Electrocatalysis selectivity

Electrodes. At least three factors need to be considered ia electrode selection as the technical development of an electroorganic reaction moves from the laboratory cell to the commercial system. First is the selection of the lowest cost form of the conductive material that both produces the desired electrode reactions and possesses stmctural iategrity. Second is the preservation of the active life of the electrodes. The final factor is the conductivity of the electrode material within the context of cell design. An ia-depth discussion of electrode materials for electroorganic synthesis as well as a detailed discussion of the influence of electrode materials on reaction path (electrocatalysis) are available (25,26). A general account of electrodes for iadustrial processes is also available (27). 

As we demonstrate in this chapter, enzymes can be extremely active electrocatalysts at ambient temperatures and mild pH, and have significantly higher reaction selectivity than precious metals. The main disadvantage in applying redox enzymes for electrocatalysis arises from their large size, which means that the catalytic active site density is low. Enzymes also have a relatively short hfetime (usually not more than a few months), making them more suited to disposable applications. 

Electrocatalysis employing Co complexes as catalysts may have the complex in solution, adsorbed onto the electrode surface, or covalently bound to the electrode surface. This is exemplified with some selected examples. Cobalt(I) coordinatively unsaturated complexes of 2,2 -dipyridine promote the electrochemical oxidation of organic halides, the apparent rate constant showing a first order dependence on substrate concentration.1398,1399 Catalytic reduction of dioxygen has been observed on a glassy carbon electrode to which a cobalt(III) macrocycle tetraamine complex has been adsorbed.1400,1401... 

The aim of this overview is first to present the general principles of electrocatalysis by metal complexes, followed by a series of selected examples published over the last 20 years illustrating the major electrochemical reactions catalyzed by metal complexes and their potential applications in synthetic and biomimetic processes, and also in the development of sensory devices. The area of metal complex catalysts in electrochemical reactions was reviewed in 1990.1... 

The targets of electrocatalysis are at the basis of recent developments in the field of water electrolysis. First, it is necessary to distinguish between materials evaluation and materials selection. The former is the search for materials with better and better properties for the wanted electrode process. The latter implies global considerations of applicability. This is probably what makes academic research differ from R D. The former is favored by scientifically exciting performance, in the latter it is necessary to find a compromise between, for instance, activity and stability or between efficiency and economic convenience. 

In this paper we report the application of bimetallic catalysts which were prepared by consecutive reduction of a submonolayer of bismuth promoter onto the surface of platinum. The technique of modifying metal surfaces at controlled electrode potential with a monolayer or sub-monolayer of foreign metal ("underpotential" deposition) is widely used in electrocatalysis (77,72). Here we apply the theory of underpotential metal deposition without the use of a potentiostat. The catalyst potential during promotion was controlled by proper selection of the reducing agent (hydrogen), pH and metal ion concentration. 

Electrocatalysis of the reduction of HNO2 and NO was demonstrated in the late 1980s independently by Anson etal. [153d] and by Keita etal. [157, 158]. Since then, this reaction has been selected and is being used worldwide as a classical test of the electrocatalytic properties of the POMs. Consideration of [Fe(H20)SiWii039] (SiWnFe for... 

B. Electrocatalysis and Selectivity of Anodic Chlorine Evolution at Ru02-Anodes... 

One could call this type of electrocatalysis, which is due to the catalytic action of adsorbed species, electrocatalysis of the second kind. Most remarkably the selectivity and commercial success of the Monsanto process— the hydrodimerisation of arylonitrile to adipodinitrile—... 

Activity and selectivity in electrocatalysis are determined, in most cases, by the activity, selectivity, structural, and electronic properties of electrode surfaces and the stability to deactivation of such surfaces. The... 

The selective facilitation of the charge transfer of the species of interest is called electrocatalysis. In such a case, the species of interest are transformed at energies substantially lower than those of the interferants. The higher selectivity therefore implies a lower applied potential at the modified working electrode, which exhibits such selective electrocatalytic properties. In such a situation, the choice of the... 

This brief review attempts to summarize the salient features of chemically modified electrodes, and, of necessity, does not address many of the theoretical and practical concepts in any real detail. It is clear, however, that this field will continue to grow rapidly in the future to provide electrodes for a variety of purposes including electrocatalysis, electrochromic displays, surface corrosion protection, electrosynthesis, photosensitization, and selective chemical concentration and analysis. But before many of these applications are realized, numerous unanswered questions concerning surface orientation, bonding, electron-transfer processes, mass-transport phenomena and non-ideal redox behavior must be addressed. This is a very challenging area of research, and the potential for important contributions, both fundamental and applied, is extremely high. 

In this chapter, it will be shown that the detection of sodium dithionite on bare gold electrodes can be improved by electrocatalysis using a cobalt(II)tetrasulphonated phthalocyanine, sodium salt (CoTSPc) or a 5,10,15,20-tetrakis-(4-sulphonatophenyl)porphyrin cobalt(II), tetrasodium salt (CoTSPor) as catalyst. The selection of these catalysts was based on... 

Selective Oxidation and Ammoxidation of Propylene by Heterogeneous Catalysis Robert K. Grasselli and James D. Burrington Mechanism of Hydrocarbon Synthesis over Fischer-Tropsch Catalysts P. Biloen and W. M. H. Sachtler Surface Reactions and Selectivity in Electrocatalysis... 

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