Direct synthesis of dimethyl carbonate ?from CH3OH AND CO2 by H3PW12O40/CexTi1-xO2 catalyst

Summary Ce_xTi_1-xO₂ and H₃PW₁₂O₄₀/Ce_xTi_1-xO₂ catalysts were prepared using a sol-gel method, and applied to the direct synthesis of dimethyl carbonate from methanol and carbon dioxide. H₃PW₁₂O₄₀/Ce_xTi_1-xO₂ showed a better catalytic performance than the corresponding Ce_xTi_1-xO₂, due to the bifunctional catalysis of Br?nsted acid sites (provided by H₃PW₁₂O₄₀) and base sites (provided by Ce_xTi_1-xO₂). H₃PW₁₂O₄₀/Ce_0.1Ti_0.9O₂ showed the highest catalytic performance among the H₃PW₁₂O₄₀/Ce_xTi_1-xO₂ catalysts.     

A facile synthetic route for the preparation of the Au/Mox/Al2O3 catalysts towards CO oxidation

Summary A new facile single-step synthetic route is reported for the preparation of Au/MO_x/Al₂O₃ catalysts. The preparation method has the merit of facility but leads to not only the simultaneous load of both gold source and MO_x precursor on Al₂O₃ support, but also the formation of Au/MO_x/Al₂O₃ with high gold loading ratio, high dispersion and high activity for CO oxidation.     

Surface of Ru/Fe2O3 catalysts used in water-gas shift reaction studied by auger electron spectrometry

Summary Carbon deposits on the surface ofRu/Fe₂O₃ catalysts used in the water-gas shift reaction have been investigated by Auger Electron Spectrometry. A correlation has been found between the thickness of the carbon deposit and the catalytic activity in WGSR. The carbon deposit covers the metallic active centers and blocks their contact with reagents. The dotting of the iron oxide support with sodium has been found to reduce the amount of carbon deposit. .      

Study of CuO/Ce0.8Zr0.2O2 catalysts for low-temperature CO oxidation

Summary Copper oxide catalysts supported on Ce_0.8Zr_0.2O₂ were prepared via an impregnation method and characterized by XRD and H₂-TPR techniques. The catalytic activity of the samples for low-temperature CO oxidation was investigated by means of a microreactor-GC system. The influence of calcination temperature, calcination time and different CuO content on the catalytic activity was studied. TPR analysis indicated that well-dispersed CuO was responsible for the low-temperature CO oxidation. The results of the investigation showed that the calcination temperature and CuO loadings had larger influence than the calcination time.     

Methanol dehydration to produce dimethyl ether over g-Al2O3

Summary The kinetic data of about 150 points for methanol dehydration were obtained at the temperature of 240~270^oC, the GHSV of 25,000~120,000 (mL/g_cat./h) and under atmospheric pressure. The data were fitted into six plausible equations. The kinetic equation derived from the molecular adsorption of methanol on two sites fit the kinetic data best, however, that from the dissociative adsorption of methanol could not be safely ruled out. The activation energy of 114.7 kJ/mol for methanol dehydration on γ-Al₂O₃ was obtained from the kinetic analysis.     

Carvone epoxidation by system “hydrogen peroxide-[Mn2L2O3][PF6]2 (L = 1,4,7-trimethyl-1,4,7-triazacyclononane)-carboxylic acid”: a combinatorial approach to the process optimization?

Summary Epoxidation of natural terpene (+)-carvone by the system consisting of a catalyst, oxalic acid (co-catalyst) and H₂O₂ (70% aqueous solution; oxidant) was studied and factorial design methods were applied for the optimization of this reaction. A dinuclear manganese(IV) complex [LMn(O)₃MnL](PF₆)₂ (L = 1,4,7-trimethyl-1,4,7-triazacyclononane) was used as a catalyst, and acetonitrile was employed as a solvent. An analysis by methods of the complete 2⁴ factorial design showed that an increase in the catalyst concentration gives a strong positive effect on the carvone conversion and selectivity. Hydrogen peroxide has a smaller positive effect on the conversion, but at high concentration, H₂O₂ leads to some decrease in the selectivity. An increase in the oxalic acid concentration has a beneficial effect on the conversion, but does not affect the selectivity.     

An investigation of the promotional effect of propylene or propane traces on the activity of sulfatedPt/g-Al2O3andPt-Sn/g-Al2O3inCH4combustion

Summary A strong promoting effect of the presence of C₃H₈or C₃H₆was determined for the combustion of CH₄in excess oxygen, over pre-sulfated 1%Pt/g-Al₂O₃and pre-sulfated 1%Pt-2%Sn/g-Al₂O₃catalysts.</o:p>     

Selective catalytic reduction of nitric oxide with propane over Ni-Al2O3: effect of Ni loading

Summary The SCR of NO by propane in excess oxygen was studied on a Ni-Al₂O₃ catalyst prepared by a coprecipitation method. The effect of Ni loading on the catalytic performance was studied and the optimal Ni loading was found to be 4 % (wt.%). Based on characterization results, highly dispersed nickel species in surface aluminate phase was regarded as the active site for NO reduction by C₃H₈ and NiO phase was the active site for C₃H₈ oxidation by oxygen.     

Effect of additive in feedstock on performance of Ag-MoO3/ZrO2 catalyst for propylene epoxidation by molecular oxygen

Summary The performance of the Ag-MoO₃/ZrO₂ catalyst for propylene epoxidation by molecular oxygen is influenced obviously by the composition of feedstock. As an additive in feedstock, the presence of organic chloride, CO₂, NO_x or H₂ at a suitable concentration can improve the catalytic performance of Ag-MoO₃/ZrO₂ catalyst for the propylene epoxidation.      

Oxidative dehydrogenation of crotonaldehyde overK2HPMo12O40catalyst

Summary The oxidative dehydrogenation of crotonaldehyde to furan and maleic anhydride was carried out over K₂HPMo₁₂O₄₀catalyst. A positive effect of water vapor on furan formation is explained by ability of the catalyst to isomerize 2E- to 2Z-crotonaldehyde.</o:p>     

Absolute rate constants for the reactions ofOHradicals withCH3CH2OH, CF2HCH2OHandCF3CH2OH

Summary Pulsed laser photolysis with resonance fluorescence monitoring of OH radicals was applied at T = 300±2 K to obtain the rate constants of k₁= (3.38±0.60)x10^-12, k₂= (2.52±0.44)x10^-13and k₃ = (1.06±0.30)x10^-13cm³molecule^-1s^-1with 2σprecision given for the overall reactions OH + CH₃CH₂OH (1), OH + CF₂HCH₂OH (2) and OH + CF₃CH₂OH (3), respectively. k₂is the first direct kinetic data for the reaction of OH radicals with CF₂HCH₂OH reported in the literature.</o:p>     

Temperature-programmed desorption/pulse surface reaction (tpd/tpsr) studies of CH4, C2H6, C2H4, and CO over a cobalt/MWNTs catalyst

Summary Temperature-programmed desorption (TPD) of CH₄, C₂H₆, C₂H₄, and CO and temperature-programmed pulse surface reactions (TPSR) of CH₄, C₂H₆, C₂H₄, CO, and CO/H₂ over a Co/MWNTs catalyst have been investigated. The TPD results indicated that CH₄ and C₂H₆ mainly exist as physisorbed species on the Co/MWNTs catalyst surface, whilst C₂H₄ and CO exist as both physisorbed and chemisorbed species. The TPSR results indicated that CH₄ and C₂H₆ do not undergo reaction between room temperature and 450^oC. Pulsed C₂H₄ can be transformed into CH₄ at 400 ^oC whilst pulsed CO can be transformed into CO₂ at 100 or 150^oC. In gaseous mixtures of CO and H₂ containing excess CO, the products of pulsed reaction were CH₃CHO and CH₃OH. When the ratio of CO and H₂ was 1:2, pulsed CO and H₂ were transformed into CH₃CHO, CH₃OH and CH₄. In H₂ gas flow, pulsed CO was transformed into a mixture of CH₃CHO and CH₄ between 200 and 250^oC and was transformed into CH₄ only above 250^oC.     

Tmperature programmed techniques study on the nature of the oxidant in/on V2O5catalyst ?

Summary The nature of the oxidising species in/on a vanadium pentoxide (V₂O₅) catalyst has been studied using a combination of transient techniques: (i) Temperature programmed desorption (TPD), (ii) Temperature programmed reduction (TPR), (iii) Temperature programmed oxidation (TPO) and (iv) Temperature programmed reaction (TPRn). Chemisorbed oxygen was found not to exist on a fully oxidised V₂O₅ catalyst by TPD. The TPR in CO over V₂O₅ catalyst gave three peak maxima at 930, 982 and 1043 K, indicating that three types of kinetically different oxygen states exist in/on the catalyst. Reoxidation of the CO reduced V₂O₅ catalyst by N₂O resulted in the quantitative replacement of the lattice oxygen. A further reduction of the N₂O reoxidised catalyst gave a significantly different TPR profile compared to the original material suggesting that a less crystalline material had formed. The presence of phosphorus in (VO)₂P₂O₇ was found to labilise the lattice oxygen.     

Simultaneous propane dehydrogenation andco2hydrogenation overCrOx/SiO2catalyst

Summary Single reverse water-gas shift (RWGS) and dehydrogenation of propane with CO₂(DH-CO₂) reactions in the presence and absence of the CrO_x/SiO₂ catalyst have been studied between 673 and 873 K. It was found that the CrO_x/SiO₂ catalyst is active both in the dehydrogenation of propane and in the RWGS reactions. The obtained results suggest that the dehydrogenation of propane to propene in the presence of CO₂on CrO_x/SiO₂can be facilitated by the RWGS reaction.</o:p>     

Phase states in the Bi4Ti3O12-BiFeO3 section in the Bi2O3-TiO2-Fe2O3 system

Specific features of the thermal behavior of Bi _{m + 1}Fe _m−3Ti₃O_{3m + 3} layered perovskite-like compounds (where m takes integer and some fractional values between 3 and 9) were considered, and the temperature limits of stability of these compounds were determined. The phase diagram of the Bi₄Ti₃O₁₂-BiFeO₃ section through the Bi₂O₃-TiO₂-Fe₂O₃ system was constructed.     

TPR studies on steam reforming of 2-propanol on Rh/Al2O3, Ru/Al2O3 and Pd/Al2O3

Reaction pathways for steam reforming of 2-propanol (isopropyl alcohol, IPA) on Rh/Al₂O₃, Ru/Al₂O₃ and Pd/Al₂O₃ have been studied by temperature-programmed reactions (TPRs) of IPA and acetone in the presence of steam. The results of TPRs suggest that that of IPA on Rh/Al₂O₃ and Ru/Al₂O₃ proceeds via acetone, while the steam reforming of IPA on Pd/Al₂O₃ takes place via propene from acetone. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermostability of Nano-TiO2 and its photocatalytic activity

Summary Thermostability of P25 nanoparticle was carried out by ascending thermal annealing. The growth of particle was observed and the activation energy of phase transition was calculated. The photocatalytic reactivity was measured in terms of the degradation rate of methylene blue. Results indicated that the specific surface area and the aggregation of TiO₂ are much important factors than the crystal phase on the photo-decoloration reaction.      

Formation of β- and β″-Al2O3 by the solid state reaction between NaAlO2 and γ-Al2O3

The solid state reaction of NaAlO₂ with γ-Al₂O₃ was investigated kinetically. Powdered compacts with various compositions (Al₂O₃/NaAlO₂ = 1–5) were fired at 700–1200°C for 1–768 hr. The amounts of the reaction product were determined by peak heights of X-ray diffraction patterns. β″-Al₂O₃ was formed predominantly from the sample with Al₂O₃/NaAlO₂ = 2. The firing time for the β″-Al₂O₃ formation was shortened as the firing temperature was raised, and the activation energy, E_a, for formation was about 130–135 kcal/mole. The sample of Al₂O₃/NaAlO₂ = 5 formed m-Al₂O₃ with the mullite structure and was observed to transform gradually to β-Al₂O₃. E_a for the m-Al₂O₃ formation and for the transition were about 55–60 and 40 kcal/mole, respectively, which resulted in E_a of about 95–100 kcal/mole for the β-Al₂O₃ formation. The mechanism of the m-Al₂O₃ formation is discussed briefly.     

Photocatalytic oxidation of gaseous trichloroethylene by UV/TiO2 process

Summary The objective of this study was to investigate the reaction behavior of the photocatalytic oxidation of gaseous trichloroethylene (TCE) using titanium dioxide at room temperature. The experiments were carried out under various humidity levels and oxygen contents of carrier gas in an annular photoreactor. Experimental results indicated that the factors affecting the photocatalysis of TCE by UV/TiO₂ process are carrier gases and humidity. It was found that increasing the relative humidity in inlet gas flow under low humidity could improve the decomposition of trichloroethylene and the mineralization of organic intermediates at an irradiation UV light intensity of 2.82 W m^-2 by UV/TiO₂ process. The photocatalytic kinetics of gaseous trichloroethylene can be described by the Langmuir-Hinshelwood rate equation.     

Tunneled Intergrowth Structures in the Ga2O3–In2O3–SnO2 System

The structures of several Ga₂O₃–In₂O₃–SnO₂ phases were investigated using high-resolution electron microscopy, X-ray diffraction, and Rietveld analysis of time-of-flight neutron diffraction data. The phases, expressed as Ga_4−4xIn_4xSn_n−4O_2n−2 (n=6 and 7–17, odd), are intergrowths between the β-gallia structure of (Ga,In)₂O₃ and the rutile structure of SnO₂. Samples prepared with n≥9 crystallize in C2/m and are isostructural with intergrowths in the Ga₂O₃–TiO₂ system. Samples prepared with n=6 and n=7 are members of an alternative intergrowth series that crystallizes in P2/m. Both intergrowth series are similar in that their members possess 1-D tunnels along the b axis. The difference between the two series is described in terms of different crystallographic shear plane operations (CSP) on the parent rutile structure.