Inhibition of the toxic byproduct during photocatalytic NO oxidation via La doping in ZnO

It is of a great challenge to develop semiconductor photocatalysts with potential possibilities to simultaneously enhance photocatalytic efficiency and inhibit generation of toxic intermediates.In this study,we developed a facile method to induce the La doping and cationic vacancie(V(Zn))on ZnO for the highly efficient complete NO oxidation.The photocatalytic NO removal efficiency increases from 36.2%to 53,6%.Most importantly,a significant suppressed NO2 production also has been realized.According to the DFT calculations,ESR spectra and in situ FTIR spectra,the introduction of La^3+induce the redistribution of charge carriers in La-ZnO,which promote the production of·O2^- and lead to the formation of V(Zn)for the formation of·OH,contributing to the complete oxidation of NO to nitrate.Besides,the conversion pathway of photocatalytic NO oxidation has been elaborated,This work paves a new way to simultaneously realize the photocatalytic pollutants removal and the inhibition of toxic intermediates generation for efficient and safe air purification.     

Enzymatic determination of phenols using peanut peroxidase

The influence of phenol and its derivatives on the kinetics of oxidation of aryldiamines (indicator-substrates) catalyzed by novel plant peroxidase—cationic peanut peroxidase—was studied. The character of influence of phenols on the kinetics of enzymatic oxidation of benzidine, o-dianisidine, and 3,3′,5,5′-tetramethylbenzidine (TMB) with hydrogen peroxide was found to depend on a correlation between redox properties of phenols and the indicator-substrate of peroxidase. Thus, the catalytic activity of peanut peroxidase is inhibited by phenols with redox potentials higher than that of aryldiamines mentioned above, whereas phenols with potentials below those of aryldiamines, play the role of second substrates of the enzyme. The enzymatic procedures for the determination of numerous phenols on the level of their concentrations 0.05–80 μM were developed using the reactions of benzidine, o-dianisidine, and TMB oxidation. Different analytical signals—the indicator reaction rate and the induction period duration—were used for the determination of phenols, belonging to various groups—the inhibitors and second substrates of the enzyme, respectively.     

Hydrothermal Synthesis of Mo-Based Oxide Catalysts and Selective Oxidation of Alkanes

Mo-V-M(=Al, Ga, Bi, Sb and Te)–O mixed oxide catalysts were synthesized hydrothermally for the first time, characterized structurally, and tested for ethane and propane oxidation after activation by various ways. These catalysts were black solids of rod-shaped (fiber like) crystals, which had a layer structure in the direction of fiber axis and a high dimensional arrangement of metal octahedra in the cross-section plane. These fresh crystalline materials became active for catalytic oxidation of alkanes after heat-treatment at 600 °C and subsequent grinding in order to increase exposed plane of the cross-section. The resulting catalysts were very active for an oxidative dehydrogenation of ethane with 80% of the ethylene selectivity in the reaction temperature range of 300 to 400 °C and also showed about 50% selectivity to acrylic acid in the propane oxidation. Multi-functional character which derived from the high dimensional structure of the catalysts and mechanism of the selective alkane oxidation were discussed.     

FTIR-ATR技术研究聚氨酯类文物保护材料的光降解

Polyurethanes are one kind of relic protection materials commonly used. During artificial photo-ageing, three polyurethanes, HDI-based polyurethane, MDI-based polyurethane and TDI-based polyurethane, have been considered to undergo UV radiation. Photochemical degradation of the polyurethanes has been monitored by means of Fourier transform infrared spectroscopy with attenuated total reflection accessory （FTIR-ATR）. It was proved that the mechanism of the photochemical degradation of polyurethanes might be the scissions of carbamate （urethane） groups and the re-reactions of radical groups formed in the scission reactions. From the experiment results HDI-based polyurethane, an aliphatic diisocyanate, could be considered to be more suitably used as relic protection materials among these three polyurethanes for its ageing products with less color.     

三核钨钼簇合物对苯乙烯氧化反应的催化

关于烯烃的催化氧化,报道较多。Takao等研究了苯乙烯在Ir和Rh络合物存在下的氧化反应;Collman曾报道环己烯在Vaska络合物[IrX(CO)(PPh_3)_2]催化下氧化成环己酮和环已烯氧化物。本文采用Cotton合成的簇合物[W_3O_2(CH_3CO_2)_6(H_2O)_3]Br_2·     

Oxidations by a H2O2-VO3 −-pyrazine-2-carboxylic acid reagent

Alkanes (cyclohexane, hexane, heptane isomers) are effectively oxidized in CH₃CN at 20–70°C by hydrogen peroxide when catalyzed by a Bu₄NVO₃-pyrazine-2-carboxylic acid system. Alkyl hydroperoxide is the main product; an alcohol and a ketone or an aldehyde are also formed. Under these conditions benzene is oxidized to give phenol, while alkyl benzenes yield oxygenation products both of the ring and the side chain. It has been assumed that the interaction of H₂O₂ with VO₃ ^– gives rise to generation of HO radicals and other radical-like vanadium containing species that abstract a hydrogen atom from an alkane, RH. The radical R^. formed reacts with O₂ to produce ROO^. which is then transformed to alkyl hydroperoxide.Presented at the VIII International Symposium on Homogeneous Catalysis (Amsterdam, 1992).Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 64–68, January, 1993.     

Aerobic alcohol oxidation catalyzed by a new, oxygen-bridged heterometallic compound [PPh4][Ru(N)Me2(μ2-O)2Pd((−)-sparteine)]

The reaction between the new hydroxy compound [PPh₄][Ru(N)(OH)₂Me₂] and Pd(OSiMe₃)₂((−)-sparteine) produces (Me₃Si)₂O, H₂O and a new heterobimetallic compound [PPh₄][Ru(N)Me₂(μ₂-O)₂Pd((−)-sparteine)] in good yield. The Ru/Pd bimetallic compound catalyzes the oxidation of aryl and allyl alcohols to the corresponding carbonyl compound in air and the rearrangement of allylic alcohols unsaturated aldehydes. It also oxidizes PPh₃ to O-PPh₃ under O₂.     

Oxidation of some catecholamines by sodium N-chloro-p-toluenesulfonamide in acid medium: A kinetic and mechanistic approach

The kinetics of the oxidation of five catecholamines viz., dopamine (A), L-dopa (B), methyldopa (C), epinephrine (D) and norepinephrine (E) by sodium N-chloro-p-toluenesulfonamide or chloramine-T (CAT) in presence of HClO₄ was studied at 30±0.1 °C. The five reactions followed identical kinetics with a first-order dependence on [CAT] _o , fractional-order in [substrate] _o , and inverse fractional-order in [H⁺]. Under comparable experimental conditions, the rate of oxidation of catecholamines increases in the order D>E>A>B>C. The variation of ionic strength of the medium and the addition of p-toluenesulfonamide or halide ions had no significant effect on the reaction rate. The rate increased with decreasing dielectric constant of the medium. The solvent isotope effect was studied using D₂O. A Michaelis-Menten type mechanism has been suggested to explain the results. Equilibrium and decomposition constants for CAT-catecholamine complexes have been evaluated. CH₃C₆H₄SO₂NHCl of the oxidant has been postulated as the reactive oxidizing species and oxidation products were identified. An isokinetic relationship is observed with β=361 K, indicating that enthalpy factors control the reaction rate. The mechanism proposed and the derived rate law are consistent with the observed kinetics.     

Direct anodic oxidation ofp-methoxytoluene in methanol. The effect of electrolysis conditions

The effect of anions of the supporting electrolyte (F^–, dialkylphosphate, TsO^–, and BF ₄ ^– and other electrolysis conditions (anode material, temperature, substrate concentration) on the selectivity of the direct anodic oxidation ofp-methoxytoluene in methanol into 4-methoxybenzaldehyde dimethylacetal was studied. The highest selectivity was obtained in the presence of fluoride anion.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 524–527, March, 1995.This work was financially supported by the Ministry of Science, High School and Technical Policy of the Russian Federation within the scope of the State scientific-technical program Ecologically harmless processes of chemistry and chemical technology (project No. 1.140 Low-tonnage chemical products) and by the International Science Foundation (Grant Ch-2-1246-0923).     

BEHAVIOR OF SUPPORTED NANO-COPPER CATALYST IN CO OXIDATION

IntroductionNanomaterialisanewkindofmaterialwithparticlesizebetWeenIurnand100urn.Becauseofthesmallparticlesizeandthelargespecificsufficearea,nanomaterialpossessesmanyparticularproperties,suchashighersufficeenergyandhighersurfaceactivity.t.[l]Thehigheracti…