Catalytic activity crystallite size

A different kind of shape selectivity is restricted transition state shape selectivity. It is related not to transport restrictions but instead to size restrictions of the catalyst pores, which hinder the fonnation of transition states that are too large to fit thus reactions proceeding tiirough smaller transition states are favoured. The catalytic activities for the cracking of hexanes to give smaller hydrocarbons, measured as first-order rate constants at 811 K and atmospheric pressure, were found to be the following for the reactions catalysed by crystallites of HZSM-5 14 n-... 

In the early days of catalysis the porous high surface area support was usually thought to be inert. It soon became obvious, however, that the catalytic activity, or turnover frequency, of a catalytic reaction on a given active phase is quite often seriously affected both by the crystallite size and by the material of the support. 

The second phenomenon, i.e. the change in catalytic activity or selectivity of the active phase with varying catalyst support, is usually termed metal-support interaction. It manifests itself even when the active phase has the same dispersion or average crystallite size on different... 

Ir catalysts supported on binary oxides of Ti/Si and Nb/Si were prepared and essayed for the hydrogenation of a,P-unsaturated aldehydes reactions. The results of characterization revealed that monolayers of Ti/Si and Nb/Si allow a high metal distribution with a small size crystallite of Ir. The activity test indicates that the catalytic activity of these solids is dependent on the dispersion obtained and acidity of the solids. For molecules with a ring plane such as furfural and ciimamaldehyde, the adsorption mode can iirfluence the obtained products. SMSI effect (evidenced for H2 chemisorption) favors the formation of unsaturated alcohol. 

Alternatively, it may be possible to demonstrate for the pure metals that the catalytic activity is independent of film weight in a certain weight range. For example, rates of ethylene oxidation were constant over pure palladium films, deposited and annealed at 400°C and weighing between 4 and 40 mg (73). Then, if electron micrographs show that the crystallite size is relatively independent of composition, a satisfactory comparison of catalytic activity can be made at the various alloy compositions. Finally, surface area measurements are less urgently needed when activity varies by orders of magnitude, or where the main interest lies outside the determination of absolute reaction rates. 

Supported metal catalysts are used in a large number of commercially important processes for chemical and pharmaceutical production, pollution control and abatement, and energy production. In order to maximize catalytic activity it is necessary in most cases to synthesize small metal crystallites, typically less than about 1 to 10 nm, anchored to a thermally stable, high-surface-area support such as alumina, silica, or carbon. The efficiency of metal utilization is commonly defined as dispersion, which is the fraction of metal atoms at the surface of a metal particle (and thus available to interact with adsorbing reaction intermediates), divided by the total number of metal atoms. Metal dispersion and crystallite size are inversely proportional nanoparticles about 1 nm in diameter or smaller have dispersions of 100%, that is, every metal atom on the support is available for catalytic reaction, whereas particles of diameter 10 nm have dispersions of about 10%, with 90% of the metal unavailable for the reaction. 

Owing to low copper content, copper-ceria catalysts are nonpyrophoric and stable, showing little or no deactivation during the experiments. The Cu0 2Ce0 x02 r catalyst prepared by coprecipitation method showed good catalytic activity for the WGS reaction. The Cu01Cc()9O2, catalyst prepared by sol-gel method was found to be less active, which could be due to lower number of active copper sites, or to different crystallite size and structure of copper-containing species. The copper-ceria catalysts were shown to be selective for the WGS reaction and no methanation reactions were observed over any catalyst under the experimental conditions used. 

Catalytic Activity of Ni0-Ce02-Zr02—Influence ofNi Crystallite Size and Support Composition... 

A marked effect of the Ce02/Zr02 composition (in samples containing 40 wt.% NiO) on the catalytic activity was noticed. The catalysts with Ce Zr =1 1 (6A) were not only more active (than 7A and 8A) but were also stable during the reaction. Sample 8A containing no zirconia in the support showed a low activity. The NiO crystallite size (Table 11.2) in these compositions varied in the order 7A < 6A < 8A. It may be recalled that on ceria-based catalysts the crystallite size of nickel metal was similar to that of NiO. The higher activity for 6A than 7A indicates that in addition to accessibility of... 

Ruthenium catalysts prepared from Ru3(CO)i2 and other related carbonyl-derived complexes have been widely used in reactions of hydrogenolysis, homologation and dimerization of alkanes [114—116]. Catalysts derived from carbonyl precursors usually show higher catalytic activities than conventionally prepared supported mthenium catalysts. This correlates well with the smaller crystallite size achieved by using carbonyl precursors. 

Assuming that Ti(IV) is distributed statistically in all tetrahedral positions, it can be easily seen that even for crystallite sizes of 0,2 m the great majority of T1(IV) is located inside the pore structure. Assuming that every Ti(IV) is a catalytic centre with equal activity, diffusion limitations for molecules of different sizes should be observed. This is in fact the case. It has been shown [27] that the rate of oxidation of primary alcohols decreases regularly as the chain length increases, while for iso-butyl alcohol a sudden drop in the rate is observed. Also the reactivity order of olefins on TS-1 is different from the order observed with homogeneous electrophilic catalysts, while as already indicated very bulky molecules are unreactive when TS-1 is used as the catalyst. All these facts can only be interpreted as due to diffusion limitations of the larger molecules, which means that the catalytic sites are located inside the pore structure of the solid. 

Returning now to the observed effect of particle size on catalytic activity, van Hardeveld and Hartog 219) have calculated that the relative concentration of C7 sites on octahedral iron crystallites decreases with decreasing particle size and that, in general, the C7 site is not a small-particle surface site. The above correlation of increased catalytic activity with increased C7 site surface concentration thus also explains the observed structure sensitivity (particle size dependence) for this reaction. Finally, this correlation is consistent with results obtained from field electron microscopy of iron (220), single crystal reaction studies on tungsten (also a bee metal) (227), and symmetry considerations (222). 

HZSM-5 and NaHZSM-5 samples with different crystallite sizes were used in our studies (Table I). They were synthesized using organic templates (8a-d), and the crystallite sizes were determined by scanning electron microscopy (Fig. 1). The A AS catalyst contained 15% AI2O3. As seen from Fig. 2, the catalytic activity per unit site is the same for all our acid catalysts. 

Details about preparation and characterization of dispersed microcrystals can be found in review chapters [322] and will not be dealt with here. All investigations indicate that the properties of microcrystals differ considerably from those of bulk metals (and from those of adatoms and thin films as well) [328], and that they can also be influenced by the nature and texture of the support. In particular, micro-deposits of precious metals on various inert supports (Ti, Ta, Zr, Nb, glassy carbon etc.) exhibit enhanced electrocatalytic effects as evaluated per metal atom, while the mechanism of H2 evolution remains the same [329], and the enhancement increases as the crystallite size decreases [326, 331] (Fig. 17). However, while this is the case with Rh, Pt, Os and Ir, Pd shows only an insignificant increase, whereas for Ru even a drastic decrease is observed [315, 332]. Thus, the effect of crystal size on the catalytic activity appears to depend on the nature of the catalyst (without any relation with the crystal structure group) [330]. 

Changes in the catalytic activity of unit accessible surface or the specific catalytic activity (SCA) has attracted the attention of researchers. In the 1950s Boreskov formulated a rule for the approximate constancy of the SCA. According to this rule, the SCA for several metal and oxide catalysts remains approximately constant with significant variations of the surface and crystallite sizes under preparative conditions. Boreskov ascribed this con-... 

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