Nickel oxide activation energy

There are few studies in the literature on the kinetics and mechanism of oxidation over base metal oxides. Blumenthal and Nobe studied the oxidation of CO over copper oxide on alumina between 122 and 164°C. They reported that the kinetics is first order with respect to CO concentration, and the activation energy is 20 kcal/mole (77). Gravelle and Teichner studied CO oxidation on nickel oxide, and found that the kinetics is also first order with respect to CO concentration (78). They suggested that the mechanism of reaction is by the Eley-Rideal mechanism... 

Just as in the case of the H2-D2 exchange on ZnO, two mechanisms are also discernible for the carbon monoxide oxidation [stage (b)] on nickel oxide below 300°C. There is a low-temperature mechanism operative between 100° and 180°C. characterized by a low activation energy of 2 kcal./mole and a high-temperature mechanism, above 180°C., with a higher activation energy of 13 kcal./mole. The kinetics are different and are respectively ... 

The main features of this investigation are the following. First, a "deactivation process similar to that observed on the pure nickel oxide was found on the modified catalysis as well, with the same logarithmic law to represent its evolution with time. Second, the kinetic equations which were found to fit the data on pure nickel oxide also apply to the modified catalysts. Thus there is a low-temperature mechanism operative between 100° and 180°C. For all the samples assembled in Table II, the activation energies were practically the same, about 2 kcal./mole and essentially equal to the value for pure nickel oxide. This indicates that, for this particular mechanism of the reaction, the added ions and the semiconductivity changes do not affect directly the catalytic process. 

Activation Energies for Carbon Monoxide Oxidation on Nickel Oxide Catalysis... 

If further work confirms our explanations which connect catalytic inversion with the inversion of physical properties of the modified nickel oxide catalysts, the correlation between semiconductivity and oxidation catalysis found in the Princeton work and in Schwab s studies will appear quite convincing. To sum up, the activation energy of the carbon monoxide oxidation has been found to decrease with increasing semiconductivity on both sides of the inversion point of physical properties of nickel oxide catalysts. 

The oxidation of carbon monoxide on nickel oxide has often been investigated (4, 6, 8, 9, II, 16, 17, 21, 22, 26, 27, 29, 32, 33, 36) with attempts to correlate the changes in the apparent activation energy with the modification of the electronic structure of the catalyst. Published results are not in agreement (6,11,21,22,26,27,32,33). Some discrepancies would be caused by the different temperature ranges used (27). However, the preparation and the pretreatments of nickel oxide were, in many cases, different, and consequently the surface structure of the catalysts—i.e., their composition and the nature and concentration of surface defects— were probably different. Therefore, an explanation of the disagreement may be that the surface structure of the semiconducting catalyst (and not only its surface or bulk electronic properties) influences its activity. 

The thermal oxidation of C2F4 was examined between 280 and 400°C in a static system by Peterson and Colwell.132 In addition to c-C3Fe they measured the total oxidation products (principally CF20) as C02. Their results were not reproducible and differed in Pyrex and nickel reactors. Nevertheless it appeared that product formation occurred with an activation energy in the neighborhood of 20-30 kcal/mole. 

The sealed nickel-metal hydride cell (more consistently metal hydride-nickel oxide cell) has a similar chemistry to the longer-established hydro-gen-nickel oxide cell considered in Chapter 9. In most respects (including OCV and performance characteristics), it is very similar to the sealed nickel-cadmium cell, but with hydrogen absorbed in a metal alloy as the active negative material in place of cadmium. The replacement of cadmium not only increases the energy density, but also produces a more environmentally friendly power source with less severe disposal problems. The nickel-metal hydride cell, however, has lower rate capability, poorer charge retention and is less tolerant of overcharge than the nickel-cadmium cell. 

Fig. 4. Activation energy of carbon monoxide oxidation over nickel oxide of different layer thickness on silver (26). (Copyright by Akademische Verlags-Gessellschaft. Reprinted with permission.)...

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