Platinum-alumina particle size

When one considers the various results from the reactions of labeled and unlabeled hexanes over supported catalysts and over thick and ultra-thin films, the conclusion emerges that catalysts with very small platinum particles (ultrathin films or 0.2% platinum/alumina) strongly favor reactions via an adsorbed C5 cyclic intermediate, but at large particle size... 

One of the most extensively used addition reactions of cyclobutanes is hydrogenolysis.36 With regard to the mechanistic aspect, evidence has been provided that hydrogenolysis of cyclobutane is structure sensitive to the particle size of the platinum on alumina catalysts.37 Moreover, a kinetic study has also revealed that the mechanism for the hydrogenolysis of cyclobutanes is likely to be different from that for cyclopropanes.37... 

The details of the sample preparation and studies of the nature of the supported-metal samples have been described in a paper dealing with the effect of surface coverage on the spectra of carbon monoxide chemisorbed on platinum, nickel, and palladium (1). The samples consist of small particles of metal dispersed on a nonporous silica which is produced commercially under the names Cabosil or Aerosil.f This type of silica is suitable as a support because it is relatively inert and has a small particle size (150-200 A.). The small particle size is important because it reduces the amount of radiation which is lost by scattering. A nonporous small particle form of gamma-alumina, known as Alon-C, is also available. This material is not so inert as the silica and will react with gases such as CO and CO2 at elevated temperatures. 

The amperometric detection of sucrose was performed with a conventional three-electrode potentiostatic system. With an LC-3D voltammo-graph (Bioanalytical Systems). The working electrode was a 2-mm diameter platinum disc, polished with alumina down to 0.05 pm particle size and rinsed thoroughly with distilled water, the reference electrode was an Ag/AgCl (3M KC1) electrode and the auxiliary electrode was a stainless-steel rod. 

A large number of heterogeneous catalysts have been tested under screening conditions (reaction parameters 60 °C, linoleic acid ethyl ester at an LHSV of 30 L/h, and a fixed carbon dioxide and hydrogen flow) to identify a suitable fixed-bed catalyst. We investigated a number of catalyst parameters such as palladium and platinum as precious metal (both in the form of supported metal and as immobilized metal complex catalysts), precious-metal content, precious-metal distribution (egg shell vs. uniform distribution), catalyst particle size, and different supports (activated carbon, alumina, Deloxan , silica, and titania). We found that Deloxan-supported precious-metal catalysts are at least two times more active than traditional supported precious-metal fixed-bed catalysts at a comparable particle size and precious-metal content. Experimental results are shown in Table 14.1 for supported palladium catalysts. The Deloxan-supported catalysts also led to superior linoleate selectivity and a lower cis/trans isomerization rate was found. The explanation for the superior behavior of Deloxan-supported precious-metal catalysts can be found in their unique chemical and physical properties—for example, high pore volume and specific surface area in combination with a meso- and macro-pore-size distribution, which is especially attractive for catalytic reactions (Wieland and Panster, 1995). The majority of our work has therefore focused on Deloxan-supported precious-metal catalysts. 

Activation (of noble metal electrodes) — Noble metal electrodes never work well without appropriate pretreatment. Polycrystalline electrodes are polished with diamond or alumina particles of size from 10 pm to a fraction of 1 pm to obtain the mirror-like surface. The suspensions of polishing microparticles are available in aqueous and oil media. The medium employed determines the final hydrophobicity of the electrode. The mechanical treatment is often followed by electrochemical cleaning. There is no common electrochemical procedure and hundreds of papers on the electrochemical activation of -> gold and platinum (- electrode materials) aimed at a particular problem have been published in the literature. Most often, -> cyclic and - square-wave voltammetry and a sequence of potential - pulses are used. For platinum electrodes, it is important that during this prepolarization step the electrode is covered consecutively by a layer of platinum oxide and a layer of adsorbed hydrogen. In the work with single-crystal (- monocrystal) electrodes the preliminary polishing of the surface can not be done. 

The small number of charge carriers in the semiconductor is partially compensated for by the small size of metal particles. By using Schwab s magnetic measurements as a clue to the number of electrons transferred to the nickel across the nickel-alumina interface it can be estimated that a change of 0.05 electron per atom would produce detectable catalytic effects. By extrapolation to the small dispersed type of metal particle being considered here, it is seen that for a particle containing 2000 atoms the equivalent transfer would be produced by 100 electrons. Despite this, if one considers contact between a 2000-atom platinum particle and a 100 alumina particle (volume 4 x 10 cc) the flow of electrons to the metal would be drastically limited by the small number of charge... 

The Pt NMR of small platinum particles on classic oxide supports show s that the clean-surface LDOS is largely independent of the support (sihca, alumina, and titania) and of the method of preparation (impregnation, ion exchange, and deposition of colloids). At a given resonance position, one always finds the same relaxation rate, independent of particle size or support. The shape of the spectrum is related to the sample dispersion. The same is true lor particles protected in fihiis of PVP. [However, samples prepared under conditions giving strong SMSIs behave differently 171)]... 

Figure 11 shows conversion to iso-heptanes to be negligible for (0.5 wt. %) platinum supported on activated carbon (Pt/C) as the only catalyst, and also for (0.4 wt. %) platinum on silica-gel (Pt/Si02). No detectable conversion was obtained with silica-alumina. A mechanical mixture of either of the Pt-bearing particles with silica-alumina of about 150 m.Vg-surface area, both in millimeter diameter particle size (1000m), immediately resulted in appreciable isomerization ( SiAl with Pt/C SiAl with Pt/Si02). Isomerization increases rapidly for smaller component particle sizes, of 70/i and S i diameters. It approaches the performance of a silica-alumina that has been directly impregnated with platinum, and which has... 

As already pointed out, the first particle size effect in skeletal rearrangement was found for the hydrogenolysis of methylcyclopentane (55). Nonselective hydrogenolysis takes place on highly dispersed catalysts, with a metal loading smaller than 0.6%, while selective rupture of bisecondary C-C bonds occurs on heavily loaded catalysts (more than 6% platinum on alumina). 

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