Reduction property and catalytic activity of Ce1-XNiXO2 mixed oxide catalysts for CH4 oxidation

Ce1-XNiXO2 oxides with X varying from 0.05 to 0.5 were prepared by different methods and characterized by XRD and TPR techniques. Ce(0.7)Mi(0.3)O(2) sample prepared by sol-gel method shows the highest reducibility and the highest catalytic activity for methane combustion. Three kinds of Ni phases co-exist in the Ce1-XNiXO2 catalysts prepared by sol-gel method: (i) aggregated NiO on the support CeO2, (ii) highly dispersed NiO with strong interaction with CeO2 and (iii) Ni atoms incorporated into CeO2 lattice. The distribution of different Ni species strongly depends on the preparation methods. The highly dispersed NiO shows the highest activity for methane combustion. The NiO aggregated on the support CeO2 shows lower catalytic activity for methane combustion, while the least catalytic activity is found for the Ni species incorporated into CeO2. Any oxygen vacancy formed in CeO2 lattice due to the incorporating of Ni atoms adsorbs and activates the molecular oxygen to form active oxygen species. So the highest catalytic activity for methane combustion on Ce0.7Ni0.3O2 catalyst is attributed not only to the highly dispersed Ni species but also to the more active oxygen species formed. (C) 2002 Elsevier Science B.V. All rights reserved.

Post-steam-treatment of Mo/HZSM-5 catalysts: An alternative and effective approach for enhancing their catalytic performances of methane dehydroaromatization

Post-steam-treatment is a facile and effective method for improving the catalytic performances of Mo/HZSM-5 catalysts in methane dehydroaromatization under nonoxidative conditions. The treatment can enhance the stability of the catalyst and also give a higher methane conversion and a higher yield of light aromatics, as well as a decrease in the formation rate of carbonaceous deposits. (27)Al, (29)Si, and (1)H multinuclear magic angle spinning nuclear magnetic resonance, X-ray photoelectron spectroscopy, X-ray diffraction, X-ray fluorescence spectroscopy, and thermogravimetric analysis measurements as well as catalytic reaction evaluations were employed to conduct comparative studies on the properties of the catalysts before and after the post-steam-treatment. The results revealed that the number of free Bronsted acid sites per unit cell decreased, while more Mo species migrated into the HZSM-5 channels for the 6Mo/HZSM-5 catalysts after the post-steam-treatment. In addition, the average pore diameter was also larger for the post-steam-treated catalysts, and this was advantageous for mass transport of the reaction products. However, a severe post-steam-treatment, i.e., with longer treating time, of the 6Mo/HZSM-5 catalyst will lead to the formation of the Al(2)(MoO(4))(3) phases, which is detrimental to the reaction.

Epoxidation of propylene over Ag-CuCl catalysts using air as the oxidant

Ag-CuCl catalysts were found to be active and selective for the epoxidation of propylene using air as the oxidant. Ag catalyst gives a propylene conversion of 31.6%, with a propylene oxide (PO) selectivity of 0.42% at a reaction temperature of 350 degreesC after 220 min of reaction. Addition of CuCl significantly improves the selectivity to PO, and suppresses the conversion of propylene. The Ag-CuCl (1/0.6) catalyst gives propylene conversion of about 3% and a PO selectivity of about 30% at a reaction temperature of 350 degreesC after 500 min of reaction. The activity of the Ag-CuCl catalyst increases with the reaction time and the selectivity to PO is very stable for this catalyst. It is found that AgCl and CuO phases formed during the catalyst preparation are beneficial to the epoxidation of propylene.

In situ IR spectroscopic studies on molybdenum nitride catalysts: active sites and surface reactions

Recent IR spectroscopic studies on the surface properties of fresh Mo2N/gamma-Al2O3 catalyst are presented in this paper. The surface sites of fresh Mo2N/gamma-Al2O3, both Modelta+ (0<δ<2) and N sites, are probed by CO adsorption. Two characteristic IR bands were observed at 2045 and 2200 cm(-1), due to linearly adsorbed CO on Mo and N sites, respectively. The surface N sites are highly reactive and can react with adsorbed CO to form NCO species. Unlike adsorbed CO on reduced passivated one, the adsorbed CO on fresh Mo2N/gamma-Al2O3 behaves similarly to that of group VIII metals, suggesting that fresh nitride resembles noble metals. It is found that the surface of Mo nitrides slowly transformed into sulfide under hydrotreating conditions, which could be the main reason for the activity drop of molybdenum nitride catalysts in the presence of sulfur-containing species. Some surface reactions, such as selective hydrogenation of 1,3-butadiene, isomerization of 1-butene, and hydrodesulfurization of thiophene, were studied on both fresh and reduced passivated Mo2N/gammaAl(2)O(3) catalysts using IR spectroscopy. The mechanisms of these reactions are proposed. The adsorption and reaction behaviors of these molecules on fresh molybdenum nitride also resemble those on noble metals, manifesting the unique properties of fresh molybdenum nitride catalysts. Mo and N sites are found to play different roles in the adsorption and catalytic reactions on the fresh Mo2N/gammaAl(2)O(3) catalyst. Generally, Mo sites are the main active sites for the adsorption and reactions of adsorbates; N sites are not directly involved in catalytic reactions but they modify the electronic properties of Mo sites.

Microcalorimetric and IR spectroscopic studies of CO adsorption on molybdenum nitride catalysts

The adsorption of CO on both nitrided and reduced passivated Mo(2)N catalysts in either alumina supported or unsupported forms was studied by adsorption microcalorimetry and infrared (IR) spectroscopy. The CO is adsorbed on nitrided Mo(2)N catalysts on three different surface sites: 4-fold vacancies, Mo(delta+) ( 0 < delta < 2) and N sites, with differential heats of CO adsorption decreasing in the same order. The presence of the alumina-support affects the energetic distribution of the adsorption sites on the nitrided Mo(2)N, i.e. weakens the CO adsorption strength on the different sites and changes the fraction of sites adsorbing CO in a specific form, revealing that the alumina supported Mo(2)N phase shows lower electron density than pure Mo(2)N. On reduced passivated Mo(2)N catalysts the CO was found to adsorb mainly on Mo(4+) sites, although some slightly different surface Mo(delta+) d (0 < delta < 2) sites are also detected. The nature, density and distribution of surface sites of reduced passivated Mo(2)N/gAl(2)O(3) were similar to those on reduced MoO(3)/gamma-Al(2)O(3).

Kinetics of acetic acid esterification with 2-ethoxyethanol over an Al-pillared clay catalyst

The Al-pillared clay catalyst obtained by exposing activated clay powder to sulfuric acid and aluminium salts and calcining in air at 373-673 K, was found to be highly active for the title reaction. The results indicated that pillared layer clay of the mixed oxide has been employed as parent catalysts for their definite structure and special properties which can be modified by the substitution of L and B acid sites cations. Solid acid catalyst of Supported aluminium was found to be highly active and selective at the 373-473 K temperature range for heterogeneous esterification. The activity is mainly attributed to the Lewis (and a considerably small number of Bronsted) acid sites whose number and strength increased due to pillaring. The water produced in the esterification can be induced by Al3+, which makes the catalyst surface to form strong B acid. Their acidities are obtained by pH measurement. If only B acid sites are > 70%, and pH < 1 in the 2-ethoxyethanol, there exists an activity of esterification. The used catalyst gave identical results with that of the fresh one. X-ray diffraction spectra show that the composition and active phase of the used catalysts are the same as the fresh ones. The kinetic study of the reaction was carried out by an integral method of analysis. The kinetic equation of surface esterification is y = 2.36x - 0.98.

Mn-containing AlPO-11 and SAPO-11 catalysts for simultaneous isomerization and dehydrogenation of n-butane

MnAPO-11 and MnAPSO-11 were synthesized hydrothermally, and supported Mn-AlPO-11 and Mn-SAPO-11 were also prepared for comparison. Characterization results showed that there were differences in acidity and reducibility caused by the different incorporation methods of manganese. The manganese species in the samples also weakened the metallic properties of the palladium particles when the latter was added into the catalysts. Catalytic testing results for dehydroisomerization of n-butane indicated that incorporation of manganese increased the selectivity toward isomerization products. The highest isobutene selectivity (34.86%) could be obtained over a Pd/MnAPO-11 catalyst. When a combined catalyst system containing Pd/SAPO-11 and MnAPSO-11 was used in a single bed of two layers, the isobutene selectivity could be greatly improved, as compared to the single catalyst alone.

Shape selectivity in methane dehydroaromatization over Mo/MCM-22 catalysts during a lifetime experiment

Dehydroaromatization of CH4 with 2% CO2 on 6Mo/MCM-22 in a 100-h lifetime test was carried out at 993 K, atmospheric pressure and 1500 mL/gh. The duration of the lifetime test can be divided into an induction stage, stable stage and deactivation stage on the basis of the selectivities of hydrocarbons and coke. The characteristics of deposited coke with different time onstream were studied using TPO and TG techniques. There were two peaks corresponding to two kinds of coke recorded in TPO profiles, and the oxidation temperature of coke shifted to higher values with less hydrogen content with the increase of coke deposits. BET and Benzene-TPD techniques were employed to study the variation of specific surface area of the external and micropore surface versus time onstream. With the accumulation of coke deposits, although the pores became partially blocked and the internal surface decreased, methane could still enter the channel and was converted to benzene with shape selectivity until a critical value of coke deposition was reached.

Performance of palladium-containing supported catalysts in the oxidation of 1-butene

Performance of palladium-containing supported catalysts in the oxidation of 1-butene was investigated in a fixed-bed flow microreactor. The Pd-Fe-HCl/Ti-Al catalyst is the best among the five Pd-Fe-HCl/X (A = SiO2, gamma-Al2O3, Al-Ti, TiO2, MCM-22) catalysts for the oxidation of I-butene to butanone. It is interesting that high propionic acid selectivity can be obtained when V and H2SO4 are added to the palladium-containing supported catalysts.

A Mossbauer study of In-Fe2O3/HZSM-5 catalysts for the selective catalytic reduction of NO by methane

The selective catalytic reduction of NO by CH4 was compared over In-Fe2O3/HZSM-5 catalysts prepared by impregnation and co-impregnation methods. It was found that the catalyst preparation method greatly affected the catalyst activity. The impregnated catalyst was very active, but the co-impregnated one showed poor activity. The In Fe2O3/HZSM-5 catalysts were investigated by Mossbauer spectroscopy. The results showed that indium cations entered into the iron oxide lattice in the co-impregnated catalyst, while the impregnated catalyst exhibited a more stable structure, when both of the catalysts were treated severely in the reaction atmosphere. Characterization by means of combined in situ temperature programmed reduction (TPR)- Mossbauer spectroscopy further revealed that the performances of the two catalysts were different in the TPR processes.

Preparation and characterization of multiwalled carbon nanotube-supported platinum for cathode catalysts of direct methanol fuel cells

Multiwalled carbon nanotube-supported Pt (Pt/MWNT) nanocomposites were prepared by both the aqueous solution reduction of a Pt salt (HCHO reduction) and the reduction of a Pt ion salt in ethylene glycol solution. For comparison, a Pt/XC-72 nanocomposite was also prepared by the EG method. The Pt/MWNT catalyst prepared by the EG method has a high and homogeneous dispersion of spherical Pt metal particles with a narrow particle-size distribution. TEM images show that the Pt particle size is in the range of 2-5 nm with a peak at 2.6 nm, which is consistent with 2.5 nm obtained from the XRD broadening calculation. Surface chemical modifications of MWNTs and water content in EG solvent are found to be the key factors in depositing Pt particles on MWNTs. In the case of the direct methanol fuel cell (DMFC) test, the Pt/MWNT catalyst prepared by EG reduction is slightly superior to the catalyst prepared by aqueous reduction and displays significantly higher performance than the Pt/XC-72 catalyst. These differences in catalytic performance between the MWNT-supported or the carbon black XC-72-supported catalysts are attributed to a greater dispersion of the supported Pt particles when the EG method is used, in contrast to aqueous HCHO reduction and to possible unique structural and higher electrical properties when contrasting MWNTs to carbon black XC-72 as a support.