Unsupported catalytic activity

Tubes—Is Unsupported Gold Catalytically Active ChemPhysChem, 8, 1911-1913. 

The platinum concentrations in the platinized carbon blacks are reported to be between 10 and 40% (by mass), sometimes even higher. At low concentrations the specific surface area of the platinum on carbon is as high as lOOm /g, whereas unsupported disperse platinum has surface areas not higher than 10 to 15m /g. However, at low platinum concentrations, thicker catalyst layers must be applied, which makes reactant transport to reaction sites more difficult. The degree of dispersion and catalytic activity of the platinum depend not only on its concentration on the carrier but also on the chemical or electrochemical method used to deposit it. 

Among various methods to synthesize nanometer-sized particles [1-3], the liquid-phase reduction method as the novel synthesis method of metallic nanoparticles is one of the easiest procedures, since nanoparticles can be directly obtained from various precursor compounds soluble in a solvent [4], It has been reported that the synthesis of Ni nanoparticles with a diameter from 5 to lOnm and an amorphous-like structure by using this method and the promotion effect of Zn addition to Ni nanoparticles on the catalytic activity for 1-octene hydrogenation [4]. However, unsupported particles were found rather unstable because of its high surface activity to cause tremendous aggregation [5]. In order to solve this problem, their selective deposition onto support particles, such as metal oxides, has been investigated, and also their catalytic activities have been studied. 

In addition to Au and noble metals, Ni-Zn nanoclusters with an amorphous structure were successfully deposited on Ti02 nanoclusters. The state of Ni was metallic. The catalytic activity of Ni-Zn/Ti02 in olefin hydrogenation was ca. 10 times higher than unsupported Ni nanoclusters. Selective deposition onto Ti02 and the addition of Zn seemed to play an important role to stabilize Ni nanoclusters and to decrease the size of Ni nanoclusters, respectively. Also, clearly Zn promoted the hydrogenation activity of Ni and inhibit the growth of the size, but did not substantially affect Ni nature itself... 

The promotion effects of Mn on unsupported Fe-based F-T catalysts were also studied by Jensen and Massoth. " These authors concluded that the incorporation of Mn chemically and electronically promotes the active Fe surface. More particularly, it appears to alter the CO hydrogenation reaction path by suppressing the direct formation of paraffins from the reactive intermediate, leading to the increased production of higher olefins. Finally, Das et al. also observed that the addition of moderated amounts of Mn promoter to unsupported Fe F-T catalysts promotes the catalytic activity as well as the selectivity towards lower alkenes. ... 

The catalytic properties of unsupported transition metal sulphides have been examined for the reaction of dehydrogenation of tetrahydrothiophene. This study has shown that a selectivity higher than 90% for thiophene formation can be obtained for the most active catalysts, essentially the second row sulphide catalysts. The comparison between the catalytic activities in both dehydrogenation of tetrahydrothiophene and... 

Although the synthesis and catalytic activity of unsupported and alumina-supported molybdenum nitride have been studied extensively, much less attention has been given to examining the surface structure and... 

The establishment of the structures and thermal transformations of the catalytically active phases of bismuth molybdate resulted in research directed toward investigating the stability of the structure under reducing conditions. Fattore et al. (38) investigated an unsupported bismuth molybdate catalyst with composition Bi2032.66M0O3 during propylene... 

Powders possessing relatively high surface area and active sites can be intrinsically catalytically active themselves. Powders of nickel, platinum, palladium, and copper chromites find broad use in various hydrogenation reactions, whereas zeolites and metal oxide powders are used primarily for cracking and isomerization. All of the properties important for supported powdered catalysts such as particle size, resistance to attrition, pore size, and surface area are likewise important for unsupported catalysts. Since no additional catalytic species are added, it is difficult to control active site location however, intuitively it is advantageous to maximize the area of active sites within the matrix. This parameter can be influenced by preparative procedures. 

In this system, the catalyst G3-I9 showed a similar reaction rate and turnover number as observed with the parent unsupported NCN-pincer nickel complex under the same conditions. This result is in contrast to the earlier observations for periphery-functionalized Ni-containing carbosilane dendrimers (Fig. 4), which suffer from a negative dendritic effect during catalysis due to the proximity of the peripheral catalytic sites. In G3-I9, the catalytic active center is ensconced in the core of the dendrimer, thus preventing catalyst deactivation by the previous described radical homocoupling formation (Scheme 4). 

Oxygen chemisorption methods were used to titrate surface vanadium sites in these studies. Raman, X-ray diffraction and isotopic labeling were done to support the dispersion results from chemisorption. A further conclusion was that as the % V increased for ethane oxidation reactions that the catalytic activity and selectivity was similar to that of unsupported vanadia. 

II. 5).204,205 Unsupported iridium catalysts have been prepared by reducing an iridium oxide of Adams type at 165°C under a stream of hydrogen206 or by reducing iridium hydroxide, prepared by addition of lithium hydroxide to an aqueous solution of irid-ium(III) chloride, at 80-90°C and 8 MPa H2.204 Unsupported and supported iridium catalysts may also be prepared by reduction of iridium(IV) chloride with sodium boro-hydride.207 It is noted that the catalytic activity of deactivated iridium can be almost completely regenerated by treatment with concentrated nitric acid.205... 

The activity of the thus prepared Cu(oxide)/SiC>2 catalyst in the oxidation of carbon monoxide is represented in Fig. 9.13. It can be seen that the activity of the fresh catalyst before reduction is rather low. In spite of the very good dispersion (high surface area), the conversion at e.g. 180°C is much lower than that of unsupported copper oxide and the less well dispersed copper oxide. However, reduction and reoxidation leads to a much higher activity, cf. Fig. 9.14. Apparently, then, the activity of copper ions in a copper hydrosilicate is much lower than that of those in an oxide. As the dispersion remains very high in the transformation of the one phase into the other, a high catalytic activity can therefore be achieved. 

The specific reaction ( activation ) conditions for the conversion of catalyst precursors to unsupported catalysts have a direct effect on the catalytic activity and dispersion. The importance of reaction intermediates in decomposition of ammonium heptamolybdate and ammonium tetrathiomolybdate, and the sensitivity of these intermediates to reaction conditions, were studied in coal liquefaction systems. Recent results indicate that optimization of activation conditions facilitates the formation of a highly dispersed and active form of molybdenum disulfide for coal liquefaction. The use of the catalyst precursors ammonium heptamolybdate, ammonium tetrathiomolybdate, and molybdenum trisulflde for the conversion of coal to soluble products will be discussed. 

When fixed on MgCl2 in this manner, Ti atoms have an extremely high catalytic activity for olefin polymerization, clearly superior to unsupported Ti atoms in TiClj-based conventional catalysts. 

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