Surface oxygen complexes desorption

Reaction temperature can also affect the order of a reaction. It is generally agreed that the rate constant for the conversion (or desorption) of the surface-oxygen complex has a higher activation energy than the rate constant for the formation of the complex. Therefore, a reaction which is zero order at low temperatures and a given pressure can become first order at the same pressure and a sufficiently high temperature. 

Stoeckli, F., Moreno-Castilla, C., Carrasco-Marin, F., and L6pez-Ram6n, M.V. (2001). Distribution of surface oxygen complexes on activated carbons from immersion calorimetry, titration and temperature-programmed desorption techniques. Carbon, 39(14), 2235-7. 

The characterization of surface oxygen complexes by diffuse reflectance infrared spectroscopy (DRIFT) and temperature programmed desorption (TPD). 

It is generally accepted that the perovskite-catalyzed combustion of soot with O2 occurs through a four-step mechanism involving (i) adsorption of O2 on the catalyst, (ii) delivery of activated oxygen species to the carbon surface, (iii) formation of surface oxygen complexes (SOCs) on the carbon surface, and (iv) desorption of SOCs [27], This general mechanism is valid not only for perovskites but also for some other soot combustion catalysts. 

As in the carbon-carbon dioxide reaction, mechanisms A and B can be treated for the cases where either the surface rearrangement or desorption of the carbon-oxygen complex is the slow step. This has no effect on the discussion except that the significance of the rate constant js in Equation (10) is altered, as previously discussed. 

In this model, the first step is the dissociation of C02 at a carbon free active site (Cfas), releasing CO and forming an oxidized surface complex [C(O)]. In the second step, the carbon-oxygen complex subsequently produces CO and a new free active site. The reverse reaction is relatively slow compared with the forward reaction, so the second reaction can be treated as an irreversible reaction. In this model, desorption of the carbon-oxygen surface complex is the rate-limiting step. The rate for this mechanism can be described by the Lang-muir-Hinshelwood rate equation. Furthermore, the C/C02 reaction rate is dependent on the CO and C02 partial pressures and is inhibited by the presence of carbon monoxide. A widely utilized reaction rate equation based on this mechanism is... 

Serval reactions occurred evidenced by a complex desorption products. First, acetaldehyde (m/e 29, 15, 44) desorbed at 390 K followed by traces of ethanol at 415 K (2 % of carbon selectivity, table 2). Three other products were observed. Butadiene and butene desorbed at 540 and 673 K respectively with a combined carbon selectivity of 21.1 %. This reaction pathway follows a reductive coupling mechanism which has been observed previously on the surfaces of Ti02 single crystal and powder [19-21]. The formation of C4 olefins is a clear example of the capacity of UO2 surfaces to abstract large amounts of oxygen from surface carbonyls, via pinacolates [19], as follow... 

The perovskite-type catalysts (ref.l), other non noble metal complex oxides catalysts (ref.2), and mixed metal oxides catalysts (ref.3) have been studied in our laboratory. The various preparation techniques of catalysts (ref.4 and 5), the adsorption and thermal desorption of CO, C2H5 and O2 (ref.6 and 7), the reactivity of lattice oxygen (ref.8), the electric conductance of catalysts (ref.9), the pattern of poisoning by SO2 (ref. 10 and 11), the improvement of crushing strength of support (ref. 12) and determination of the activated surface of complex metal oxides (ref. 13) have also been reported. 

In the first sample (Figure 3.a), desorption of CO and CO2 was observed. CO2 desorbs at low temperature (200-400°C) while CO desorption begins at 200°C to become important at 550°C. CO and CO2 arise from surface carbon-oxygen complexes. The TPD curves of catalyst (Figure 3.b) show two important desorbed species CO2 and O2. CO2 certainly results from the decomposition of residual carbonated components remaining during the preparation. O2 may... 

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