Hydrogenation structure sensitivity

Except for support effects, structure sensitivity has usually appeared in one of two aspects, variation of rate with svirface crystal face or with particle size. In ICC 1 Gwathmey reported in one of the first experiments with single crystal faces that different faces machined fi om Ni single crystal spheres catalyzed the hydrogenation of ethylene at different rates (ICC 1 paper 5). 

The kinetics of ethylene hydrogenation on small Pt crystallites has been studied by a number of researchers. The reaction rate is invariant with the size of the metal nanoparticle, and a structure-sensitive reaction according to the classification proposed by Boudart [39]. Hydrogenation of ethylene is directly proportional to the exposed surface area and is utilized as an additional characterization of Cl and NE catalysts. Ethylene hydrogenation reaction rates and kinetic parameters for the Cl catalyst series are summarized in Table 3. The turnover rate is 0.7 s for all particle sizes these rates are lower in some cases than those measured on other types of supported Pt catalysts [40]. The lower activity per surface... 

This review covers the personal view of the authors deduced from the literature starting in the middle of the Nineties with special emphasis on the very last years former examples of structure-sensitive reactions up to this date comprise, for example, the Pd-catalyzed hydrogenation of butyne, butadiene, isoprene [11], aromatic nitro compounds [12], and of acetylene to ethylene [13], In contrast, benzene hydrogenation over Pt catalysts is considered to be structure insensitive [14] the same holds true for acetonitrile hydrogenation over Fe/MgO [15], CO hydrogenation over Pd [16], and benzene hydrogenation over Ni [17]. For earlier reviews on this field we refer to Coq [18], Che and Bennett [9], Bond [7], as well as Ponec and Bond [20]. 

Structure sensitivity of 1,3-butadiene hydrogenation was recently investigated by Rupprechter et al. [59] on well-defined Pd/Al203/NiAl(l 1 0) single crystals. 

Figure 7. Structure-sensitivity of prenal (3-methyl-crotonalde-hyde) hydrogenation over Pt single crystals (ph2 = 200Torr, Pprenai = 0.007 Torr, T= 353 K) [74].

An example for a non-structure-sensitive reaction is provided by Davis et al. [102], who investigated the liquid-phase hydrogenation of glucose over carbon and silica based ruthenium catalysts with particle sizes between 1.1 and 2.4 run. Depending on catalyst loading which was between 0.56 wt.% and 5 wt.%, dispersion decreased from 91% to 43%. At the same time, TOFs varied only insignificantly in a range between 0.21 1/s and 0.32 1/s. 

ME technique is of special interest in the preparation of catalytically active materials, as the control of particle size and monodispersity are very important for structure-sensitive reactions, like hydrogenations [15]. Metal... 

The used Pd/ACF catalyst shows a higher selectivity than the fresh Lindlar catalyst, for example, 94 1% versus 89 + 2%, respectively, at 90% conversion. The higher yield of 1-hexene is 87 + 2% with the used catalyst versus 82 + 3% of the Lindlar in a 1.3-fold shorter reaction time. Higher catalyst activity and selectivity is attributed to Pd size and monodispersity. Alkynes hydrogenation is structure-sensitive. The highest catalytic activity and alkene selectivity are observed with Pd dispersions <20% [26]. This indicates the importance of the Pd size control during the catalyst preparation. This can be achieved via the modified ME technique. 

In general, the results point to the edges and/or corners (small particles) favoring hydrogenation of the C=C bond whereas the planes (large particles) favor hydrogenation of the C=0 bond. This seems to be true for all compounds on Pt (see Table 2.6, lines 10-27, and 29-30) and for cinnamaldehyde on Ru and Rh (see Table 2.6, lines 33, 34, 37, and 38) however, citral on Ru did not exhibit this effect (see Table 2.6, lines 35 and 36), according to the authors statement. The reasons for this latter result are not clear. Why, for example should other alkyl-substituted a,P-unsaturated aldehydes exhibit this structure sensitivity and citral not Clearly, other factors are also at play. 

A mild structure sensitivity accompanies hydrogenation of nitrosobenzene over a series of dispersed 1% Pd/Si02.294 The lower dispersed catalysts (larger particle sizes) catalyze faster rates, suggesting that planes are more active than either edges or corners for catalyzing the hydrogenation of nitrosobenzene. 

On Pt, Pd, Ni, and Rh the regioselectivity depends on the conditions. Mainly ester is formed at low hydrogen pressures, whereas mainly diol monoether is formed at higher pressures.30 31 Selectivity is structure-sensitive more ester is formed on highly dispersed catalysts. 

Both the data on hydrogen adsorption and formic acid oxidation show pronounced structural sensitivity, thus confirming a paramount role of surface structure in electrocatalytic reactions. It can be concluded that each crystallographic orientation represents a distinct electrochemical (chemical) entity. The investigation of stepped surfaces seems to be necessary to reach an understanding of these systems on a molecular level. Hydrogen adsorption shows dependences on the terrace orientation, step orientation, and step density. All the... 

The hydrogenation of butadiene is structure-sensitive on Pd and Rh but lacks particle-size dependence in the case of platinum. The strong complexation of the diene to atoms of low coordination number is a possible explanation for this phenomenon where it occurs37,38. 

Much experience concerning the hydrogenation of conjugated dienes was obtained with butadiene hydrogenation. On Pt single crystals the reaction was found to be structure sensitive the activity sequence of different planes (marked with Miller s index) is... 

Asymmetric diarylmethanes, hydrogenolytic behaviors, 29 229-270, 247-252 catalytic hydrogenolysis, 29 243-258 kinetics and scheme, 29 252-258 M0O3-AI2O3 catalyst, 29 259-269 relative reactivity, 29 255-257 schematic model, 29 254 Asymmetric hydrogenations, 42 490-491 Asymmetric synthesis, 25 82, 83 examples of, 25 82 Asymmetry factor, 42 123-124 Atom-by-species matrix, 32 302-303, 318-319 Atomic absorption, 27 317 Atomic catalytic activities of sites, 34 183 Atomic displacements, induced by adsorption, 21 212, 213 Atomic rate or reaction definition, 36 72-73 structure sensitivity and, 36 86-87 Atomic species, see also specific elements adsorbed... 

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