Highly efficient selective oxidation of alcohols to carbonyl compounds catalyzed by ruthenium (III) meso-tetraphenylporphyrin chloride in the presence of molecular oxygen.

Efficient selective oxidation of alcohols to carbonyl compounds by molecular oxygen with isobutyraldehyde as oxygen acceptor in the presence of metalloporphyrins has been reported. Ruthenium (III) meso-tetraphenylporphyrin chloride (Ru(TPP)Cl) showed excellent activity and selectivity for oxidation of various alcohols under mild conditions. Moreover, different factors influencing alcohols oxidation, for example, catalyst, solvent, temperature, and oxidant, have been investigated. In large-scale oxidation of benzyl alcohol, the isolated yield of benzaldehyde of 89% was observed.

[The surface adsorption and selective catalytic reaction of NO on Cu-ZSM-5 using in situ DRIFTS].

The prepared Cu-ZSM-5 catalyst presents higher activity at low temperature during the selective catalytic reduction (SCR) of NO, and the conversion from NO to N2 is 70.6% at 613 K. The in situ diffuse reflectance FTIR spectroscopy (in situ DRIFTS) is an important method for studying surface adsorption of catalyst and mechanism of catalytic reaction, and was used to study the surface adsorbed species and the selective catalytic reduction reaction of NO on Cu-ZSM-5 catalyst in the presence of propene as reductant, with excess O2 and at 298-773 K. Based on the in-situ DRIFTS, a reaction mechanism is proposed that on Cu-ZSM-5, NO is first transformed to a series of NO(x) surface adsorbates, then these species react with the activating species of propene (C(x)H(y) or C(x)H(y)O(x)) to form organo-intermediates, including a process from organo-NH to organo-CN again to organo-NO(x) (organo-nitro or organo-nitrito), and finally these key intermediates react to form nitrogen. The role of Cu is to promote NO(x) content. Propene is easily activated on Cu-ZSM-5 with oxygen, and furthermore, the presence of oxygen is necessary to form organo-NO(x) intermediates.

[In situ diffuse reflectance FTIR spectroscopy characterization of titanium silicalite-1 catalytic oxidization of styrene].

The Stability of framework of titanium silicalite-1 (TS-1) was investigated by high temperature diffuse reflectance FT-IR spectroscopy (DRIFTS), and the results showed that the 960 cm(-1) peak belonging to Ti-framework was stabilized at 673 K, but the two peaks belonging to framework shifted to lower frequencies by about 13 cm(-1) at 673 K. The effect on the framework after H2O2 adsorption was discussed. The results showed that the 960 cm(-1) peak lowered and shifted to high frequencies by about 11 cm(-1), but it recovered with vacuum or heating up. It was suggested that the 960 cm(-1) peak characterizes Ti==O, and this explained why the 960 cm(-1) peak shifted to high frequencies well. TS-1 catalytic oxidization of styrene was investigated by in situ DRIFTS. The reaction process was detected and phenyl aldehyde was the main product. Based on in situ analysis, it was proposed that H2O2 was adsorbed on Ti in framework of TS-1 to form active center.

Selective oxidation of sulfides to sulfoxides catalyzed by ruthenium (III) meso-tetraphenylporphyrin chloride in the presence of molecular oxygen.

Highly efficient selective oxidation of sulfides to sulfoxides by molecular oxygen catalyzed by ruthenium (III) meso-tetraphenylporphyrin chloride (Ru(TPP)Cl) with isobutyraldehyde as oxygen acceptor has been reported. In large-scale experiment of thioanisole oxidation, the isolated yield of sulfoxide of 92% was obtained and the turnover number reached up to 92,000.

[In situ diffuse reflectance FTIR spectroscopy study of the selective catalytic reduction reaction of NO over Ag/SAPO-34 catalysis].

An in situ diffuse reflectance FTIR spectroscopy (DRIFTS) study of the selective catalytic reduction (SCR) of NO with propene in the presence of excess O2 was carried out over Ag/SAPO-34 catalyst. The SCR reaction was investigated at temperatures from 573 to 773 K, and the role of oxygen in the NO reduction process was determined by comparing experiments using an initial reaction mixture containing oxygen and without oxygen. The results show that both NO and propene are easily activated in oxygen. Furthermore, the presence of oxygen is necessary to form organo-NOx adsorbed species. Based on these experiments, a reaction mechanism is proposed that NO, propene and oxygen react to form organo-nitro and organo-nitrito adsorbed species as key intermediates, and then these intermediates decompose to nitrogen.

[The study of adsorption properties of SAPO-34 molecular sieve by in situ DRIFTS].

The adsorption of H2O, NH3 and NO in molecular sieve SAPO-34 was studied by in situ DRIFTS at temperatures from 298 K to 773 K. The results show that the phenomenon of adsorption is reversible for H2O, but not for NH3 and NO. The water in SAPO 34 is absolutely deadsorbed at 623 K and the bridged Si-OH-Al group is observed at 3,625-3,600 cm-1. It is found that SAPO-34 displays good adsorption-catalysis activity for NH3 and NO. After adsorbing NH3, the bridged hydroxyls disappear, but three peaks appear at 3,135, 3,032 and 1,399 cm-1 at 423 K, and reach their climax at 673 K. The height of the peaks are 3.9, 1.7 and 6.7 times as much as SAPO-34 framework peak's, respectively. A strong and sharp peak is also observed at 1,364 cm-1 after NO adsorption at room temperature, and it exhibit approximately the same intensity with the framework peak. Analysis of these peaks indicate that there could produce new species NO3-.