Catalytic electrode materials

It is clear that the majority of electrochemical hydrogenations - those carried out at a Pb or similar electrode - have very little in common with the stoicheiometrically similar gas-phase reaction. But in respect of the sizeable number of electrochemical reductions carried out on catalytic electrode materials (e.g., transition metals), it seems that further work is useful to establish how much the two types of process have in common. The only way to do such studies is design electrochemical experiments to match existing gas-phase results or vice versa. But it could well be that from such studies, a store of newly available quantitative information would become available to practitioners of either discipline, and if this were to be the case, such a study would be a most worthwhile and cost-effective exercise. 

Bedioui, R, J. Devynck, and C. Bied-Charreton (1996). Electropolymerized manganese porphyrin films as catalytic electrode materials for biomimetic oxidations with molecular oxygen. J. Mol. Catalysis 113, 3-11. 

Cauquis, G., S. Cosnier, A. Deronzier, B. Galland, D. Limosin, J.C. Moutet, J. Bizot, D. Deprez, and J.P Pulicani (1993). Poly(pyrrole-manganese porphyrin)—a catalytic electrode material as a model system for olefin epoxidation and drug-metabolism with molecular-oxygen./. Electroanal. Chem. 352,181-195. 

In the other examples, the electrode materials are not involved in the reactions chemically, but constitute the source [sink] of electrons. Such electrodes are called nonconsumable. The term inert electrodes sometimes used is unfortunate insofar as the electrode itself is by no means inert rather, it has a strong catalytic effect on the electrode reaction. For reactions occurring at such electrodes, the terms oxidation- reduction... 

The search for new, more highly active and less expensive materials for catalytic electrodes and the attempts at reducing the loading of expensive platinum catalysts has led to numerous studies in the area of binary and multicomponent metal systems. These included various metal alloys as well as mixed microdeposits containing several... 

Another metal that has attracted interest for use as electrode material is rhodium, inspired by its high activity in the catalytic oxidation of CO in automotive catalysis. It is found that Rh is a far less active catalyst for the ethanol electro-oxidation reaction than Pt [de Souza et al., 2002 Leung et al., 1989]. Similar to ethanol oxidation on Pt, the main reactions products were CO2, acetaldehyde, and acetic acid. Rh, however, presents a significant better CO2 yield relative to the C2 compounds than Pt, indicating a... 

This last equation contains the two essential activation terms met in electrocatalysis an exponential function of the electrode potential E and an exponential function of the chemical activation energy AGj (defined as the activation energy at the standard equilibrium potential). By modifying the nature and structure of the electrode material (the catalyst), one may decrease AGq, thus increasing jo, as a result of the catalytic properties of the electrode. This leads to an increase in the reaction rate j. 

So far, certain biomimetic catalysts (1 and 2b in Fig. 18.17) have been shown to reduce O2 to H2O under a slow electron flux at physiologically relevant conditions (pH 7,0.2-0.05 V potential vs. NHE) and retain their catalytic activity for >10" turnovers. Probably, only the increased stability of the turning-over catalyst is of relevance to the development of practical ORR catalysts for fuel cells. In addition, biomimetic catalysts of series 1,2,3, and 5, and catalyst 4b are the only metalloporphyrins studied in ORR catalysis with well-defined proximal and distal environments. For series 2, which is by far the most thoroughly studied series of biomimetic ORR catalysts, these well-defined environments result in an effective catalysis that seems to be the least sensitive among all metalloporphyrins to the electrode material (whether the catalyst is adsorbed or in the film) and to chemicals present in the electrolyte or in the O2 stream, including typical catalyst poisons (CO and CN ). 

Iridium as an electrode material has received considerable attention in the last decade not only because of its excellent catalytic properties but also in relation to the electrochromic effect observed for anodic iridium oxide films (AIROF). Electrochromism of iridium was thought to be of technical relevance for display applications and triggered several studies of the electrochemical and optical properties of AlROFs [67, 85-88],... 

The catalytic properties of a Pt/Sn combination were observed on different kinds of electrode materials alloys [90], electro co-deposits of Pt and Sn [89, 90], underpotential deposited tin [42] or a mixture of tin oxide and platinum deposited on glass [95], All different materials present a marked influence on methanol electrooxidation. 

Modified electrodes containing cyclam derivatives have been prepared. The approach utilizing cyclam incorporated in Nafion film on a carbon electrode shows that the catalytic efficiency of the system is much lower than observed when the catalyst is adsorbed on the mercury. With electrodes prepared following the Langmuir Blodgett technique, only the electrode materials that allow the orientation of the monolayer so that the tail points to the substrate were found to be electrocatalytically active.165... 

In addition, it has been shown that the performance of the four-electron 02 reduction depends not only on the diporphyrin structure, but also on the electrode material upon which it is absorbed. Attempts to affix these catalysts onto electrode surfaces other than EPG, whilst preserving the four-electron catalytic activity, have been largely unsuccessful.18 One explanation is that some axial coordination of the porphyrin by the EPG electrode occurs which plays an important role. 

Carbon blacks are promising electrode materials due to their relatively high activities and long lifetimes in contrast to the lower activity or rapid deactivation of the other carbonaceous materials [16-20]. These catalytic characteristics of carbon blacks are attributed to their microstructure that has many active sites consisting of edges and defects in nanosized graphitic layers [19-21]. 

Electrocatalytic hydrogenation has the advantage of milder reaction conditions compared to catalytic hydrogenation. The development of various electrode materials (e.g., massive electrodes, powder cathodes, polymer film electrodes) and the optimization of reaction conditions have led to highly selective electrocatalytic hydrogenations. These are very suitable for the conversion of aliphatic and aromatic nitro compounds to amines and a, fi-unsaturated ketones to saturated ketones. The field is reviewed with 173 references in [158]. While the reduction of conjugated enones does not always proceed chemoselectively at a Hg cathode, the use of a carbon felt electrode coated with polyviologen/Pd particles provided saturated ketones exclusively (Fig. 34) [159]. 

For further contributions on the dia-stereoselectivity in electropinacolizations, see Ref. [286-295]. Reduction in DMF at a Fig cathode can lead to improved yield and selectivity upon addition of catalytic amounts of tetraalkylammonium salts to the electrolyte. On the basis of preparative scale electrolyses and cyclic voltammetry for that behavior, a mechanism is proposed that involves an initial reduction of the tetraalkylammonium cation with the participation of the electrode material to form a catalyst that favors le reduction routes [296, 297]. Stoichiometric amounts of ytterbium(II), generated by reduction of Yb(III), support the stereospecific coupling of 1,3-dibenzoylpropane to cis-cyclopentane-l,2-diol. However, Yb(III) remains bounded to the pinacol and cannot be released to act as a catalyst. This leads to a loss of stereoselectivity in the course of the reaction [298]. Also, with the addition of a Ce( IV)-complex the stereochemical course of the reduction can be altered [299]. In a weakly acidic solution, the meso/rac ratio in the EHD (electrohy-drodimerization) of acetophenone could be influenced by ultrasonication [300]. Besides phenyl ketone compounds, examples with other aromatic groups have also been published [294, 295, 301, 302]. 

The functions of porous electrodes in fuel cells are 1) to provide a surface site where gas/liquid ionization or de-ionization reactions can take place, 2) to conduct ions away from or into the three-phase interface once they are formed (so an electrode must be made of materials that have good electrical conductance), and 3) to provide a physical barrier that separates the bulk gas phase and the electrolyte. A corollary of Item 1 is that, in order to increase the rates of reactions, the electrode material should be catalytic as well as conductive, porous rather than solid. The catalytic function of electrodes is more important in lower temperature fuel cells and less so in high-temperature fuel cells because ionization reaction rates increase with temperature. It is also a corollary that the porous electrodes must be permeable to both electrolyte and gases, but not such that the media can be easily "flooded" by the electrolyte or "dried" by the gases in a one-sided manner (see latter part of next section). 

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