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The results of studies on the TiO2 photocatalytic oxidation of model air pollutants are summarized. The kinetics of photocatalytic oxidation of CO and the vapors of a number of simple organic substances was studied in detail. It was found that, in the course of reaction, all of the test substances underwent complete mineralization. Gaseous substrates were converted with the participation of several types of reaction centers. The photocatalytic oxidation of sulfur- and phosphorus-containing substances resulted in gradual deactivation of the photocatalyst; however, its activity can be restored by washing the photocatalyst with water. It was found that, along with oxidation, the steps of hydrolysis play an important role in the photocatalytic degradation of air pollutants, such as dimethyl methylphosphonate and 2-chloroethyl sulfide.__________Translated from Kinetika i Kataliz, Vol. 46, No. 3, 2005, pp. 450–465.Original Russian Text Copyright © 2005 by Vorontsov, Kozlov, Smirniotis, Parmon.  相似文献   
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The MoZSM-5 (4.0 wt % Mo) catalyst has been characterized by high-resolution transmission electron microscopy, EDXA, and EPR. Two types of molybdenum-containing particles are stabilized in the catalyst in the course of nonoxidative methane conversion at 750°C. These are 2-to 10-nm molybdenum carbide particles on the zeolite surface and clusters smaller than 1 nm in zeolite channels. According to EPR data, these clusters contain the oxidized molybdenum form Mo5+. The surface Mo2C particles are deactivated at the early stages of the reaction because of graphite condensation on their surface. Methane is mainly activated on oxidized molybdenum clusters located in the open molecular pores of the zeolite. The catalyst is deactivated after the 420-min-long operation because of coke buildup on the zeolite surface and in the zeolite pores.  相似文献   
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The ESE method was successfully used for investigating the texture of the adsorbents and catalysts. Equations were obtained for the kinetics of ESE signal decay due to dipole-dipole interaction between motionless paramagnetic centers distributed uniformly on the fractal surface of solid.
, . , , .
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By using 13C MAS NMR spectroscopy (MAS = magic angle spinning), the conversion of selectively 13C-labeled n-butane on zeolite H-ZSM-5 at 430-470 K has been demonstrated to proceed through two pathways: 1) scrambling of the selective 13C-label in the n-butane molecule, and 2) oligomerization-cracking and conjunct polymerization. The latter processes (2) produce isobutane and propane simultaneously with alkyl-substituted cyclopentenyl cations and condensed aromatic compounds. In situ 13C MAS NMR and complementary ex situ GC-MS data provided evidence for a monomolecular mechanism of the 13C-label scrambling, whereas both isobutane and propane are formed through intermolecular pathways. According to 13C MAS NMR kinetic measurements, both pathways proceed with nearly the same activation energies (E(a) = 75 kJ mol(-1) for the scrambling and 71 kJ mol(-1) for isobutane and propane formation). This can be rationalized by considering the intermolecular hydride transfer between a primarily initiated carbenium ion and n-butane as being the rate-determining stage of the n-butane conversion on zeolite H-ZSM-5.  相似文献   
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The specific features of luminescence of colloidal solutions of Q-CdS with particles of different size and the regularities of luminescence quenching by quenchers of various nature were studied. The luminescence spectra of Q-CdS consist of several bands, which are shifted to the long-ware region as the particle size increases. The dependence of the integral quantum yield of luminescence on the particle size has a sharp maximum at a particle diameter of ?23Å. A Stem—Volmer-type equation including the adsorption isotherm of the quencher molecules on the surface of the Q-CdS colloidal particles was used to describe the regularities of luminescence quenching of Q-CdS colloidal solutions. The CdS particle size was found to affect the efficiency of luminescence quenching. The regularities of luminescence quenching depend both on the rate constant of electron transfer to the quencher molecules and on the ability of the quencher molecules to be adsorbed on the surface of the CdS colloidal particle.  相似文献   
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Catalysts of water oxidation to dioxygen by Ru(bpy) 3 3+ have been obtained by immobilization of colloidal Co(III) hydroxide on supports of the hydroxide types. These supports are found to be able either to enhance (Al(III), Bi(III), Sn(IV) and Ce(IV) hydroxides) or to weaken (Fe(III) and Mn(IV) hydroxides) the catalytic efficiency of the initial sol. The possible nature of the influence of the support is discussed.
Ru(bpy) 3 3+ Co(III). - , ( Al(III), Bi(III), Sn(IV), Ce(IV)), ( Fe(III), Mn(IV)) . .
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Post-irradiation luminescence of irradiated, finely dispersed polycrystals of CaO is shown to result from the tunneling recombination of radiation-induced F s + - and V- centers. The temperature dependence of the rate constant of this tunneling recombination in the temperature range of 85–180 K is determined from the data on thermally stimulated luminescence.
, CaO F s + - V-. 85–180 .
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10.
Tunneling recombination between surface Fss +- and bulk V-centers has been studied by ESR technique over the temperature range of 77–240 K. The activation energy has been measured.
Fs +- V- 77–240 .
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