Transition-metal sulfide catalysts selectivity

The catalysts applied in hydroprocessing operations are typically sulfided CoO—Mo03—A1203 or NiO—M0O3—A1203. The results of relevant studies281 and the application in refinery processes of these and other transition-metal sulfide catalysts were reviewed.282 Selection of catalysts and reactors for particular feeds and products is also an important issue.257,280,283,284... 

In this section, we will emphasize the importance of the electronic structure, the crystallographic structure and the sulfur vacancies in understanding catalytic activity and selectivity of transition-metal sulfide catalysts. 

The chapter Fundamental Studies of Transition-Metal Sulfide Catalytic Materials by Chianelli, Daage, and Ledoux reviews current understanding of the relationship between structural and other properties of these catalysts and their catalytic activity and selectivity in hydrodesulfurization. In view of increasing environmental demands, this field has been heavily researched. The authors show how systematic studies and applications of novel methods can provide considerable understanding of these important catalysts. 

We need to develop methods to understand trends for complex reactions with many reaction steps. This should preferentially be done by developing models to understand trends, since it will be extremely difficult to perform experiments or DFT calculations for all systems of interest. Many catalysts are not metallic, and we need to develop the concepts that have allowed us to understand and develop models for trends in reactions on transition metal surfaces to other classes of surfaces oxides, carbides, nitrides, and sulfides. It would also be extremely interesting to develop the concepts that would allow us to understand the relationships between heterogeneous catalysis and homogeneous catalysis or enzyme catalysis. Finally, the theoretical methods need further development. The level of accuracy is now so that we can describe some trends in reactivity for transition metals, but a higher accuracy is needed to describe the finer details including possibly catalyst selectivity. The reliable description of some oxides and other insulators may also not be possible unless the theoretical methods to treat exchange and correlation effects are further improved. 

Not only metals but some oxide catalysts are active in diene hydrogenation ZnO modified by Sn(CH3)4 afforded 1-butene in hydrogenation of butadiene at room temperature. Reduced and sulfided moUbdena on alumina catalyst hydrogenated butadiene and cyclohexadiene selectively5 . When the transition metal complex Mo(CO)6 was encapsulated in NaY zeolite cages, it converted //wnv-l, 3-pcnladicnc to cA-2-pentene and 1,4-pentadiene to c -l,3-pentadiene at 150°C °. Cr(CO)3 encaged in LiX or NaX zeolite was efficient and selective in butadiene hydrogenation to cw-2-butene . ... 

The use of transition-metal (Ti, Mo, V, Fe, W, Re, Ru) complexes as active catalysts for the selective oxidation of thioethers by H2O2 in homogeneous conditions has been reported by various authors [3-10]. Recently, it has been shown that some of these metals (Ti,V) incorporated in a zeolitic framework, such as MFI or MEL, are able to catalyse the oxidation reaction of thioethers with H2O2 [11,12]. However, no detailed studies on this reaction are available. The scope of this work was to investigate the influence of thioether structure, solvent nature, reaction temperature and shape selectivity effect of catalyst on the performances of TS-1 and Ti-beta samples in the sulfoxidation of organic sulfides with H2O2... 

Neumann and co-workers have used sandwich-type polyoxometalates as catalysts for such reactions.305 The sandwich consists of transition metal ions between two Keggin anions, as in Ki2WZnMn(II)2(ZnW9034)2. In some cases, quaternary ammonium salts were used as the cations to take the catalyst into organic solvents. Sulfides were oxidized to sulfoxides with 30% aqueous hydrogen peroxide in 85-90% yields, with some sulfone also being formed. The system was more than 99% selective in the conversion of cyclooctene to its epoxide. The system also shows good selectivity between double bonds (6.57), probably the result of the bulky anion and the increased electron density in alkyl-substituted double bonds. 

Oxides and sulfides of the transition metals are the most active, most selective, and industrially most important catalysts. According to electronic theory, numerous other semiconductors should have good catalytic properties, which could be... 

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