Catalytic combustion of toluene over Fe–Mn mixed oxides supported on cordierite

The catalytic combustion of toluene over Fe–Mn mixed oxides supported on cordierite was investigated. The catalysts were synthesized by the impregnation method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and BET specific surface area measurement. The effects of the mole ratio of Fe to Mn, the loading of Fe–Mn mixed oxides on the catalyst support and the calcination temperature were all investigated. The results indicate that Fe–Mn/cordierite catalysts with a 4 mol ratio of Fe to Mn, used with 10 wt% loading, and calcined at 500 ^°C showed the highest catalytic activities as measured by the oxidation of toluene. Compared to unsupported powder catalysts of Fe–Mn mixed oxides, the Fe–Mn/cordierite catalyst showed higher activity for the catalytic combustion of toluene with less active component.     

Catalytic Decomposition of Methane Over M–Co–Al Catalysts (M = Mg,Ni, Zn,Cu)

Abstract  

The catalytic decomposition of methane over M–Co–Al (M = Mg, Ni, Zn, Cu) was studied. The samples were prepared by co-precipitation and characterized by S_BET, TGA, DTA, TPR and XRD. The carbon produced in the reaction was characterized by SEM and TPO. Activity tests were carried out in a thermobalance between 500 and 750 °C. The results show that the textural properties of the calcined samples did not change significantly with the partial substitution of Co by Mg, Ni, Zn or Cu. On the other hand, there were marked differences in the reduced samples. There was a strong influence on the reducibility of cobalt oxides in the presence of Ni or Cu. Nickel promoted the reduction of Co₃O₄ at the same temperature as the NiO phase, whereas copper strongly decreased the reduction temperature of both Co₃O₄ and CoAl₂O₄ due to a synergistic effect between Cu and Co. The sample containing Cu resulted in low catalytic activity in the whole temperature range because the reduction conditions promoted the formation of a Cu–Co alloy. In the reaction carried out at 700 °C, the observed activity was Co–Al > Mg–Co–Al > Ni–Co–Al. All the samples were deactivated by encapsulation under these conditions due to high rates of carbon deposition. The carbon produced was mainly carbon nanotubes, except for the Cu–Co–Al sample, which produced mostly amorphous carbon.     

Characteristics of methane combustion over La–Cr–O catalysts

The catalytic activities of methane combustion of La–Cr–O catalysts prepared with and without polyacrylic acid as a template have been compared. The polymer-templated catalyst had a higher BET surface area, 12.3 m² g⁻¹, than that obtained from the conventional precipitation method, 2.9 m² g⁻¹. The results of XRD and SEM experiments suggested that the structural characteristics were almost similar. Surprisingly, the areal rate of methane combustion over the catalyst with a small surface area was ten times larger than that of the catalyst with a large surface area. However, the site time yields (STY) based on the oxygen adsorption capacity were similar, independent of the surface area and preparation conditions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ceramic monolith supported Mn–Ce–M ternary mixed-oxide (M=Cu,Ni or Co) catalyst for VOCs catalytic oxidation

The MO_x (M=Cu, Ni or Co) modified manganese-cerium mixed-oxide catalysts supported on ceramic monolith were prepared by sol-gel method and examined for the catalytic combustion of o-xylene. Results show that the addition of CuO_x could significantly enhance the catalytic properties of the monolithic catalysts, which may be correlated with the Mn-Cu synergistic interaction. The effects of the preparation parameters including the Cu content, the total amount of active phase and the calcination temperature and time, as well as the reaction conditions, i.e., the space velocity and concentration of o-xylene, on the catalytic performance for the combustion of o-xylene were also investigated. It is shown that the MnCeCu_0.4/monolith catalyst with the active phase loading of 11.4 wt% and calcined at 500 °C for 3 h displays the highest catalytic activity. When the concentration of o-xylene is 1000 ppm and the space velocity is 10,000 h⁻¹, the temperature at which 90% o-xylene conversion is reached is 277 °C. It is also seen that the optimum catalyst has a good catalytic stability and exhibits an excellent activity not only at a rather high space velocity but also within a wide range of o-xylene concentration. Furthermore, the optimum catalyst also show the high combustion performance for other hydrocarbons, e.g., n-butanol and styrene.     

Selective oxidation of soot over Cu doped ceria/ceria–zirconia catalysts

Copper doped ceria and ceria–zirconia mixed oxides were prepared using the citric acid sol–gel method. The temperature-programmed oxidation (TPO) results showed that the Cu modification helped to improve the activity and selectivity of ceria and ceria–zirconia for soot catalytic oxidation. The CO-TPR results showed that Cu–Ce had a better reducibility than pure ceria at low temperatures. After ageing at 800 °C for 20 h in flow air, CuO–CeO₂ showed the maximum soot oxidation rate at 378 and 519 °C under tight and loose contact conditions, respectively, achieving a nearly 100% selectivity to CO₂ production. This effect may be attributed to the existence of well dispersed copper oxide species strongly interacting with the ceria surface, which may decrease the activation energy of soot oxidation. A conceivable mechanism of this synergetic effect was proposed.     

Kinetics of methane combustion over Pt and Pt–Pd catalysts

A kinetic study was performed over thermally aged and steam-aged Pt and Pt–Pd catalysts to investigate the effect of temperature, and methane and water concentrations on the performance of catalysts in the range of interest for environmental applications. It was found that both catalysts permanently lose a large portion of their initial activity as result of exposure to 5 vol.% water in the reactor feed. Empirical power-law and LHHW type of rate equations were proposed for methane combustion over Pt and Pt–Pd catalysts respectively. Optimization was used to determine the parameters of the proposed rate equations using the experimental results. The overall reaction orders of one and zero in methane and water concentration was found for stabilized steam-aged Pt catalyst in the presence and absence of water. The apparent self-inhibition effect caused by methane over Pt–Pd catalyst in the absence of water was associated with the inhibiting effect of water produced during the combustion of methane. A significant reversible inhibition effect was also observed over steam-aged Pt–Pd catalyst when 5 vol.% water vapor was added to the reactor feed stream. A significant reduction in both activity and activation energy was observed above temperatures of approximately 550 °C for steam-aged Pt–Pd catalyst in the presence of water (the activation energy dropped from a value of 72.6 kJ/mol to 35.7 kJ/mol when temperature exceeded 550 °C).     

Synthesis of natural gas from CO methanation over SiC supported Ni–Co bimetallic catalysts

A series of SiC supported bimetallic Ni–Co catalysts with different Ni/Co ratios was investigated for CO methanation reaction. Compared with monometallic Ni- and Co-based catalysts, the bimetallic Ni–Co catalysts showed higher methanation activity and the Ni/Co ratios significantly affected the methanation activity. The highest activity was obtained over 6Ni4Co/SiC bimetallic catalyst, which also showed excellent stability during the methanation reaction. Further characterizations revealed that the surface enrichment of metal components occurred on the bimetallic catalysts. The interaction between Ni and Co and higher metal dispersion might improve the adsorption and activation of CO and thus enhance the methanation activity of the bimetallic catalysts.     

Photocatalytic hydrogen production by Au–MxOy (MAg,Cu, Ni) catalysts supported on TiO2

Au–M_xO_y (MAg, Cu, Ni) nanoparticles supported on TiO₂–P25 were prepared by the deposition–precipitation method and were evaluated for the photocatalytic water splitting reaction for hydrogen production, using a mixture of water–methanol (1:1). The combinations of Au–Cu₂O/TiO₂ and Au–NiO/TiO₂ effectively increased the hydrogen production (2064 and 1636 μmol·h^− 1·g^− 1) obtained by Au/TiO₂ (1204 μmol·h^− 1·g^− 1). The higher photoactivities achieved by Au–Cu₂O and Au–NiO nanoparticles deposited on TiO₂ were attributed to an enhancement of the electron charge transfer from TiO₂ to the Au–M_xO_y systems and the effect of surface plasmon resonance of gold nanoparticles.     

Synthesis of Co–Ni and Cu–Ni based-catalysts for dry reforming of methane as potential components for SOFC anodes

In this work, we report a comparative study of Ni-based anode compositions, made of Cu and Co (40 and 80 mol%) and gadolinia-doped ceria (CGO) matrices, for application the dry reforming of methane (DRM) reaction using Solid Oxide Fuel Cells (SOFCs). The new compositions are synthesized by a one-step synthesis route, using citric acid as chelating agent, and characterized at three different stages: i) after synthesis, ii) after reduction, and iii) after DRM. X-ray diffraction (XRD) analysis combined with thermodynamic calculations is used to understand phase evolution along the different stages, revealing that complete solid solutions of NiCo- and NiCu-based alloys are formed after DRM reaction. Transmission Electron Microscopy (TEM) shows the formation of nanocrystalline powders, while surface area (S_BET) measurements show higher values in the case of the NiCo-based samples. Moreover, the Co-containing compositions exhibit higher reducibility and stronger metal-ceramic interactions than the Cu-containing samples, according to the Temperature Programmed Reduction (TPR) results. Finally, DRM results demonstrate higher CO₂ and CH₄ conversions in the case of the Co-containing samples, as well as increased resistance towards carbon deposition, as confirmed by Thermogravimetric and Differential Scanning Calorimetry analyses (TG-DSC). Overall, the Co-based compositions are highly beneficial for their use as anodes for the CO₂ reforming of methane in SOFCs.     

Hydrogenation of Sunflower Oil over M/SiO2 and M/Al2O3 (M = Ni,Pd, Pt,Co, Cu) Catalysts

This work is aimed at evaluating the performance of several catalysts in the partial hydrogenation of sunflower oil. The catalysts are composed of noble (Pd and Pt) and base metals (Ni, Co and Cu), supported on both silica and alumina. The following order can be proposed for the effect of the metal on the hydrogenation activity: Pd > Pt > Ni > Co > Cu. At a target iodine value of 70 (a typical value for oleomargarine), the production of trans isomers is minimum for supported nickel catalysts (25.7–32.4 %, depending on the operating conditions). Regarding the effect of the support, Al₂O₃ allows for more active catalysts based on noble metals (Pd and Pt) and Co, the effect being much more pronounced for Pt. Binary mixtures of catalysts have been studied, in order to strike a balance between catalyst activity and product distribution. The results evidence that Pd/Al₂O₃–Co/SiO₂ mixture has a good balance between activity and selectivity, and leads to a very low production of trans isomers (11.8 %) and a moderate amount of saturated stearic acid (13.5 %). Consequently, the utilization of cobalt‐based catalysts (or the addition of cobalt to other metallic catalysts) could be considered a promising alternative for the hydrogenation of edible oil.     

Comparative studies on direct conversion of methane to methanol/formaldehyde over La–Co–O and ZrO2 supported molybdenum oxide catalysts

The selective oxidation of methane with molecular oxygen over MoO_x/La–Co–O and MoO_x/ZrO₂ catalysts to methanol/formaldehyde has been investigated in a specially designed high-pressure continuous-flow reactor. The properties of the catalysts, such as crystal phase, structure, reducibility, ion oxidation state, surface composition and the specific surface area have been characterized with the use of XRD, LRS, TPR, XPS and BET methods. MoO_x/La–Co–O catalysts showed high selectivity to methanol formation while MoO_x/ZrO₂ revealed the property for the formation of formaldehyde in the selective oxidation of methane. 7 wt MoO_x/La–Co–O catalyst gave 6.7 methanol yield (ca. 60 methanol selectivity) at 420°C and 4.2 MPa. On the other hand, the maximal yield of formaldehyde ca. 4 (47.8 formaldehyde selectivity) was obtained over 12wt MoO_x/ZrO₂ catalyst at 400 °C and 5.0MPa. 7MoO_x/La–Co–O catalyst showed higher modified H₂-consumption than 12MoO_x/ZrO₂ catalyst. The reducibility and the O^–/O^2– ratio of the catalysts may play important roles on the catalytic performance. The proper reducibility and the O^–/O^2– ratio enhanced the production of methanol in selective oxidation of methane. [MoO₄]^2– species in MoO_x/ZrO₂ catalysts enable selective oxidation of methane to formaldehyde.     

Comparison of the Activity of Pd–M (M: Ag,Co, Cu,Fe, Ni,Zn) Bimetallic Electrocatalysts for Oxygen Reduction Reaction

Topics in Catalysis - Carbon-supported 7.5 wt% Pd–2.5 wt% M (M: Ag, Co, Cu, Fe, Ni, Zn) bimetallic catalysts were synthesized via wet impregnation and assessed as...     

Synthesis of multiwalled carbon nanotubes supported on M/MCM-41 (M = Ni,Co and Fe) mesoporous catalyst by chemical vapour deposition method

Aim of this research is to develop an effective way in producing multi-walled carbon nanotubes (MWNTs) via chemical vapour deposition method using acetylene as carbon source and synthesized mesoporous M/MCM-41 (M?=?Ni, Co and Fe) as catalyst. The mesoporous MCM41 is synthesized by using sodium metasilicate as silica source of frameworks and cetyltrimethylammonium bromide as template. The effect of temperatures and growth times are investigated to produce MWNTs with high yield and high quality. The low-angle X-ray diffraction (XRD), Fourier transform infrared spectroscopy and scanning electron microscopy results verified the formation of MCM41. Meanwhile, high-angle XRD, Raman spectra and transmission electron microscopy results confirmed the synthesized carbon nanotubes at 600?°C and growth time for 30 min are multi-walled. The yield obtained is 1353 mg in 30 min. It shows that the MCM-41 has a promising potential to produce MWNTs at low cost and shorter duration.     

Comparative Study on Catalytic Performances for Low-temperature CO Oxidation of Cu–Ce–O and Cu–Co–Ce–O Catalysts

Two series of Cu–Ce–O and Cu–Co–Ce–O catalysts were prepared by co-precipitation method. The prepared catalysts were characterized by XRD, IR, TPR, XPS, BET and ICP-AES. The catalytic activities of the catalysts for low-temperature CO oxidation were evaluated through a microreactor-GC system. TPR results indicate that the addition of cobalt to the Cu–Ce–O can increase the dispersion of copper oxide, and the interaction between cobalt and copper can enhance the reducibility of each other. XPS analysis show that Ce⁴⁺, Cu²⁺, along with Co₃O₄, are present on the surface of Cu_0.4Co_0.6Ce₄ catalyst. The Co/Cu atomic ratio and the calcination temperature have significant effect on the activities of the catalysts. Compared with Cu₁Ce₄ catalyst, the Cu_0.4Co_0.6Ce₄ catalyst has better activity and thermal stability.     

Pd–Pt bimetallic catalyst supported on SAPO‐5 for catalytic combustion of diluted methane in the presence of water vapor

The examination of the combustion of a trace amount of methane over Pd‐ion‐exchanged silicoaluminophosphate‐5 (Pd‐SAPO‐5) at low temperature in the presence of water vapor reveals that water vapor strongly depresses methane combustion and causes a significant decrease in catalytic activity with time. The newly prepared bimetallic catalyst Pd–Pt‐SAPO‐5, on the other hand, shows higher performance for methane combustion under similar conditions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Separation of Xenon and Krypton in the Metal–Organic Frameworks M2(m-dobdc) (M=Co,Ni)

The separation of Xe and Kr from air is challenging owing both to the very low atmospheric concentrations of these gases and the need for their distillation at cryogenic temperatures. Alternatively, separation processes based on adsorption could provide a less energy-intensive route to the isolation of these gases. Here, we demonstrate that the metal–organic frameworks M₂(m-dobdc) (M=Co, Ni; m-dobdc⁴⁻=4,6-dioxido-1,3-benzenedicarboxylate) effectively separate Xe and Kr at ambient temperatures based on the different adsorption enthalpies of each gas at the coordinatively-unsaturated M²⁺ sites in each material. In situ Xe- and Kr-dosed powder X-ray diffraction studies further reveal key differences in the binding of Xe and Kr within the materials. In particular, while both gases adsorb near the framework open metal sites at 200 K, much higher Xe occupancies are observed at these sites relative to Kr, corroborating a stronger interaction of the polarizing M²⁺ cations with Xe. Further, while krypton is only found located above the open metal sites, two additional adsorption sites are observed for xenon, correlating with the stronger adsorption of Xe over Kr in these materials. These results suggest the possible utility of employing M₂(m-dobdc) materials in the adsorptive separation of Xe and Kr.     

Water-gas shift reaction over Cu–Zn,Cu–Fe,and Cu–Zn–Fe composite-oxide catalysts prepared by urea-nitrate combustion

Water-gas shift reaction was investigated over Cu–Zn, Cu–Fe and Cu–Zn–Fe composite-oxide catalysts at atmospheric pressure from 200 to 375 °C in terms of reducing the CO content with maximal H₂ yield. The Cu_0.15ZnFe₂ spinel catalyst expressed a higher CO conversion level and H₂ yield at a lower temperature compared to the Cu_0.15Zn and Cu_0.15Fe catalysts. Adding H₂O to the feed up to 30% (v/v), but not above, increased the CO reduction level, presumably by increasing the hydroxyl species to react with the adsorbed CO. Increasing the W/F ratio to 0.24 g s cm^?3 increased the CO conversion level to 0.76 at 275 °C with the Cu_0.15ZnFe₂ catalyst, and could be further increased to 0.86 at 350 °C by increasing the Cu molar ratio to 0.30 (Cu_0.30ZnFe₂). Nevertheless, increasing the Cu molar content to 0.50 reduced the CO conversion level. No requirement for adding O₂ when using the Cu_0.30ZnFe₂ catalyst at >260 °C was observed. Increasing the CO content in the reactant decreased its conversion level. The performance of the Cu_0.30ZnFe₂ catalyst was stable over a test period in a CO-rich condition. No undesired product was detected, suggesting a higher selectivity for hydrogen production with a low CO content.     

Structured hierarchical Mn–Co mixed oxides supported on silicalite-1 foam catalyst for catalytic combustion

Silicalite-1 (S1) foam was functionalized by supporting manganese–cobalt (Mn–Co) mixed oxides to develop the structured hierarchical catalyst (Mn–Co@S1F) for catalytic combustion for the first time. The self-supporting S1 foam with hierarchical porosity was prepared via hydrothermal synthesis with polyurethane (PU) foam as the template. Subsequently, Mn–Co oxide nano sheets were uniformly grown on the surface of S1 foams under hydrothermal conditions to prepare the structured hierarchical catalyst with specific surface area of 354 m²·g⁻¹, micropore volume of 0.141 cm³·g⁻¹ and total pore volume of 0.217 cm³·g⁻¹, as well as a good capacity to adsorb toluene (1.7 mmol·g⁻¹ at p/p₀ = 0.99). Comparative catalytic combustion of toluene of over developed structured catalyst Mn–Co@S1F was performed against the control catalysts of bulk Mn–Co@S1 (i.e., the crushed Mn–Co@S1F) and unsupported Mn–Co oxides (i.e., Mn–Co). Mn–Co@S1F exhibited comparatively the best catalytic performance, that is, complete and stable toluene conversion at 248 °C over 65 h due to the synergy between Mn–Co oxides and S1 foam, which provided a large number of oxygen vacancies, high redox capacity. In addition, the hierarchical porous structure also improved the accessibility of active sites and facilitated the global mass transfer across the catalyst bed, being beneficial to the catalysis and catalyst longevity.     

Dry reforming of methane over palladium–platinum on carbon nanotube catalyst

A dry reforming (DR) catalyst based on bimetallic Pd–Pt supported on carbon nanotubes is presented. The catalyst was prepared using a microwave-induced synthesis. It showed enhanced DR activity in the 773–923?K temperature range at 3 atm. Observed carbon balances between the reactant and product gases imply minimal carbon deposition. A global three-reaction (reversible) kinetic model—consisting of DR, reverse water gas shift, and CH₄ decomposition (MD)—adequately simulates the observed concentrations, product H₂/CO ratios, and reactant conversions. Analysis shows that, under the conditions of this study, the DR and MD reactions are net forward and far from equilibrium, while the RWGS is near equilibrium.