assumption in view of the very high (10-200) recycle ratio values used in the present work. For the batch electrocatalytic version we also neglect volume changes and assume linear kinetics for steps 1,3 and 4 of the consecutive OCM network (1), i.e. ... 

Methane can be oxidatively coupled to ethylene with very high yield using the novel gas recycle electrocatalytic or catalytic reactor separator. The ethylene yield is up to 85% for batch operation and up to 50% for continuous flow operation. These promising results, which stem from the novel reactor design and from the adsorptive properties of the molecular sieve material, can be rationalized in terms of a simple macroscopic kinetic model. Such simplified models may be useful for scale up purposes. For practical applications it would be desirable to reduce the recycle ratio p to lower values (e.g. 5-8). This requires a single-pass C2 yield of the order of 15-20%. The Sr-doped La203... 

In the present chapter we want to look at certain electrochemical redox reactions occurring at inert electrodes not involved in the reactions stoichiometrically. The reactions to be considered are the change of charge of ions in an electrolyte solution, the evolution and ionization of hydrogen, oxygen, and chlorine, the oxidation and reduction of organic compounds, and the like. The rates of these reactions, often also their direction, depend on the catalytic properties of the electrode employed (discussed in greater detail in Chapter 28). It is for this reason that these reactions are sometimes called electrocatalytic. For each of the examples, we point out its practical value at present and in the future and provide certain kinetic and mechanistic details. Some catalytic features are also discussed. 

Electrocatalytic effects cannot be studied in depth without a detailed knowledge of the kinetics and mechanism of the electrochemical reaction being examined. In fact, diverse effects can be exerted on the reaction ... 

The above brief analysis underlines that the porous structure of the carbon substrate and the presence of an ionomer impose limitations on the application of porous and thin-layer RDEs to studies of the size effect. Unless measurements are carried out at very low currents, corrections for mass transport and ohmic limitations within the CL [Gloaguen et ah, 1998 Antoine et ah, 1998] must be performed, otherwise evaluation of kinetic parameters may be erroneous. This is relevant for the ORR, and even more so for the much faster HOR, especially if the measurements are performed at high overpotentials and with relatively thick CLs. Impurities, which are often present in technical carbons, must also be considered, given the high purity requirements in electrocatalytic measurements in aqueous electrolytes at room temperature and for samples with small surface area. 

As the generality of equations of type (5.2.3) should not be exaggerated (e.g. in the presence of strong adsorption, such as in electrocatalytic processes, they are no longer valid), the basic features of electrochemical kinetics will be explained by using the simple electrode reaction... 

The reduction of organic halides is of practical importance for the treatment of effluents containing toxic organic halides and also for valuable synthetic applications. Direct electroreduction of alkyl and aryl halides is a kinetically slow process that requires high overpotentials. Their electrochemical activation is best achieved by use of electrochemically generated low-valent transition metal catalysts. Electrocatalytic coupling reactions of organic halides were reviewed in 1997.202... 

A number of mechanistic pathways have been identified for the oxidation, such as O-atom transfer to sulfides, electrophilic attack on phenols, hydride transfer from alcohols, and proton-coupled electron transfer from hydroquinone. Some kinetic studies indicate that the rate-determining step involves preassociation of the substrate with the catalyst.507,508 The electrocatalytic properties of polypyridyl oxo-ruthenium complexes have been also applied with success to DNA cleavage509,5 and sugar oxidation.511... 

Techniques for attaching such ruthenium electrocatalysts to the electrode surface, and thereby realizing some of the advantages of the modified electrode devices, have been developed.512-521 The electrocatalytic activity of these films have been evaluated and some preparative scale experiments performed. The modified electrodes are active and selective catalysts for oxidation of alcohols.5 6-521 However, the kinetics of the catalysis is markedly slower with films compared to bulk solution. This is a consequence of the slowness of the access to highest oxidation states of the complex and of the chemical reactions coupled with the electron transfer in films. In compensation, the stability of catalysts is dramatically improved in films, especially with complexes sensitive to bpy ligand loss like [Ru(bpy)2(0)2]2 + 51, 519 521... 

HydrophiIic versus hydrophobic coadsorption. The contrast between the hydrophilic and hydrophobic coadsorption seen on Rh(111) and Pt(lll), if confirmed under normal electrochemical conditions, might be of electrocatalytic importance. On Rh(lll), where net attractive CO-HgO interactions produce a mixed phase in which CO is displaced to a three-fold binding site which is not occupied in the absence of water, CO and water appear to occupy adjacent binding sites. Such thorough mixing of the oxygen source (water) and the intermediate [or poison] (CO) should improve electrooxidation rates for C 0 H fuels (11). On Pt(lll), where net repulsions cause condensation of CO and water into separate patches, reaction between the adsorbed species could occur only at the boundaries between patches, and one would expect slower kinetics. 

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