Carbon monoxide anodic oxidation

According to Faraday s law, one Faraday (26.80 Ah) should deposit one gram equivalent (8.994 g) of aluminum. In practice only 85—95% of this amount is obtained. Loss of Faraday efficiency is caused mainly by reduced species ( Al, Na, or A1F) dissolving or dispersing in the electrolyte (bath) at the cathode and being transported toward the anode where these species are reoxidized by carbon dioxide forming carbon monoxide and metal oxide, which then dissolves in the electrolyte. Certain bath additives, particularly aluminum fluoride, lower the content of reduced species in the electrolyte and thereby improve current efficiency. 

Oscillatory reactions carbon monoxide oxidation, 388 electrochemical promotion of, 389 Overpotential activation, 124 anodic, 122 cathodic, 122 cell, 123... 

Sol-gel technique has also been applied to modify the anode/electrolyte interface for SOFC running on hydrocarbon fuel [16]. ANiA SZ cermet anode was modified by coating with SDC sol within the pores of the anode. The surface modification of Ni/YSZ anode resulted in an increase of structural stability and enlargement of the TPB area, which can serve as a catalytic reaction site for oxidation of carbon or carbon monoxide. Consequently, the SDC coating on the pores of anode leads to higher stability of the cell in long-term operation due to the reduction of carbon deposition and nickel sintering. 

PEMFC)/direct methanol fuel cell (DMFC) cathode limit the available sites for reduction of molecular oxygen. Alternatively, at the anode of a PEMFC or DMFC, the oxidation of water is necessary to produce hydroxyl or oxygen species that participate in oxidation of strongly bound carbon monoxide species. Taylor and co-workers [Taylor et ah, 2007b] have recently reported on a systematic study that examined the potential dependence of water redox reactions over a series of different metal electrode surfaces. For comparison purposes, we will start with a brief discussion of electronic structure studies of water activity with consideration of UHV model systems. 

Anode Investigations using cyclovoltammetry confirm an important effect of surface oxides (see Vols. 3, 4). A known example of the different anodic activity is the poisoning of platinum by adsorbed carbon monoxide species, for example, in the direct methanol fuel cell (DMFC),... 

For the transfer of redox electrons (inner-sphere electron transfer) in which redox particles are adsorbed on a thin superficial film that covers a metal electrode, the transfer current of redox electrons is not always decreased but rather increased by the presence of the thin film. Such an increase in the reaction ciurent will occur, if the film acts as a reaction catalyst providing the adsorbed state of redox particles favorable for the redox electron transfer. For example, the anodic oxidation of carbon monoxide is catalyzed by the presence of an anodic oxide film on... 

Carbon Monoxide The presence of CO in a H2-rich fuel has a significant effect on anode performance because CO affects Pt electrodes catalysts. The poisoning is reported to arise from the dual site replacement of one H2 molecule by two CO molecules on the R surface (40, 41). According to this model, the anodic oxidation current at a fixed overpotential, with (ico) and without (in2) CO present, is given as a function of CO coverage (0co) by Equation (5-11) ... 

Carbon monoxide (CO) and hydrocarbons such as methane (CH4) can be used as fuels in SOFCs. It is feasible that the water gas shift involving CO (CO + H2O H2 + CO2) and the steam reforming of CH4 (CH4 + H2O 3H2 + CO) occur at the high temperature environment of SOFCs to produce H2 that is easily oxidized at the anode. The direct oxidation of CO in fuel cells also is well established. It appears that the reforming of CH4 to hydrogen predominates in... 

When designing an MCFC power system, several requirements must be met. An MCFC system must properly condition both the fuel and oxidant gas streams. Methane must be reformed into the more reactive hydrogen and carbon monoxide. Carbon deposition, which can plug gas passages in the anode gas chamber, must be prevented. To supply the flow of carbonate ions, the air oxidant must be enriched with carbon dioxide. Both oxidant and fuel feed streams must be heated to their proper inlet temperatures. Each MCFC stack must be operated within an acceptable temperature range. Excess heat generated by the MCFC stacks must be recovered and efficiently utilized. 

Electrooxidation of carbon monoxide to carbon dioxide at platinum has been extensively studied mainly not least because of the technological importance of its role in methanol oxidation in fuel cells [5] and in poisoning hydrogen fuel cells [6]. Enhancing anodic oxidation of CO is critical, and platinum surfaces modified with ruthenium or tin, which favor oxygen atom adsorption and transfer to bound CO, can achieve this [7, 8]. 

This section addresses the role of chemical surface bonding in the electrochemical oxidation of carbon monoxide, CO, formic acid, and methanol as examples of the electrocatalytic oxidation of small organics into C02 and water. The (electro)oxidation of these small Cl organic molecules, in particular CO, is one of the most thoroughly researched reactions to date. Especially formic acid and methanol [130,131] have attracted much interest due to their usefulness as fuels in Polymer Electrolyte Membrane direct liquid fuel cells [132] where liquid carbonaceous fuels are fed directly to the anode catalyst and are electrocatalytically oxidized in the anodic half-cell reaction to C02 and water according to... 

Here iii " and mout denote the mass flow rate of the mixture entering from the inlet and leaving from the outlet respectively. Rate of consumption and rate of production of each species A is denoted by m sed and mv d. These rates include the flux of reactants, which take part in electrochemical reactions, across the chan-nel/electrode interfaces and also the consumption and production of species due to methane reforming reaction on the anode side. Both hydrogen and carbon monoxide electrochemistry was considered and it was assumed that n2, the fraction of the current that is produced from H2 oxidation, is known. Thus the specie consump-... 

The equilibrium limitations of these two reforming reactions are overcome by continuous removal of hydrogen and carbon monoxide which are directly oxidized electrochemically at the anodic electrode. There, these components react with carbonate ions from the electrolyte to produce carbon dioxide, water and electrons according to the following stoichiometric relationships ... 

While these experiments, which were carried out without giving a theoretical insight into the nature of the electrochemical reaction, yielded almost all the possible oxidation products in the oxidation of methyl alcohol, Elbs and Brunner 2 have discovered a method which gives 80% of the current yield in formaldehyde. This is exactly the substance which could not be proven present up to that time among the electrolytic oxidation products of methyl alcohol. Elbs and Brunner electrolyzed an aqueous solution of 160 g. methyl alcohol and 49 to 98 g. sulphuric acid in a litre. They employed a bright platinum anode in an earthenware cylinder, using a current density of 3.75 amp.1 and a temperature of 30°. Only traces of formic acid and carbonic acid and a little carbon monoxide, aside from the 80 per cent, of formaldehyde, were formed. Plating the platinum anode with platinum decreased the yield of formaldehyde at the expense of the carbon dioxide. With an anode of lead peroxide the carbon dioxide exceeded the aldehyde. 

In an alkaline solution it is possible to so increase the oxidation that the benzoic acid is destroyed. The decomposition prod- ueLs which then appear at the anode are carbon dioxide, carbon monoxide, and sometimes acetylene. The odor of bitter almonds is also frequently observed. 

Carbon-supported Pt can also be used as the anode catalyst. However, this requires pure H2. Contaminants such as carbon monoxide (CO) poison the catalyst, because CO can strongly adsorb on Pt, blocking the catalytic sites and reducing platinum s catalytic activity. In H2 produced from the reforming of other fuels, CO is always present. Thus, to improve contaminant tolerance, carbon-supported PtRu was developed and now is always used as the anode catalyst. Ru can facilitate the oxidation of CO, releasing the catalytic sites on Pt through the following reactions ... 

The basic elements of a SOFC are (1) a cathode, typically a rare earth transition metal perovskite oxide, where oxygen from air is reduced to oxide ions, which then migrate through a solid electrolyte (2) into the anode, (3) where they combine electrochemically with to produce water if hydrogen is the fuel or water and carbon dioxide if methane is used. Carbon monoxide may also be used as a fuel. The solid electrolyte is typically a yttrium or calcium stabilized zirconia fast oxide ion conductor. However, in order to achieve acceptable anion mobility, the cell must be operated at about 1000 °C. This requirement is the main drawback to SOFCs. The standard anode is a Nickel-Zirconia cermet. 

Alumina membranes made by anodic oxidation were tested for separating hydrogen and carbon monoxide at a temperature up to 9T C [Itaya, 19S4], The ideal separation factor only achieved 3.5. See Table 7.4. Wu et al. [1993] also examined the use of alumina membranes for this application at an even higher temperature of 300 C and obtain a maximum separation factor of only 2.2. The alumina membranes used in the above studies all have pore diameters larger than 4 nm. Their separation factors for the H2/CO gas pair are no higher than the Knudsen diffusion values of 3.7 most likely as a result of the limitation imposed by the relatively large pores involved. 

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