Preparation and Characterization of SnO2-Based Composite Metal Oxides: Active and Thermally Stable Catalysts for CH4 Oxidation

A series of SnO₂-based catalysts modified by Fe, Cr and Mn were prepared by the combination of redox reaction and co-precipitation methods, and applied to catalytic CH₄ oxidation. The modified catalysts show generally higher activity than the unmodified SnO₂. XRD analysis indicates that Fe, Cr and Mn cations could be incorporated into the lattice of rutile SnO₂ (cassiterite) to form solid solution structure. As a result, more reducible and active oxygen species was formed in the samples, as substantiated by the H₂-TPR results. Moreover, the specific surface areas of the modified catalysts are much higher than that of pure SnO₂ and their crystallite sizes are smaller, indicating they are more resistant to thermal sintering. Indeed, the high specific surface areas and the formation of more active oxygen species in the modified samples are believed to be the predominant reasons leading to their enhanced CH₄ oxidation activity. Eventually, it is noted that SnCrO displays not only remarkable CH₄ oxidation activity, but also potent resistance to SO₂ and water deactivation, which makes it a promising catalyst with the potential to be applied in some real CH₄ oxidation processes.     

Selective Conversion of Methane to C2 Hydrocarbons Using Carbon Dioxide over Mn-SrCO3 Catalysts

The combination of Mn with SrCO₃ leads to effective catalysts for the selective conversion of CH₄ to C₂ hydrocarbons using CO₂ as an oxidant; C₂ selectivities approach 88 and 79.1% with a C₂ yield of 4.3 and 4.5% over catalysts with an Mn/Sr ratio of 0.1 and 0.2, respectively. It is assumed that the Mn³⁺/Mn²⁺ couple formed in the reaction plays an important role in the activation of CO₂ and CH₄.     

Effect of Mn content on physical properties of CeOx–MnOy support and BaO–CeOx–MnOy catalysts for direct NO decomposition

A series of manganese–cerium mixed oxides were prepared by a glycothermal method, and the NO decomposition activities of the Ba-loaded Ce–Mn oxides were examined. Among the catalysts examined, the highest NO conversion was obtained on the BaO/Ce–Mn oxide catalyst with a Mn/(Ce+Mn) ratio of 0.25. The X-ray diffraction and Raman analyses indicated the formation of Ce–Mn oxide solid solutions with a cubic fluorite structure. The electron spin resonance analysis indicated the presence of paramagnetic Mn²⁺ species in the composite catalysts. Incorporation of Mn²⁺ in the fluorite structure of CeO₂ causes an increase in the concentration of oxygen vacancies, which play an important role in the NO decomposition activity of the catalysts. The catalysts were also characterized by X-ray photoelectron spectroscopy and temperature-programmed reduction techniques. Based on the results obtained, the relationship between the physical properties of the catalysts and their NO decomposition activities was discussed.     

Investigating the effect of metal oxide additives on the properties of Cu/ZnO/Al2O3 catalysts in methanol synthesis from syngas using factorial experimental design

The Cu/ZnO/Al₂O₃ catalysts, prepared by co-precipitation method, have been modified by adding small amount of Mn, Mg, Zr, Cr, Ba, W and Ce oxides using design of experiments (1/16 full factorial design). The structure and morphology of catalysts were studied by X-ray diffraction (XRD) and BET. Performance of the prepared catalysts for CO/CO₂ hydrogenation to methanol was evaluated by using a stainless steel fixed-bed reactor at 5 MPa and 513 K. The oxide additives were found to influence the catalytic activity, dispersion of Cu, Cu crystallite size, surface composition of catalyst and stability of catalysts during their operations. The results showed that the Mn and Zr promoted catalysts have high performance for methanol synthesis from syngas.     

High-temperature in situ FTIR spectroscopy study of LaOF and BaF2/LaOF catalysts for methane oxidative coupling

In situ FTIR spectroscopy was used to characterize the oxygen adspecies and its reactivity with CH₄ over LaOF and 15 mol% BaF₂/LaOF catalysts at OCM temperature (750-800°C). It was found that gas-phase oxygen was activated on the surface of LaOF and 15 mol% BaF₂/LaOF, which had been pretreated under vacuum at 750 or 800°C, forming O ₂ ^- species at high temperature (750-800°C). At 750°C, the adsorbed O ₂ ^- species can react with pure CH₄ accompanied by formation of gas-phase C₂H₄ and CO₂, and there is a good correlation between the rate of disappearance of surface O₂and the rate of formation of gas-phase C₂H₄. The O ₂ ^- species was also observed over the catalysts under working condition, and it reacted with CH₄ in a manner that was consistent with its role in a catalytic cycle. These results suggest that O ₂ ^- may be the active oxygen species for OCM reaction over these catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

A contrastive study of the introduction of cobalt as a modifier for active components and supports of catalysts for NH3-SCR

Three catalysts Mn/Ce–ZrO_X, Mn–Co/Ce–ZrO_X and Mn/Co–Ce–ZrO_X were used for low-temperature NH₃-SCR of NO. XRD, TPR and XPS were performed to characterize the physicochemical property of the catalysts. Experimental results showed that Mn/Co–Ce–ZrO_X had a higher dispersion of manganese oxides, a better redox property, more surface acid sites and more surface adsorbed oxygen species and Mn⁴⁺ ion. These facts caused a better low-temperature activity for Mn/Co–Ce–ZrO_X which was 99.0% at 180 °C. Furthermore, Mn/Co–Ce–ZrO_X showed the best resistance to SO₂ and H₂O which mainly because the introduction of cobalt inhibited the formation of sulfate salts and hydroxyls on the surface of Mn/Co–Ce–ZrO_X.     

Characterization of Ti/Si binary oxides prepared by the sol-gel method and their photocatalytic properties: The hydrogenation and hydrogenolysis of CH3CCH with H2O

Titanium-silicon (Ti/Si) binary oxides having different Ti content were prepared by the sol-gel method and utilized as photocatalysts for the hydrogenation and hydrogenolysis of CH₂CCH with H₂O. The photocatalytic reactivity and selectivity of these catalysts were investigated as a function of the Ti content and it was found that the hydrogenolysis reaction (C₂H₆ formation) was predominant in regions of low Ti content, while the hydrogenation reaction (C₃H₆ formation) proceeded in regions of high Ti content. The in situ photoluminescence, diffuse reflectance absorption, FT-IR, XAFS (XANES and EXAFS), and XPS spectroscopic investigations of these Ti/Si binary oxides indicated that the titanium oxide species are highly dispersed in the SiO₂ matrices and exist in a tetrahedral coordination exhibiting a characteristic photoluminescence spectrum. The charge transfer excited state of the tetrahedrally coordinated titanium oxide species plays a significant role in the efficient photoreaction with a high selectivity for the hydrogenolysis of CH₃CCH to produces mainly C₂H₆ and CH₄, while the catalysts involving the aggregated octahedrally coordinated titanium oxide species show a high selectivity for the hydrogenation of CH₃CCH to produce C₃H₆, being similar to reactions of the powdered TiO₂ catalysts. The good parallel relationship between the yield of the photoluminescence and the specific photocatalytic reactivity of the Ti/Si binary oxides as a function of the Ti content clearly indicates that the high photocatalytic reactivity of the Ti/Si binary oxides having low Ti content is associated with the high reactivity of the charge transfer excited state of the isolated titanium oxide species in tetrahedral coordination, [Ti³⁺-O⁻]*.     

Studies on cobalt catalyst supported on silica with different pore size for Fischer–Tropsch synthesis

The adsorption and surface reactions of acetonitrile and acetonitrile-oxygen gas mixture were studied on TiO₂-supported Au catalysts at 300–673 K. FTIR spectra show different kinds of molecularly adsorbed CH₃CN:acetonitrile can be bonded to weak Lewis acid sites (2295 cm⁻¹), to strong Lewis acid sites (2337 cm⁻¹) of titania; it can be coordinated linearly through the lone electron pair of the N atom on Au sites and η² (C,N) CH₃CN species can be formed on Au particles. CH₃CN dissociates on Au sites, the resulting CN_(a) can be oxidized in small extent by lattice oxygen and in a greater extent by gaseous oxygen into NCO surface species. The formation of other products (CH₃NH₂, H₂, CO₂, CH₄, C₂H₄ and CO) was demonstrated and discussed.     

Reduction of lean NOx by ethanol over Ag/Al2O3 catalysts in the presence of H2O and SO2

The reduction of lean NOx using ethanol in simulated diesel engine exhaust was carried out over Ag/Al₂O₃ catalysts in the presence of H₂O and SO₂. The Ag/Al₂O₃ catalysts are highly active for the reduction of lean NOx by ethanol but the reaction is accompanied by side reactions to form CH₃CHO, CO along with small amounts of hydrocarbons (C₃H₆, C₂H₄, C₂H₂ and CH₄) and nitrogen compounds such as NH₃ and N₂O. The presence of H₂O enhances the NOx reduction while SO₂ suppresses the reduction. The presence of SO₂ along with H₂O suppresses the formation of acetaldehyde and NH₃. By infrared spectroscopy, it was revealed that the reactivity of NCO species formed in the course of the reaction was greatly enhanced in the presence of H₂O. The NCO species readily reacts with NO in the presence of O₂ and H₂O at room temperature, being converted to N₂ and CO₂ (CO). Addition of SO₂ suppresses the formation of NCO species and lowers the reactivity of the NCO species. However, the reduction of NOx is still kept at high conversion levels in the presence of H₂O and SO₂ over the present catalysts. About 80% of NOx in the simulated diesel engine exhaust was removed at 743 K. This revised version was published online in July 2006 with corrections to the Cover Date.     

Homogeneous reduction of nitrobenzene to aniline under CO/H2O, catalyzed by cis-[Rh(CO)2(amine)2]PF6. The role of the amine effect

The CO₂ reforming of methane over reduced NiO/MgO solid solution catalysts was studied at 800°C by a novel transient method, which couples a broadened pulse of CH₄/CO₂ with a step change to the carrier gas and/or with a sharp isotopic pulse of either ¹⁸O₄, CO¹⁸ ₂ or ¹³CO¹⁶ ₂. The response curves indicated that two kinds of oxygen were formed over the catalysts during reaction: adsorbed oxygen which reacts fast with C species and lattice oxygen which reacts more slowly with C species. One concludes that a redox cycle of lattice oxygen formation through the oxidation of Ni and its reaction with C species takes place on the catalyst surface. This revised version was published online in August 2006 with corrections to the Cover Date.     

Methanol synthesis pathway over Cu/ZrO2 catalysts: a time‐resolved DRIFT 13C‐labelling experiment

X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) have been used to characterize a series of Cu/Ce/Al₂O₃ catalysts. Catalysts were prepared by incipient wetness impregnation using metal nitrate and alkoxide precursors. Catalyst loadings were held constant at 12 wt% CuO and 5.1 wt% CeO₂. Mixed oxide catalysts were prepared by impregnation of cerium first, followed by copper. The information obtained from surface and bulk characterization has been correlated with CO and CH₄ oxidation activity of the catalysts. Cu/Al₂O₃ catalysts prepared using Cu(II) nitrate (CuN) and Cu(II) ethoxide (CuA) precursors consist of a mixture of copper surface phase and crystalline CuO. The CuA catalyst shows higher dispersion, less crystalline CuO phase, and lower oxidation activity for CO and CH₄ than the CuN catalyst. For Cu/Ce/Al₂O₃ catalysts, Ce has little effect on the dispersion and crystallinity of the copper species. However, Cu impregnation decreases the Ce dispersion and increases the amount of crystalline CeO₂ present in the catalysts, particularly in Ce modified alumina prepared using cerium alkoxide precursor (CeA). Cerium addition dramatically increases the CO oxidation activity, however, it has little effect on CH₄ oxidation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of CeO2 and La2O3 on the Activity of CeO2−La2O3/Al2O3-Supported Pd Catalysts for Steam Reforming of Methane

The effect of the addition of CeO₂ or La₂O₃ on the surface properties and catalytic behaviors of Al₂O₃-supported Pd catalysts was studied in the steam reforming of methane. The FTIR spectroscopy of adsorbed CO and the Pd dispersion suggest the partial coverage of Pd⁰ by ceria or lanthana species. This could lead to the formation of an adduct MPd _x O (M = Ce or La) at the surface of the metal crystallites. The addition of ceria or lanthana resulted in an increase of the turnover rate and specific rate for steam reforming of methane. One possible explanation if that the Pd⁰*Pd^δ+O–M interfacial species (M = Ce or La) are oxidized by H₂O or CO₂, promoting the O* transfer to the metal surface. This could facilitate the removal of C* species from the metal surface, resulting in the increase of specific reaction rate and increase of the accessibility of CH₄ to metal active sites.     

Propane Oxidative Dehydrogenation over Metal Pyrophosphates Catalysts

Metal pyrophosphates (M–P₂O₇, where M is V, Zr, Cr, Mg, Mn, Ni or Ce) have been found to catalyze the oxidative dehydrogenation of propane to propene. The reaction was conducted at 1 atm, 450–550°C and feed flowrate of 75 cm³/min (20 cm³/min propane, 5 cm³/min oxygen and the balance is helium). All catalysts showed increase in degrees of conversion and decrease in olefins selectivity with increase in reaction temperature. At 550°C, MnP₂O₇ exhibited the highest activity (40.7% conversion) and total olefins (C₃H₆ and C₂H₄) yield (29.3%). The other catalysts, indicated by their respective metals, may be ranked (based on olefins yield) as V (16.9%) < Cr (17.5%) < Ce (25.1%) < Zr (26.2%) < Ni (26.8%) < Mg (27.9%). The reactivity of the lattice oxygen was estimated from energy of formation of the corresponding metal oxides. Correlation between the selectivity to propene and the standard energy of formation was attempted. Although there was no clear correlation, the result suggested that the lattice oxygen play a key role in the selectivity-determining step.     

The promotional effect of Cr on catalytic activity of Pt/ZSM-35 for H2-SCR in excess oxygen

Selective catalytic reduction of NO by hydrogen was studied over Cr modified Pt/ZSM-35 catalysts. The preparation process greatly influenced catalytic activity and sample prepared by co-impregnation method exhibits the best activity. In situ DRIFT studies revealed that on Pt–Cr/ZSM-35, (1) new Pt-NO^δ+ and NO species adsorbed on Pt were detected upon NO + O₂ adsorption; (2) much more ammonia species were formed under reaction condition. Cr addition not only enhanced the adsorption of NO_x but also promoted the formation of surface NH₄⁺ species, which should be the origin of promotional effect of Cr on Pt/ZSM-35 for H₂-SCR reaction.     

Promotional effect of Ce on the activity of In/W–ZrO2 for selective reduction of NO x with methane

The Ce modified In/W–ZrO₂ catalysts were prepared by impregnation and mechanical mix method. Their activities for SCR of NO _x with methane were investigated. The activity of the In/W–ZrO₂ catalyst was enhanced by addition of Ce with both methods, while the promotional effect was more pronounced for catalyst prepared by mechanical mix method compared to impregnation method. The function of Ce was to improve the oxidation of NO to NO₂. The maximum NO _x conversion over the mechanical mixed catalyst can be stabilized at 74% at 450 °C in a dry gas flow and 37% at 500 °C in wet flow (24,000 h⁻¹). For the impregnated catalysts, Ce was found to compete with In to adsorb on strong acid site over W–ZrO₂ support and inhibited the formation of InO⁺, which resulted in the lower activity of these catalysts than mechanical mixed catalysts.     

Cerium promoted Pd/HZSM-5 catalyst for methane combustion

A series of Pd/HZSM-5 (Si/Al₂ = 165) catalysts without and with additives of oxides of La, Ce, Sm, Nd and Tb were prepared by the impregnation method, and characterized by XRD, Raman spectra, N₂-adsorption, CO-chemisorption, O₂-TPD and CH₄-TPR techniques. The catalysts were investigated for low-temperature CH₄ combustion, and CeO₂ was found to have a significant promoting effect on the activity of Pd/HZSM-5. Pd–Ce/HZSM-5 showed the best methane combustion activity and the improved thermal/hydrothermal reaction stability among tested catalysts. The characterization results of catalysts indicated that CeO₂ can effectively promote the formation of crystalline PdO and weaken the bond strength of Pd–O on Pd–Ce/HZSM-5, resulting in that Pd–Ce/HZSM-5 possessed lower temperatures for oxygen desorption and CH₄ reduction than Pd/HZSM-5. This could be ascribed to the covalent property and large oxygen storage/supplying capacity of CeO₂. It is believed that more active PdO species on Pd/HZSM-5 for low-temperature methane combustion process could be effectively promoted due to the introduction of CeO₂.     

EXAFS and XPS Investigations of Cu/ZnO Catalysts and Their Interaction with CO and Methanol

Several investigations have been carried out on Cu/ZnO catalysts by employing extended Xray absorption fine structure (EXAFS) and Xray photoelectron spectroscopy (XPS). EXAFS investigations of Cu/ZnO catalysts subjected to hydrogen reduction show the presence of Cu¹⁺ species and Cu microclusters. The proportion of Cu¹⁺ depends on the rate of increase of the reduction temperature and on the amount of alumina added. An XPS study of the interaction of CO with model Cu/ZnO catalysts prepared in situ in the electron spectrometer shows the formation of CO₂ ^-, CO₃ ^2- and C₂O₄ ^2- species, their proportion relative to CO increasing with the Cu¹⁺/Cu⁰ ratio. A study of the interaction of CH₃OH with Cu clusters deposited on ZnO films reveals reversible molecular adsorption and the formation of CH₃O on clean Cu clusters. If the Cu clusters are pretreated with oxygen, however, both CH₃O and HCOO^- species are produced. Model Cu/ZnO catalyst surfaces containing both Cu¹⁺ and Cu⁰ species show interesting oxidation properties. On a Cu⁰-rich catalyst surface, only the CH₃O species is formed on interaction with CH₃OH. On a Cu¹⁺rich surface, the HCOO^- ion is the predominant species.     

The promotion effects of Ba on manganese oxide for CH4 deep oxidation

A series of catalysts based on high specific surface area MnO₂ precursor and modified by various amount of Ba were prepared and applied in CH₄ deep oxidation. The catalysts were characterized by means of N₂-BET, XRD, TG-DTA, H₂-TPR and CH₄-TPR techniques. The catalytic evaluation results show that CH₄ oxidation activity of the modified catalysts was enhanced, with the optimal Ba/Mn mol ratio being 0.1. Whereas, comparative study demonstrates that CO oxidation activity of the modified catalysts was not improved. It was shown previously that the reactivity of the oxygen species in a catalyst is crucial for CO oxidation, but not critical for CH₄ oxidation. In this study, TPR results verify that the mobility and reactivity of the lattice oxygen of Ba-modified catalysts is not improved, thus leading to no enhancement of their CO oxidation activity. However, the addition of Ba into manganese oxides is supposed to improve the basicity of the lattice O^2– of the prepared catalysts, which is favorable for the rupture of the first C–H bond in CH₄, the rate-determining step of the reaction. It is thus concluded that the enhanced CH₄ oxidation activity of the modified catalysts can be attributed to this modification effect of Ba.     

The design of Ti-, V-, Cr-oxide single-site catalysts within zeolite frameworks and their photocatalytic reactivity for the decomposition of undesirable molecules—The role of their excited states and reaction mechanisms

Transition metal oxides (Ti, V, Mo, Cr, etc.) incorporated within the framework of zeolites were found to exhibit high and unique photocatalytic reactivity as single-site heterogeneous catalysts for various reactions such as the decomposition of NOx (NO, N₂O) into N₂ and O₂, the reduction of CO₂ with H₂O to produce CH₄ and CH₃OH, the preferential oxidation of CO in the presence of H₂ (PROX), the partial oxidation of various hydrocarbons with O₂ or NO or N₂O and the epoxidation and metathesis reaction of alkenes. In situ spectroscopic investigations of these photofunctional systems applying photoluminescence, XAFS (XANES and FT-EXAFS), ESR and FT-IR revealed that the photo-excited states of the transition metal oxides play a vital role in the photocatalytic reactions. The high photocatalytic efficiency and selectivity of these single-site catalysts for significant reactions, which could not be observed with semiconducting bulk photocatalysts, were found to depend strongly on the unique and isolated local structure of the catalysts constructed within the restricted framework structure of the zeolites.     

Role of support in reforming of CH4 with CO2 over Rh catalysts

The reforming of CH₄ with CO₂ over supported Rh catalysts has been studied over a range of temperatures (550–1000 K). A significant effect of the support on the catalytic activity was observed, where the order was Rh/Al₂O₃>Rh/TiO₂>Rh/SiO₂. The catalytic activity of Rh/SiO₂ was promoted markedly by physical mixing of Rh/SiO₂ with metal oxides such as Al₂O₃, TiO₂, and MgO, indicating a synergetic effect. The role of the metal oxides used as the support and the physical mixture may be ascribed to the promotion in dissociation of CO₂ on the surface of Rh, since the CH₄ + CO₂ reaction is first order in the pressure of CO₂, suggesting that CO₂ dissociation is the rate-determining step. The possible model of the synergetic effect was proposed.