Surface over-oxidation

Ethylene conversion to acetic acid can be increased in at least two ways. One is making the catalyst surface more acidic, which will strengthen ethylene adsorption on the surface to give more time for its oxidation to acetic acid. A more acidic surface will also facilitate desorption of acetic acid thus reducing its surface over-oxidation to carbon oxides. This approach has been realized by adding small amounts of P, B and Te to the MoVNb oxide catalyst. Table 11.2 presents the results of adding phosphorus. 

Tartronic acid was oxidised to mesoxalic acid on 6%Pt2%Bi/C, prepared by exchange/redox, under acidic conditions (reaction f, Scheme 1) (29% yield at 53% conversion, pH=1.5). Figure 10 shows that the conversion rate of tartronic acid is high at first but decreases as the reaction proceeds, probably because the formed mesoxalic acid is more strongly adsorbed on the surface than tartronic acid. The initial high selectivity tapers off due to over-oxidation. 

The purpose of this work was to increase the A3 selectivity at low conversion through a catalyst modification. Previous studies of phenol alkylation with methanol (the analogue reaction) over oxides and zeolites showed that the reaction is sensitive to acidic and basic properties of the catalysts [3-5]. It is the aim of this study to understand the dependence of catalyst structure and acidity on activity and selectivity in gas phase methylation of catechol. Different cations such as Li, K, Mg, Ca, B, incorporated into y-Al203 can markedly modify the polarisation of the lattice and consequently influence the acidic and basic properties of the surface [5-8] which control the mechanism of this reaction. 

At least for ethylene hydrogenation, catalysis appears to be simpler over oxides than over metals. Even if we were to assume that Eqs. (1) and (2) told the whole story, this would be true. In these terms over oxides the hydrocarbon surface species in the addition of deuterium to ethylene would be limited to C2H4 and C2H4D, whereas over metals a multiplicity of species of the form CzH D and CsHs-jD, would be expected. Adsorption (18) and IR studies (19) reveal that even with ethylene alone, metals are complex. When a metal surface is exposed to ethylene, selfhydrogenation and dimerization occur. These are surface reactions, not catalysis in other words, the extent of these reactions is determined by the amount of surface available as a reactant. The over-all result is that a metal surface exposed to an olefin forms a variety of carbonaceous species of variable stoichiometry. The presence of this variety of relatively inert species confounds attempts to use physical techniques such as IR to char-... 

Chatterjee, A. and Kawazoe, A. 2007. Application of the reactivity index to propose intra and intermolecular reactivity in metal cluster interaction over oxide surface. Mater. Trans. 48 2152-2158. 

In the sorption experiments of Icopini et al. (2004), the measured isotopic contrast between Fe(II)aq and the goethite starting material was -0.8%o after Fe(II) had sorbed to the surface over 24 hours in this case, the isotopic fractionation between sorbed Fe(II) and Fe(II)aq is not the 0.8%o measured difference, but is approximately +2.1%o based on an inferred 8 Fe value for the sorbed component as calculated from Fe mass balance (Fig. 4), as was noted in that study. Measured differences in Fe isotope compositions between ferric oxide/hydroxide and Fe(II)aq during dissimilatory Fe(III) reduction and photosynthetic Fe(II) oxidation have been proposed to reflect fractionation between soluble Fe(II) and Fe(III) species, where the soluble Fe(III) component is postulated to be bound to the cell and is not directly measured (Beard et al. 2003a Croal et al. 2004). In the case of dissimilatory Fe(III) reduction, assuming a static model simply for purposes of illustration, if 50% of the Fe in a pool that is open to... 

Potential excursions provoking surface oxidations and surface reconstructions of crystalline surfaces. These phenomena can be monitored on noble metal surfaces over a wide range of potentials. With the unique atomic resolution of in situ STM/AFM, it is possible to follow corrosion processes in real time at the atomic level. 

Promotion and deactivation of unsupported and alumina-supported platinum catalysts were studied in the selective oxidation of 1-phenyl-ethanol to acetophenone, as a model reaction. The oxidation was performed with atmospheric air in an aqueous alkaline solution. The oxidation state of the catalyst was followed by measuring the open circuit potential of the slurry during reaction. It is proposed that the primary reason for deactivation is the destructive adsorption of alcohol substrate on the platinum surface at the very beginning of the reaction, leading to irreversibly adsorbed species. Over-oxidation of Pt active sites occurs after a substantial reduction in the number of free sites. Deactivation could be efficiently suppressed by partial blocking of surface platinum atoms with a submonolayer of bismuth promoter. At optimum Bi/Ptj ratio the yield increased from 18 to 99 %. 

There are numerous indications in the literature on catalyst deactivation attributed to over-oxidation of the catalyst (3-5). In the oxidative dehydrogenation of alcohols the surface M° sites are active and the rate of oxygen supply from the gas phase to the catalyst surface should be adjusted to that of the surface chemical reaction to avoid "oxygen poisoning". The other important reason for deactivation is the by-products formation and their strong adsorption on active sites. This type of... 

In experiments run over a number of cycles, the activity was observed to increase after the first cycle, unlike the y-A Os counterpart which deactivated. Using BN, no Pt sintering occurred and this was ascribed to the high thermal conductivity of BN, ensuring that no local hot-spots were formed. On the basis of XPS, the locus of Pt particle attachment was proposed to be surface boron oxide impurities. Taylor and Pollard have compared the activities of silica (194 m g ) and boron nitride (7 m g ) supported vanadium oxide catalysts for propane oxidation. The use of boron nitride was reported to significantly... 

Oxidation and oxidative dehydrogenation reactions over oxide catalysts have been widely studied in recent years. The precise role of oxygen in these reactions remains elusive, but slowly a more detailed picture is emerging which suggests that both oxide ions of the lattice and oxygen species on the surface can play an important role (/, 2). 

The OJ ion plays an important role in exchange reactions over oxides through the reaction of gas-phase oxygen with 0 on the surface ... 

E.m.f. oscillations during the oxidation of hydrogen over nickel have been studied further by Stoukides and co-workers.41,42 Oscillations occurring in the temperature range 510 to 618 were also explained in terms of the formation and destruction of surface nickel oxide 42... 

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