The goal of our studies was to determine the nature of interactions between catalytic active samples, such as polypyrrole (PPy) doped with: chloride anions, heteropolyacids such as H5PMo10V2O40, or H4SiW12O40, and oxygen particles. In order to reveal the mechanism of the linkage between the catalysts and oxygen we provided the electron paramagnetic resonance (EPR) measurements of synthesized samples in O2 and N2 flow. Moreover, the X-ray photoelectron spectroscopy (XPS) measurements were performed to show the properties of doped heteropolyacids and the state of nitrogen in polypyrrole matrix. The results of EPR studies of PPy(Cl), PPy(H4SiW12O40), PPy(H5PMo10V2O40) samples, show that the polypyrrole doped with chloride anions interacts much easier with oxygen than polypyrrole doped with heteropolyacids (in the above given order, of preference with the most active polypyrrole system first). It correlates with XPS results, which show that a molybdenium-vanadium anion is more reduced than a silicon-tungsten one. The redox reactions of heteropolyacids involve the oxidation-reduction of the conjugated polymer chain, leaving no or little place for interactions with oxygen. Polypyrrole doped with H4SiW12O40 shows some oxygen sensitivity as observed in the EPR studies, as opposed to polypyrrole doped with H5PMo10V2O40, which is in line with the XPS results. 相似文献
Alumina-silica possessing various Al2O3/SiO2 ratios was used as a carrier of surface titanium complexes. The systems obtained were examined as models for the investigation of the macroligand (inorganic gel) influence on the physicochemical properties of supported transition metal complexes. The titanium complexes were prepared first by the reaction of CpTiCl3, with the hydroxyl groups of the gel and then reduced by an excess of BuLi. The influence was established of the basic gel properties on: (a) the amount of titanium(IV) and titanium(III) complexes on the alumina-silica gel surfaces; (b) the symmetry of the surface TiIII surface complexes; (c) the electron density around the surface-TiIII ions, ionic or covalent bonds character in a complex; and (d) the catalytic activity in olefin hydrogenation. 相似文献
Oxidative-reductive properties on the acid-base surfaces of the oxide compositions Sn-Ce-Rh-O and Zr-Mg-Y-O, active as catalysts in the ketonization of secondary alcohols were determined based on the isopropanol conversion selectivity. The kinetics of isopropanol conversion was measured in the oxygen-free atmosphere. Activation energies for both directions of conversion (dehydration to propylene and dehydrogenation to acetone) were calculated. The results were compared with the kinetics over SnO2 and ZrO2. Both oxide compositions, Sn-Ce-Rh-O and Zr-Mg-Y-O are oxidative-reductive catalysts containing Lewis acid centers. 相似文献
The main objective of our work was to investigate the possibility and usefulness of indirect methods in X-ray microanalysis
for the quantification of biologically important compounds. Metallothionein-like proteins (MT-like proteins) from kidney and
liver, rich in sulfur were chosen as an indicator of heavy metal presence in cells and their environment. Tissues from goldfish
(Carassius auratus gibelio) were sampled after short and prolonged periods of exposure to Co+2, CrO4−2, Pb+2, Cu+2 and control treatment and prepared for histochemical staining for peroxidated thiolate groups. Commonly used –S–S– bonds
dye (Nitro Red) was replaced with iodine atoms and they were quantified at L line by means of X-ray microanalysis combined
with SEM. After fish treatments with heavy metal solutions changes in MT-like proteins and in I atom contents were expected.
There was statistically significant decrease in MT-like proteins level in kidney after lead treatment (Pb/C = 0.62). In liver
a statistically significant increase in MT-like proteins concentration was observed after chromium, cobalt and lead ions treatment
in comparison to control animals. The following ratios were noted: 3.04 for Cr/C, 2.18 for Co/C and 2.10 for Pb/C. Our finding
indicates that the method of indirect measurement of MT-like proteins in fish and other animal tissues is possible. The concentration
of iodine atoms is above their detection level by EDS and their changes are possible to identify. During histochemical procedures
it is worth taking into account sample preparation methods which might disturb the quality and quantity of the analysed material. 相似文献
The concentrations of diisopropylnaphtalene (DIPN) isomers in experimental equilibrium mixtures obtained on amorphous aluminosilicate and HY zeolite have been measured by GC method. The total energy and Gibbs free energy of the isomers were calculated by DFT method at the B3PW91/3-21G level. Comparison of the populations based on the DFT energies with the experimental concentrations of DIPN isomers are in good agreement. This fact can suggest that isomerization is mainly determined by thermodynamic equilibrium. 相似文献
Results of TG and DTA studies as well as an analysis of the liberated gas products have led us to recognize differences in the mechanisms of transformations taking place in the systems NH4ReO4/Al2O3-SiO2 (25 wt% SiO2 and NH4ReO4/Al2O3 containing 1.1, 3.3 and 3.3, 9.9, 17.8 wt% NH4ReO4. Thermal decomposition of NH4ReO4 on the supports used begins with release of ammonia, which is strongly bound with the surface in the system of 3.3 wt% NH4ReO4/Al2O3, and undergoes oxidation to nitrogen oxides in the air atmosphere. In the other systems studied, the process of ammonia release starts already at 473 K and ammonia does not get oxidized. Moreover, it has been established that ammonia perrhenate supported on the surface of Al2O3-SiO2 in the amount of 1.1 or 3.3 wt% undergoes partial thermal decomposition to ReO2 which is further oxidized in the air atmosphere. As follows from the thermal studies as well as the measurements of activity in a reaction of 1-hexene metathesis, the active centres of the reaction of olefin metathesis are formed on the surface of the studied systems after their calcination at 473 K. 相似文献
The compounds (η5-C5H5)TiCl2(OC6H4X), where X = NO2, Cl, CH3, have been obtained from the reaction of CpTiCl3 with suitable substituted phenols in 1 : 1 ratio. Some of the IR and NMR bands of the compounds correlate directly with Hammett σ factors. 相似文献
The title compound crystallizes in the orthorhombic space groupP212121, withZ=4,a=4.770(1)Å,b=6.620(1)Å,c=37.550(7)Å,R=0.04. The most important factors affecting conformation of the molecules are: the protonation state of the N(9) atom andortho-substitution of the benzene ring in the acetanilide system. Protonation promotes an extended form of the molecule and 2,6-substitution forces a twist of at least 60° between the benzene ring and amide group planes. The resulting separation of lipophilic (xylidine) and amine groups, being two important pharmacophores, equals about 5Å in tocainide and all other structures comprising the amino-2,6-dimethylacetanilide system. 相似文献
The catalytic properties of the (n = 0–3) system, resulting from the reaction of (C3H5)2Ni with hydroxide groups of silica gel and complexation with a Lewis acid, MeAlCl2, have been studied in the oligomerization of propylene. It has been ascertained that when n > 3 the excess of MeAlCl2 is carried out from the catalyst bed by the products. The yield of the product is influenced by the rate of propylene flow and the composition of the catalyst. The yield of products increases with the rise in the propylene flow rate. The highest yield was obtained for n = 1 and the flow of propylene = 360 ml/min g. The elimination by the olefin of the allyl group from the complex in the initial stages of oligomerization was ascertained. This testifies to the formation of new forms of the surface nickel complex that should contain catalytically active NiH or NiR bonds. The EPR studies determined the valence of nickel in this system (n = 1) to be +2 and thus made it possible to propose its structure. 相似文献
A study of modified catalyst systems composed of palladium or its chloride and a co-catalyst such as metallic Fe-powder, iodine, and pyridine was used in the reduction of nitrobenzene to aniline with carbon monoxide and water at 180°C and 2.5-4 MPa pressure. The reaction is complete in 2 h with a nitrobenzene conversion of 98-100% and a 100% selectivity with respect to aniline. 相似文献