CO oxidation activities

Almost simultaneously, Lindahl and co-workers proposed that Cluster C is the CO oxidation site based on EPR and ENDOR studies of the cyanide adduct of the enzyme (134). That proposal was based on the premise that CO and cyanide compete for the same binding site. Additionally, Xia and Lindahl have shown that, by mild SDS treatment, they can partially dissociate CODH/ACS, which is a tetra-meric enzyme with an subunit composition, into an isolated a subunit and an form (135). The form has the same level of CO oxidation activity as the native protein indicating that the a subunit is not involved in CO oxidation and that the /8 subunit must contain the clusters required for CO oxidation (135). In addition, CO2 alters the g values of the Credi form of the enzyme (136). 

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 catalysts were tested for their CO oxidation activity in an automated microreactor apparatus. The catalysts were tested at space velocities of 7,000 -60,000 hr . A small quantity of catalyst (typically 0.1 - 0.5 g.) was supported on a frit in a quartz microreactor. The composition of the gases to the inlet of the reactor was controlled by mass flow controllers and was CO = 50 ppm, CO2 = 0, or 7,000 ppm, HjO = 40% relative humidity (at 25°C), balance air. These conditions are typical of conditions found in spacecraft cabin atmospheres. The temperature of the catalyst bed was measured with a thermocouple placed half way into the catalyst bed, and controlled using a temperature controller. The inlet and outlet CO/CO2 concentrations were measured by non-dispersive infrared (NDIR) monitors. 

Recent studies [193] of the CO oxidation activity exhibited by highly dispersed nano-gold (Au) catalysts have reached the following conclusions (a) bilayer structures of Au are critical (b) a strong interaction between Au and the support leads to wetting and electron rich Au (c) oxidative environments deactivate Au catalyst by re-ox-idizing the support, which causes the Au to de-wet and sinter. Recent results have shown that the direct intervention of the support is not necessary to facilitate the CO oxidation reaction therefore, an Au-only mechanism is sufficient to explain the reaction kinetics. 

In our case the chemical composition and, consequently, the structure of the iron oxide is changed with time during reaction. Gold diffusion from film and nanoparticles underneath may occur but seem not to be the decisive factor in promoting the CO oxidation activity. 

The determination of the external mass transfer coefficient of CO, k, (see Equation 3) deserves brief comments. Since the complex geometry and flow characteristics in the reactor cell precluded a reliable estimation of k based on correlations given in the literature, the CO oxidation activities of the catalyst... 

K. Fukushima, G. H. Takaoka, J. Matsuo, and 1. Yamada, Effects on CO oxidation activity of nano-scale Au islands and Ti02 support prepared by the ionized cluster beam method, Japan. J. Appl. Phys. Part 1—Regul. Pap. Short Notes Rev. Pap. 36(2), 813-818 (1997). 

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. 

Au/TiOz catalyst prepared from AuCls possesses reduced Au and oxidized Au sites which exhibit high CO oxidation activity. The catalyst produce carbonate and... 

In these experiments, shown in Figure 1, the CO oxidation reactor system was charged with supported, in tact Au-DENs/Ti02, and CO oxidation activity was monitored as a function of time on stream at various temperatures (100, 125, and 150 °C). The time required to reach maximum activity varied from 8 hours at 150 °C to 24 ... 

Au-DENs were prepared via literature procedures (2) and deposited onto Degussa P25 Titania by stirring at pH 6 overnight. In situ infrared spectroscopy, catalyst activation, and CO oxidation experiments were performed using previously described procedures.(3) Catalyst activation under CO oxidation conditions were used 23 mg catalyst samples diluted 10 1 with a-Al203. In CO oxidation activity measurements, the feed composition was 1.1% CO, 27% O2 balance He, and the flow rate was kept constant at 20 mL/min. Conversion was measured as a function of temperature and rate data was determined only for conversions between 1 and 12%. 

CO oxidation activity of (Ceo.g.Lao.OOpgs and (Ce0.8,Zr0.2)O2 heated at 1,000°C are shown in Fig. 8. The activity of Ce02 is extremely improved by the addition of La and Zr into Ce02. The reaction kinetics is controlled by the diffusion of lattice oxygen and is described by the following equation ... 

Fig. 28. Data recorded for CO oxidation on platinumfl 1 0) with an STM in a flow reactor. The upper panel shows mass spectrometer signals recorded directly from the reactor cell. The STM images show the surface morphology at different stages, corresponding to the curves in the mass spectrometer signal. High CO oxidation activity was correlated with the observation of a rough, oxidic platinum surface. With permission from Reference (163).

In contrast to lead, the possible poisoning by metallic elements, derived from the vehicle system, is not easily documented. Many formulations of automotive catalysts contain both base and noble metals, but the detailed effect of such combinations on the particular reactions is rarely known with precision. One study was concerned with the effect of Cu on noble metal oxidation catalysts, since these, placed downstream from Monel NOx catalysts, could accumulate up to 0.15% Cu (100). The introduction of this amount of Cu into a practical catalyst containing 0.35% Pt and Pd in an equiatomic ratio has, after calcination in air, depressed the CO oxidation activity, but enhanced the ethylene oxidation. Formation of a mixed Pt-Cu-oxide phase is thought to underlie this behavior. This particular instance shows an example, when an element introduced into a given catalyst serves as a poison for one reaction, and as a promoter for... 

Fig. 8.3 Comparison of CO oxidation activity at 353 K among 12 metal oxides with/without one of five precious metal ions.

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