Temperature CO Oxidation in

One particular application for which supported Au catalysts may find a niche market is in fuel cells [4, 50] and in particular in polymer electrolyte fuel cells (PEFC), which are used in residential electric power and electric vehicles and operate at about 353-473 K. Polymer electrolyte fuel cells are usually operated by hydrogen produced from methane or methanol by steam reforming followed by water-gas shift reaction. Residual CO (about 1 vol.%) in the reformer output after the shift reaction poisons the Pt anode at a relatively low PEFC operating temperature. To solve this problem, the anode of the fuel cell should be improved to become more CO tolerant (Pt-Ru alloying) and secondly catalytic systems should be developed that can remove even trace amounts of CO from H2 in the presence of excess C02 and water. 

For successful operation a selective CO oxidation catalyst in a reformer-PEFC system must be operated at ca. 353-373 Kin a complex feed consisting of CO, 02, H2, C02, H20 and N2, and be capable of reducing CO concentrations from about 1% to below 50 ppm - this is equivalent to a CO conversion of at least 99.5% [4, 54, 60], In addition, this conversion must be achieved with the addition of equimolar 02 (twice the stoichiometric amount) and the competitive oxidation of H2 must be minimized. This is expressed as selectivity, which is defined as the percentage of the oxygen fed consumed in the oxidation of CO for commercial operation a selectivity of 50% is acceptable, since at this selectivity minimal H2 is oxidized to water. 

Mechanism for CO Oxidation Over Supported Cold Nanoparticles 

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Currently, low-temperature CO oxidation over Au catalysts is practically important in connection with air quality control (CO removal from air) and the purification of hydrogen produced by steam reforming of methanol or hydrocarbons for polymer electrolyte fuel cells (CO removal from H2). Moreover, reaction mechanisms for CO oxidation have been studied most extensively and intensively throughout the history of catalysis research. Many reviews [4,19-28] and highlight articles [12, 29, 30] have been published on CO oxidation over catalysts. This chapter summarizes of the state of art of low temperature CO oxidation in air and in H2 over supported Au NPs. The objective is also to overview of mechanisms of CO oxidation catalyzed by Au. 

In summary, external recycle reactors are expensive and their usefulness is limited. They can be practical for simple chemical systems where no condensation can occur and neither high pressure nor high temperature is needed. For example Carberry et al (1980) preferred an external recycle reactor over a spinning basket reactor for the study of CO oxidation in dry air at atmospheric pressure. 

The catal5fsts were tested for CO oxidation in a flow reactor using a 2.5 % CO in dry air mixture at a fixed flow rate of 200 seem. Thirty milligrams of the catalyst were used for each experimental run. The reaction was conducted at 298, 323, 373 and 473 K with 75 minutes duration at each temperature. The carbon monoxide conversion to carbon dioxide was monitored by an online gas chromatogr h equipped with a CTR-1 column and a thermal conductivity... 

Room temperature CO oxidation has been investigated on a series of Au/metal oxide catalysts at conditions typical of spacecraft atmospheres CO = 50 ppm, COj = 7,000 ppm, H2O = 40% (RH) at 25 C, balance = air, and gas hourly space velocities of 7,000- 60,000 hr . The addition of Au increases the room temperature CO oxidation activity of the metal oxides dramatically. All the Au/metal oxides deactivate during the CO oxidation reaction, especially in the presence of CO in the feed. The stability of the Au/metal oxide catalysts decreases in the following order TiOj > FejO, > NiO > CO3O4. The stability appears to decrease with an increase in the basicity of the metal oxides. In situ FTIR of CO adsorption on Au/Ti02 at 25 C indicates the formation of adsorbed CO, carboxylate, and carbonate species on the catalyst surface. 

The objective of this study was to develop a low temperature CO oxidation catalyst that continually removes low concentrations of CO from the atmospheres of space stations. CO is a major contaminant in spacecraft environments. Since... 

CO oxidation on 1%Au supported on various metal oxide catalysts was carried out to determine the effect of metal oxide on the activity and stability of the catalysts during room temperature CO oxidation. Figure 4 shows the CO conversion as a function of time on stream on 1%Au supported on various metal oxides such as CO3O4, Fe Oj, NiO, ZrOj, and TiO. All the catalysts showed high initial CO conversions. The stability of the catalysts decreased in the following order TiO > ZrOj > NiO > FejOj > CO3O4. The stability of the catalysts appears to decrease with increasing basicity of the metal. 

Au-Pd alloys with compositions close to that of the bulk components and that particle sizes were ca. 25 to 50 nm in diameter. The catalysts that were effective for H2O2 synthesis were found to be wholly inactive for CO oxidation at ambient temperature, and catalysts that were effective for low temperature CO oxidation were inactive for H2O2 synthesis. This shows that selective oxidation reactions active may utilize very different sites than those for the oxidation of CO. 

Supported noble metals such as Au and Pt are active for CO oxidation. Since Pt-based catalysts operate at relatively higher reaction temperatures (403 to 473 K), they are not very selective for CO oxidation in hydrogen-rich streams. Au catalysts. 

Owing to the very reactive nature of RuO relatively few solvents are suitable for its reactions. It is soluble in water to the extent of some 2% and is stable in such solutions, but reacts violently with diethyl ether, benzene and pyridine [236]. It has often been used catalytically in a biphasic system, with the co-oxidant in the aqueous layer. Under these circumstances the RuO formed from reduction of RuO by the substrate is re-oxidised at the organic - aqueous interface, so that oxidations with such systems can be much enhanced by stirring, shaking or sonication. In some cases (e.g. oxidation of aUcenes) it may be necessary to cool the reactants below room temperature, but in most cases ambient temperatures suffice, as indeed they do for the vast majority of organic oxidations catalysed by Ru complexes. 

Supported Au catalysts have been extensively studied because of their unique activities for the low temperature oxidation of CO and epoxidation of propylene (1-5). The activity and selectivity of Au catalysts have been found to be very sensitive to the methods of catalyst preparation (i.e., choice of precursors and support materials, impregnation versus precipitation, calcination temperature, and reduction conditions) as well as reaction conditions (temperature, reactant concentration, pressure). (6-8) High CO oxidation activity was observed on Au crystallites with 2-4 nm in diameter supported on oxides prepared from precipitation-deposition. (9) A number of studies have revealed that Au° and Au" play an important role in the low temperature CO oxidation. (3,10) While Au° is essential for the catalyst activity, the Au° alone is not active for the reaction. The mechanism of CO oxidation on supported Au continues to be a subject of extensive interest to the catalysis community. 

Onken, H. U. and Wicke, E. (1986). Statistical fluctuations of temperature and conversion at the catalytic CO oxidation in an adiabatic packed bed reactor. Ber. Bunsenges. Phys. Chem., 90, 976-81. 

Catalyst coking may involve carbonaceous species such as partially hydrogenated fragments (QHy) and may be initiated on metal or than acidic-oxide sites [1]. Three types of carbonaceous deposits may be formed on say Pt [2], which may be differentiated by temperature-programmed oxidation. SnO,-promoted Pt catalysts are important in reforming of alkanes [3] and low temperature CO oxidation [4]. Of course Sn02 is an n-type semiconductor and certainly in photoelectrolysis one expects metal-oxide electron transfers across the junction [51, but the nature of the Pt-SnOt interaction in catalytic systems remains unclear. 

Monitoring pollutants in a variety of composition ranges in motor vehicle and chemical process exhaust gases is a major area of research in pollution abatement technology. Low-temperature CO oxidation catalysts are needed for zero emission vehicles, CO gas sensors, selective oxidation of CO in H2 rich streams in fuel cell applications,1,2 and in closed-cycle C02 lasers used for remote sensing in space applications.3"5 Effective oxidation of CO during... 

Since Haruta s initial report (Sanchez et al., 1997) of the unexpected activity of supported gold catalysts for low-temperature CO oxidation, there has been a resurgence of research and interest in gold-mediated catalysis. Supported gold clusters have since been found to be active in a... 

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