Anode catalyses

Scheme 9.1. Oxidation of aldehydes at a platinum anode catalysed by macrocycle 5 in methanol.

Poisoning of platinum fuel cell catalysts by CO is undoubtedly one of the most severe problems in fuel cell anode catalysis. As shown in Fig. 6.1, CO is a strongly bonded intermediate in methanol (and ethanol) oxidation. It is also a side product in the reformation of hydrocarbons to hydrogen and carbon dioxide, and as such blocks platinum sites for hydrogen oxidation. Not surprisingly, CO electrooxidation is one of the most intensively smdied electrocatalytic reactions, and there is a continued search for CO-tolerant anode materials that are able to either bind CO weakly but still oxidize hydrogen, or that oxidize CO at significantly reduced overpotential. 

Liu H, Songa C, Zhang L, Zhang J, Wang H, Wilkinson DP. 2006. A review of anode catalysis in the direct methanol fuel cell. J Power Sources 155 95-110. 

Reddington et al. (66) reported the synthesis and screening of a 645-member discrete materials library L9 as a source of catalysts for the anode catalysis of direct methanol fuel cells (DMFCs), with the relevant goal of improving their properties as fuel cells for vehicles and other applications. The anode oxidation in DMFCs is reported in equation 1 (Fig. 11.12). At the time of the publication, state-of-the-art anode catalysts were either binary Pt-Ru alloys (67) or ternary Pt-Ru-Os alloys (68). A systematic exploration of ternary or higher order alloys as anode catalysts for DMFCs was not available, and predictive models to orient the efforts were also lacking. 

As hydrocarbons will most likely be used for the foreseeable future, the development of hydrocarbon anode catalysis is another area of research that could potentially provide significant breakthroughs. 

T. Takeguchi, R. Kikuchi, T. Yano, K. Eguchi, and K. Murata. Effect of precious metal addition to Ni-YSZ cermet on reforming of CH4 and electrochemical activity as SOFC anode. Catalysis Today 84, (2003) 217-222. 

A review of anode catalysis in the direct methanol fuel cell. /... 

The integration of cofactor-dependent enzymes as anodic catalysis clearly faces a number of technical hurdles that must be considered and addressed. To some extent, the stability of the NAD" /NADH couple has been addressed by introduction of electropolymerized polymers that has directly led to extended bioanode lifetimes. 

Improving bioanodes performances and efficiencies will be the most important task in future studies of enzymatic anodic catalysis. Based on research carried out in the past few years, trends for improving performance rely on better electron transport methods and higher enzyme loading. Electron transport could be improved, for example, by developing novel mediators and redox polymers for MET or by controlling orientation of enzymes to improve DET. Enzyme loading techniques could be improved to increase active enzyme concentration per unit of electrode area or volume. 

The scope of oxidation chemistry is enormous and embraces a wide range of reactions and processes. This article provides a brief introduction to the homogeneous free-radical oxidations of paraffinic and alkylaromatic hydrocarbons. Heterogeneous catalysis, biochemical and hiomimetic oxidations, oxidations of unsaturates, anodic oxidations, etc, even if used to illustrate specific points, are arbitrarily outside the purview of this article. There are, even so, many unifying features among these areas. 

I.V. Yentekakis, Y. Jiang, S. Neophytides, S. Bebelis, and C.G. Vayenas, Catalysis, Electrocatalysis and Electrochemical Promotion of the Steam Reforming of Methane over Ni Film and Ni-YSZ cermet Anodes, Ionics 1, 491-498 (1995). 

Solid oxide fuel cell, SOFC anodes, 97 catalysis in, 98,410 cathodes, 96... 

This presentation reports some studies on the materials and catalysis for solid oxide fuel cell (SOFC) in the author s laboratory and tries to offer some thoughts on related problems. The basic materials of SOFC are cathode, electrolyte, and anode materials, which are composed to form the membrane-electrode assembly, which then forms the unit cell for test. The cathode material is most important in the sense that most polarization is within the cathode layer. The electrolyte membrane should be as thin as possible and also posses as high an oxygen-ion conductivity as possible. The anode material should be able to deal with the carbon deposition problem especially when methane is used as the fuel. 

Over the anode, the hydrogen and CO produced via reactions (1) and (2) are then oxidized at the anode by reacting with the oxygen species transported from the cathode. The catalysis of the fuel such as methane at the anode and oxygen at the cathode becomes increasingly important with demanding catalytic activity as the SOFC operation temperature decreases, which is the aim under intensive research efforts. 

The additivity principle was well obeyed on adding the voltammograms of the two redox couples involved even though the initially reduced platinum surface had become covered by a small number of underpotential-deposited mercury monolayers. With an initially anodized platinum disk the catalytic rates were much smaller, although the decrease was less if the Hg(I) solution had been added to the reaction vessel before the Ce(lV) solution. The reason was partial reduction by Hg(l) of the ox-ide/hydroxide layer, so partly converting the surface to the reduced state on which catalysis was greater. 

Mikroreaktoren sind so klein wie ein Fingerhut, Handdsblatt, May 1998 Steep progress in microelectronics, sensor and analytical techniques in the past transport intensification for catalysis first catalytic micro reactors available partial oxidation to acrolein partial hydrogenation to cyclododecene anodically oxidized catalyst supports as alternatives to non-porous supports study group on micro reactors at Dechema safety, selectivity, high pressure exclusion of using particle solutions limited experience with lifetime of micro reactors [236],... 

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