Surface modifiers catalytic activity

In some instances, there still exist conflicting reports about the surface acidity-catalytic activity correlation. These differences may arise not only from the use of different reaction conditions and different approaches to preparing or modifying the catalysts but also from a poor characterization of the materials employed. Indeed, the detailed physicochemical characterization of the catalytic materials, as well as the study of their interaction with reagents and products, still represents well-recognized problems in the use of heterogeneous catalysis for organic syntheses. 

Metals other than A1 have been successfully introduced in numerous zeolite frameworks. Aluminum substitution by other metals, such as Fe, Ga, Zn, Co or Cu in the zeolite framework results in modified acidity, and subsequently modified catalytic activity, for certain reactions such as selective catalytic reduction of NOx by hydrocarbons. For example, a calorimetric and IR spectroscopic study of the adsorption of N2O and CO at 303 K on Cu(II)-exchanged ZSM-5 zeolites with different copper loadings has been performed by Rakic et al. [92]. The active sites for both N2O and CO are Cu (I) ions, which are present on the surface as a result of the pre-treatment in vacuum at 673 K. The amounts of chemisorbed species adsorbed by the investigated systems and the values of the differential heats of adsorption of both nitrous oxide (between 80 and 30 kJ mof ) and carbon monoxide (between 140 and 40 kJ mol ) demonstrate the dependence of the adsorption properties on the copper content. 

The catalytic properties of the shock-modified rutile whose defect properties have been reported in previous sections of this chapter have been studied in a flow reactor used to measure the oxidation of CO by Williams and coworkers [82G01, 86L01]. As shown in Fig. 7.7 the effect of shock activation is substantial. Whereas the unshocked material displays such low activity that an effect could only be observed at the elevated temperature of 400 °C, the shock-modified powder shows substantially enhanced catalytic activity with the extent of the effect depending on the shock pressure. After a short-time transient is annealed out, the activity is persistent for about 8 h. Although the source of the surface defects that cause the activity is not identified, the known annealing behavior of the point defects indicates that they are not responsible for the effect. 

Mass loss determinations refer to the total change resulting from reactant decomposition and usually include contributions from a mixture of product compounds, some of which would normally be condensed under conditions used for accumulatory pressure measurements. Such information concerned with the overall process is, however, often usefully supplemented by evolved gas analyses (EGA) using appropriate analytical methods. Sestak [130] has made a detailed investigation of the effects of size and shape of reactant container on decomposition kinetics and has recommended that the sample be spread as a thin layer on the surfaces of a multiple plate holder. The catalytic activity of platinum as a reactant support may modify [131] the apparent kinetic behaviour. 

CATALYTIC ACTIVITY ON SURFACES MODIFIED BY PROMOTERS OR POISONS... 

Surface faceting may be particularly significant in chiral heterogeneous catalysis, particularly in the N i/P-ketoester system. The adsorption of tartaric add and glutamic acid onto Ni is known to be corrosive and it is also established that modifiers are leached into solution during both the modification and the catalytic reaction [28]. The preferential formation of chiral step-kink arrangements by corrosive adsorption could lead to catalytically active and enantioselective sites at step-kinks with no requirement for the chiral modifier to be present on the surface. 

Instead of the absorption of chiral modifiers on metal surfaces, a new method using a slightly different approach attaches chiral moieties directly to metal surfaces through chemical bonds. Chiral silyl ethers have been attached to Pd surface atoms these new catalysts have the form (Pd)s=Si-0-R(,< orS) 42 Their synthesis arose from studies of the effects of siliconation on the catalytic activities and selectivities of dispersed, supported Pd and Pt.43-47 The results from... 

The catalytic activity of hierarchical and conventional Beta zeolites for acylation of 2-MN is displayed in Figure 2(a) The Beta (PHAPTMS) sample shows a superior catalytic activity than the conventional one, due to its enhanced textural properties. In this case, the bulky nature of both substrate and products may cause the existence of diffusional problems inside the zeolitic channels, which are attenuated in the modified Beta sample due to the presence of the hierarchical porosity. Regarding the product distribution (Figure 2(b)), two main products are observed and a third isomer, 8-A,2-MN isomer is produced just in minor amounts. Interestingly, the selectivity towards the desired isomer increases in the material obtained from silanized seeds, reaching values around 75%. Probably, the active sites located on the surface of the secondary porosity are able to catalyze also the formation of 6-A,2-MN by transacylation. However, this reaction is expected to be strongly hindered in the conventional Beta zeolite since it requires the participation of two bulky molecules as reactants. 

CD-modified nanoparticles sites. These studies afford an interesting example of tunable catalyst design at the molecular level. Manipulation of the surface of cat-alytically active metal nanoparticles seems possible, and can be used to modulate the catalytic activity on demand. 

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