Influence of Reaction Parameters on the Hydrogenolysis of Hydroxymatairesinol Over Carbon Nanofibre Supported Palladium Catalysts

The density functional theory (DFT/B3LYP) calculations were applied to investigate the interaction of a Pt₆ particle with the ZSM-5 zeolite framework. The electronic structure of the metal particle is strongly affected by the interaction with basic framework oxygens and acid sites of the zeolite support. Adsorption on basic sites (E_ads = 6 kcal/mol) favors the formation of the electron enriched metal cluster. Interaction of the platinum cluster with the acid site characterized by stabilization energy of 47 kcal/mol results in oxidation of the metal particle and suppression of Brønsted acidity of the support. The hypothesis is put forward that the oxidized platinum particle can function as an active site for the alkane isomerisation on platinum supported high silica zeolites.     

Mechanism of the skeletal isomerisation of linear butenes over ferrierite: analysis of side reactions

An investigation of the effect of reaction conditions on product distribution in the skeletal isomerisation reaction of linear butenes has been carried out. The main reaction routes over ferrierite have been identified. Beside the main product isobutene, major by-product formation occurs. The unwanted reactions include dimerisation of butene to form octenes, hydrogen transfer yielding small amounts of saturated C₃ and C₄ hydrocarbons and disproportionation producing propene and pentenes. The most abundant by-products were pentene and propene, though these were not formed in equimolar amounts as could be expected. Oligomerisation experiments of propene over ferrierite produced large amounts of butene and pentene, revealing the presence of adsorbed nonene. The cracking of this surface species to hexene and propene is the most likely reaction route for the excess propene formation. This additional path to propene formation operates mainly at temperatures above 623 K.     

Sweet-tasting protein monellin is related to the cystatin family of thiol proteinase inhibitors

The structure of the intensely sweet protein monellin, isolated from an African berry, and the structures of two thiol proteinase inhibitors, cystatin and stefin B, are found to be very similar. An alignment of sequences of monellin and the inhibitors, deduced from the structural comparisons, has been extended to include other members of the cystatin superfamily. There is a significant homology (up to 23% identical residues) with oryzacystatins, the only well defined plant cystatins. These results clearly indicate that monellin is a close relative of cystatins. Monellin and cystatins do not have the same sequence in the regions homologous to the cystatin active site. It is suggested here, however, that this region in monellin may be essential for a function in situ, because one of the loops comprising this part of the structure is found to be cleaved.     

Hydrogenation of Citral Over a Polymer Fibre Catalyst

A polymer-supported Pd catalyst was investigated in hydrogenation of citral (3,7-dimethyl-2,6-octadienal), which is a stereoisomer with an isolated and a conjugated double bond as well as a carbonyl group. The catalyst was a fibrous polymer-supported catalyst modified with functional groups and immobilized metals. A comparison of the polymer-supported catalyst with conventional catalysts was made.     

Liquid-phase stereoselective thymol hydrogenation over supported nickel catalysts

The stereoselective hydrogenation of thymol was studied in liquid phase over several nickel catalysts, modified by coimpregnation of inorganic compounds containing chlorine. The total activity of all catalysts studied was decreased and was on the same order of magnitude, indicating that chlorine even after reduction remains on the surface and is responsible for the poisoning effects. Such blocking of accessible sites results in similar reaction rates for the catalysts studied. Selectivity and stereoselectivity to menthols and menthones changed significantly. The modifiers could influence the rate of keto-enol transformations, which is thought to be the key selectivity and stereoselectivity governing step.     

Furfural Oxidation with Hydrogen Peroxide Over ZSM-5 Based Micro-Mesoporous Aluminosilicates

Micro-mesoporous aluminosilicates based on ZSM-5 zeolite, obtained by a dual template method, as well as in the presence of a dual-functional template (i.e. a Gemini-type surfactant), were tested in the oxidation of furfural with hydrogen peroxide. Even substantial changes in acidity and porosity of the catalysts result in minor variations of selectivity towards the desired products. Application of the synthesized zeolite-based materials in the oxidation of furfural with hydrogen peroxide leads to formation of 2(5H)-furanone (yield up to 28.5%) and succinic acid (up to 19.5%) as the main C4 reaction products. The kinetic model developed previously to treat the results for oxidation of furfural over sulfated zirconia was able to describe the data also for micro-mesoporous aluminosilicates.

Graphical Abstract

     

On the rate of heterogeneous catalytic reactions with ionic intermediates

A facile way to compute the rate law of a catalytic reaction with ionic intermediates is proposed, based on the theory of complex reactions. When the ionic nature of intermediates is taken into account it is necessary to add balance equations which correspond to the electroneutrality of the catalyst. Several mechanisms of the olefin hydrogenation were considered as examples.