Carbon potential effect electrochemical oxidation

The electrochemical behaviour of silyl-substituted nitrogen compounds is also interesting. The introduction of a silyl group at the carbon adjacent to the nitrogen of carbamates causes a significant decrease in the oxidation potentials, although such effect is much smaller for amines. Preparative electrochemical oxidation of silyl-substituted carbamates in methanol results in smooth and selective cleavage of the C Si bond and introduction of methanol at the a-... 

The application of surface-enhanced Raman spectroscopy (SERS) for monitoring redox and other processes at metal-solution interfaces is illustrated by means of some recent results obtained in our laboratory. The detection of adsorbed species present at outer- as well as inner-sphere reaction sites is noted. The influence of surface interaction effects on the SER spectra of adsorbed redox couples is discussed with a view towards utilizing the frequency-potential dependence of oxidation-state sensitive vibrational modes as a criterion of reactant-surface electronic coupling effects. Illustrative data are presented for Ru(NH3)63+/2+ adsorbed electrostatically to chloride-coated silver, and Fe(CN)63 /" bound to gold electrodes the latter couple appears to be valence delocalized under some conditions. The use of coupled SERS-rotating disk voltammetry measurements to examine the kinetics and mechanisms of irreversible and multistep electrochemical reactions is also discussed. Examples given are the outer- and inner-sphere one-electron reductions of Co(III) and Cr(III) complexes at silver, and the oxidation of carbon monoxide and iodide at gold electrodes. 

The above CVs (Figs. 24 and 25) display well-formed reduction peaks independent of the blank solution and the type of active carbon materials. The combined shape of the cathodic peaks indicates that surface species participate in electrochemical processes in different local environments, or with various structures but convergent peak potentials. The effect of anodic polarization is more readily observed in a basic environment than in an acid solution. Similarly, a positive shift of cathodic peak potential with a decrease in anodic sweep potential limit takes place. Similar results were obtained for studies of electrochemical oxidation of graphite [17] and glass-like carbon [222] electrodes. There was considerable enlargement of both anodic and cathodic peaks after anodic polarization in 20% sulfuric acid (Fig. 26) [17]. 

Gallagher KG, Wong DT, Fuller TF (2008) The effect of transient potential expostffe on the electrochemical oxidation of carbon black in low-temptaatiire fuel cells. J Electrochem Soc... 

The most effective CO tolerance is found to be with Pt/Ru alloys. Pt/Ru alloy catalysts, supported on carbon were found to be effective upto 2% CO without a significant drop in performance. However, the other promising metals are Co and Ni. It may be noted that the Ru attracts the CO molecules, thus keeping the Pt free for hydrogen oxidation. Additionally on Ru, the oxidation of CO to CO2 occurs at a lesser potential of about 0.35 w.r.t. (SHE) at 50 atom% Ru and at 0.2V (SHE) for 90 atom% Ru. Thus, at a lesser polarization the electrochemical oxidation of CO starts for Pt/Ru based catalysts. These two effects make Pt/Ru based anode catalyst as the most accepted CO tolerant PAFC catalyst. As Ru percent increases, CO tolerance is enhanced at a cost of activity due to less Pt availability. In view of this, a trade-off is required, and the optimal composition that most of the developers claim is 1 1 atomic ratio of Pt Ru. 

It is well established that sulfur compounds even in low parts per million concentrations in fuel gas are detrimental to MCFCs. The principal sulfur compound that has an adverse effect on cell performance is H2S. A nickel anode at anodic potentials reacts with H2S to form nickel sulfide. Chemisorption on Ni surfaces occurs, which can block active electrochemical sites. The tolerance of MCFCs to sulfur compounds is strongly dependent on temperature, pressure, gas composition, cell components, and system operation (i.e., recycle, venting, and gas cleanup). Nickel anode at anodic potentials reacts with H2S to form nickel sulfide. Moreover, oxidation of H2S in a combustion reaction, when recycling system is used, causes subsequent reaction with carbonate ions in the electrolyte [1]. Some researchers have tried to overcome this problem with additional device such as sulfur removal reactor. If the anode itself has a high tolerance to sulfur, the additional device is not required, hence, cutting the capital cost for MCFC plant. To enhance the anode performance on sulfur tolerance, ceria coating on anode is proposed. The main reason is that ceria can react with H2S [2,3] to protect Ni anode. 

Although little information has been available for the effect of a-silyl substitution on the electrochemical properties of heteroatom compounds, extensive studies have been carried out on the effect of /f-silyl substitution [10,13]. For the -substituted heteroatom compounds (substitution at the a carbon), the introduction of a silyl group results in a significant decrease of the oxidation potentials, although the magnitude depends upon the nature of the heteroatom. This effect is explained in terms of the interaction between the C Si a orbital and the nonbonding p orbital of the heteroatom (Fig. 5). This interaction raises the HOMO level which in turn favours the electron transfer. 

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