Reforming of Diesel Fuel for Hydrogen Production over Catalysts Derived from LaCo1−x M x O3 (M = Ru, Fe)

Catalysts derived from perovskite type oxides LaCo_1?x M _x O₃ (M = Ru or Fe, x = 0.2) synthesized by a modified citrate sol–gel method were tested in the oxidative reforming of diesel for hydrogen production. Physicochemical characterization of the samples revealed differences in the surface area, crystalline size, reducibility and relative distribution of the cobalt active phase on the surface of catalyst. These properties have important implications in the catalytic behaviour of the samples in the oxidative reforming of diesel. The increase in reducibility and metal exposition implies higher reforming activity as it was observed for the catalyst derived from LaCo_0.8Ru_0.2O₃.     

Ni–Nb-Based Mixed Oxides Precursors for the Dry Reforming of Methane

Perovskite-related mixed-oxides based on La Ni Nb and La Sr Ni Nb were synthesized by the auto combustion method to use as precursors materials for the catalytic reforming of methane at 700 ºC, atmospheric pressure, CH₄:CO₂ = 1:1. LaNiO₃ and LaNbO₄ were used as reference. XRD analysis show that the synthesis method produce a new series of precursor family formed by a mixture of oxides where Ni crystallized as part of a perovskite and Ruddlesden–Popper structure while Nb formed lanthanum orthoniobate LaNbO₄, a scheelite-type structure alternating with oxide layers, with phase distribution depending on niobium content. For Nb (x ≤ 0.3) Ni crystallizes as LaNiO₃ perovskite-type oxide while for Nb (x ≥ 0.7) it forms mainly the orthoniobate phase LaNbO₄ a scheelite-type structure. At higher calcined temperatures (~1100 °C) La₂Ni_0.8Nb_0.2O₄ was formed with a Ruddlesden–Popper structure consisting of three perovskite type layers along the c-axis alternating with a layer of the rock salt type phase. TEM analysis showed the presence of cubic particles with sizes varying between 5 and 60 nm depending on the extent of substitution of Ni by Nb. Reduction of the perovskite-related precursor oxides produced a series of Ni⁰/La₂O₃–NbOx oxides with high metallic dispersion which favors the activity and stability of the catalysts. Introduction of doping quantities of Sr into LaNi_0.8Nb_0.2O_3±λ structure produced a mixture of oxides with Sr dissolved in the lanthanum orthoniobate LaNbO₄ scheelite-type structure due to the similarity of ionic radii of La and Sr. Under the reaction conditions conversions near the thermodynamic equilibrium were attained which remains for long periods of time assessing the stability of the synthesized catalysts.     

Co3O4 and Mn3O4 Nanoparticles Dispersed on SBA-15: Efficient Catalysts for Methane Combustion

Co₃O₄ and Mn₃O₄ nanoparticles were successfully impregnated on SBA-15 mesoporous silica. A high dispersion of these metal oxide particles was achieved while using a “two-solvents” procedure, allowing a proper control of the metal oxides loading (7 wt%) and size (10–12 nm). These Co₃O₄ and Mn₃O₄ supported oxides on SBA-15 were characterised by means of XRD, BET and TEM techniques. The influence of the nature of the silica support was investigated in terms of porosity and specific surface area. Since, an improved catalytic activity was achieved over SBA-15 mesoporous silica; it appears that its organised porous meso-structure creates a confinement medium which permits a high dispersion of metal oxide nanoparticles. Supported Co₃O₄/SBA-15 (7 wt%) showed the highest catalytic performance in the combustion of methane under lower explosive limit conditions, comparable to perovskites. These materials become therefore novel efficient combustion catalysts at low metal loading.     

The role of Sb and Nb in rutile-type Sn/V/Nb/Sb mixed oxides, catalysts for propane ammoxidation to acrylonitrile

This paper describes the role of Sb and Nb, components of Sn/V/Nb/Sb mixed oxides catalysts for the gas-phase ammoxidation of propane to acrylonitrile. In samples without Nb and with atomic ratios Sn/V/Sb 1/0.2/x (x = 0 to 3), Sb in the form of amorphous oxide is necessary in order to obtain an active and selective catalyst. However, during reaction the dispersed Sb oxide segregates to α-Sb₂O₄, and the yield to acrylonitrile decreases considerably. The addition of Nb gives rise to the formation of Nb-containing SbO_x and non-stoichiometric rutile-type V/Nb/Sb mixed oxides. The presence of these compounds enhances the catalytic activity and the selectivity to acrylonitrile. Moreover, the catalyst shows a stable catalytic performance, with no segregation of α-Sb₂O₄.     

Ordered Crystalline Mesoporous Oxides as Catalysts for CO Oxidation

Crystalline mesoporous metal oxides have attracted considerable attention recently, but their catalytic applications have rarely been studied. In this work, a series of crystalline three-dimensional mesoporous metal oxides (i.e., CeO₂, Co₃O₄, Cr₂O₃, CuO, Fe₂O₃, β-MnO₂, Mn₂O₃, Mn₃O₄, NiO, and NiCoMnO₄) were prepared using the mesoporous silica KIT-6 as a hard template. These ordered mesoporous metal oxides with highly crystalline walls were characterized by PXRD, TEM, N₂ adsorption and evaluated as CO oxidation catalysts. These mesoporous materials, except for mesoporous Fe₂O₃, exhibit much higher catalytic activities than their bulk counterparts. In particular, mesoporous Co₃O₄, β-MnO₂, and NiO show appreciable CO oxidation activity below 0 °C, and the catalytic activities of mesoporous β-MnO₂, and NiO are even higher than those of their nanoparticulate counterparts with large surface areas. β-MnO₂ is particularly interesting because it combines low cost and low toxicity with high activity (T ₅₀ = 39 °C).     

Vanadium, niobium and tantalum modified mesoporous molecular sieves as catalysts for propene epoxidation

SBA-3 mesoporous molecular sieves doped with transition metal ions (Fe, V, Nb and Ta) have been applied for selective oxidation of propene towards propylene oxide in the presence of N₂O as an oxidant. The kind and amount of applied modifiers significantly affected the catalytic activity. V/SBA-3 was found to be the most active among the catalyst under study. In spite of relatively high selectivity towards propylene oxide (reaching up to 23%), the main oxidation product was still propionaldehyde. Surprisingly, CO_x was not formed over V, Nb and Ta modified SBA-3 catalysts. Additional modification of V containing samples (V/SBA-3) with iron complexes resulted in the further increase in the catalysts activity for epoxidation reaction. A PO selectivity of about 20% could be achieved at a propylene conversion of 17% over mixed Fe/V/SBA-3 catalytic system.     

Supported Ni–W–O Mixed Oxides as Selective Catalysts for the Oxidative Dehydrogenation of Ethane

Mixed Ni–W–O catalysts (with a W/(Ni + W) atomic ratio of 0.3) supported on γ-Al₂O₃ or on mesoporous alumina have been prepared, characterized and tested in the oxidation of ethane. For comparison unsupported and supported NiO as well as bulk Ni–W–O mixed oxides catalysts have also been studied. Supported Ni–W–O materials show interesting catalytic performances in the oxidative dehydrogenation of ethane. They show similar catalytic activities than the corresponding unsupported Ni–W–O catalysts. However, the selectivity to ethylene over supported catalysts was higher than that achieved over unsupported samples (the selectivity to ethylene followed the trend: mesoporous-supported > γ-Al₂O₃-supported > unsupported Ni–W–O). In addition, it has also been observed that Ni–W–O catalysts are more efficient than the corresponding W-free NiO catalysts. The discussion of the catalytic results will be undertaken on the basis of the modification of active sites of NiO when incorporating WO₃ and/or metal oxide supports.     

La1−x Ca x NiO3 Perovskite Oxides: Characterization and Catalytic Reactivity in Dry Reforming of Methane

Perovskite-type oxides such as La_1?x Ca _x NiO₃ (x = 0.0, 0.05, 0.1, 0.3, 0.5 and 0.8) have been prepared from citrate precursors and characterized by XRD, TPR, TG-H₂ and XPS. Catalytic experiments in the reforming of CH₄ with CO₂ have been carried out in a tubular reactor at 750 °C and atmospheric pressure. After the catalytic tests the catalysts were studied by TPO and SEM. Partial substitution of La by Ca was performed to stabilize Ni particles and to prevent carbon deposition. The XRD profiles showed that the perovskite structure is the only compound identified within the 0 ≤ x ≤ 0.05 range, whereas for x ≥ 0.1 compounds such as spinel-type La₂NiO₄, NiO and CaO were observed in addition to the perovskite oxide. On the other hand, segregation of NiO, even in the unsubstituted perovskite (x = 0.0), was confirmed by TPR and XPS. The catalytic tests showed that the replacement of La by Ca, which has a lower ionic radius, favored a higher activity and stronger resistance to carbon deposition. However, this coking resistance depended on the Ca-loading and the catalysts with x = 0.05 and x = 0.8 were the most stable against deactivation.     

Fe3+-substituted aluminium oxide nano-flakes: Structural,morphological, optical,and gas sensing properties

Mixed metal oxides with chemical formula Fe_xAl_2-xO₃ (where x = 0.2–1.0) (FANF) was synthesized via sol-gel auto combustion process. X-ray diffraction, field emission scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy were employed to characterize produced oxide materials. The final product FANF was sintered for 5 h at 1100 °C. The TG-DTA validated the mixed metal oxides phase evolution and steady-state temperature. The replacement of aluminium ions results in orthorhombohedral structure in mixed metal oxides (MMO). The bandgap decreased from 3.72 eV to 3.21 eV and the crystallite size decreased from 28 nm to 14 nm as the iron content increased in the sample Fe_xAl_2-xO₃ (where x = 0.2–1.0). The FT-IR confirmed no impurity peaks and the single phase with iron oxide band is near 432 cm^?1, while the aluminium oxide band is 565–600 cm^?1. Microstructural investigation shows flake-like growth, and EDS confirmed a stoichiometric ratio of MMO. Iron-substituted aluminate gas sensors detected CO, H₂S, and NO₂ at temperature ranging from 25 to 300 °C. Fe_0.6Al_1.4O₄ (F₃ANF) sensor responded 46.69% towards 100 ppm H₂S at 200 °C. Overall, the results showed that a flake-like FANF sensor can be used effectively as a H₂S gas sensor.     

High Catalytic Activity in CO Oxidation over MnO x Nanocrystals

Manganese oxides of various stoichiometry were prepared via Mn-oxalate precipitation followed by thermal decomposition in the presence of oxygen. A non-stoichiometric manganese oxide, MnO _x (x = 1.61…1.67) was obtained by annealing at 633 K and demonstrated superior CO oxidation activity, i.e. full CO conversion at room temperature and below. The activity gradually decreased with time-on-stream of the reactants but could be easily recovered by heating at 633 K in the presence of oxygen. CO oxidation over MnO _x in the absence of oxygen proved to be possible with reduced rates and demonstrated a Mars—van Krevelen—type mechanism to be in operation. A TEM structural analysis showed the MnO _x phase to form microrods with large aspect ratio which broke up into nanocrystalline manganese oxide (MnO _x ) particles with diameters below 3 nm and a BET specific surface area of 525 m²/g. Annealing at 798 K rather than 633 K produced well crystalline Mn₂O₃ which showed lower CO oxidation activity, i.e. 100% CO conversion at 335 K. The catalytic performance in CO oxidation of various Mn-oxides either studied in this work or elsewhere was compared on the basis of specific reaction rates.     

Redox Properties and Catalytic Oxidation Activities of Polyatom-Substituted H n PW11M1O40 (M = V, Nb, Ta, and W) Keggin Heteropolyacid Catalysts

Redox properties and catalytic oxidation activities of polyatom-substituted H _n PW₁₁M₁O₄₀ (M = V, Nb, Ta, and W) Keggin heteropolyacids (HPAs) were examined. Reduction potentials and UV–visible absorption edge energies of H _n PW₁₁M₁O₄₀ (M = V, Nb, Ta, and W) HPA catalysts in solution were determined by an electrochemical method and UV–visible spectroscopy measurements, respectively. It was observed that reduction potentials of H _n PW₁₁M₁O₄₀ (M = V, Nb, Ta, and W) HPA catalysts increased and UV–visible absorption edge energies of the HPA catalysts decreased with decreasing electronegativity of substituted polyatom. It was also found that the lower absorption edge energy corresponded to the higher reduction potential of the HPA catalyst. Vapor-phase oxidation of benzyl alcohol was carried out as a model reaction to probe the redox properties of H _n PW₁₁M₁O₄₀ (M = V, Nb, Ta, and W) HPA catalysts. Yield for benzaldehyde increased with increasing reduction potential and with decreasing absorption edge energy of the HPA catalyst, and in turn, with decreasing electronegativity of substituted polyatom. Reduction potential of H _n PW₁₁M₁O₄₀ (M = V, Nb, Ta, and W) HPA catalysts measured by an electrochemical method and absorption edge energy of the HPA catalysts measured by UV–visible spectroscopy could be utilized as a probe of oxidation catalysis of the HPA catalysts.     

Catalytic performance of metal ion doped MCM-41 for methanol dehydration to dimethyl ether

Metal ion doped MCM-41 mesoporous molecular sieves (M-MCM-41, M = Al, Ga, Sn, Zr and Fe) were prepared using a hydrothermal synthesis method, with metal chlorides serving as the dopant sources. The M-MCM-41 structures were characterized by Fourier transform infrared spectroscopic (FTIR) analysis, X-ray diffraction, energy dispersive spectroscopy and N₂ adsorption–desorption measurement. The surface of M-MCM-41 acidities were determined by NH₃ temperature-programmed desorption and pyridine-adsorption FTIR analysis, and their catalytic performance for methanol dehydration to dimethyl ether (DME) was evaluated. The results showed that the prepared M-MCM-41, which exhibited a structure similar to that of MCM-41 with long-range ordered mesoporous structure, contained weak acidic sites. The number of weak acid sites in Al-MCM-41 increased as the Al content increased. The Al content in Al-MCM-41 had an important effect on its catalytic performance, where the highest catalytic activity was 80 and 100 % DME selectivity was achieved at a Si/Al molar ratio of 10. For MCM-41 doped with various types of metal ions, M-MCM-41 (M = Al, Ga, Sn and Zr) also presented a similar wide distribution of acidity, and their catalytic activities were ranked in the following order: Al-MCM-41 > Ga-MCM-41 > Zr-MCM-41 > Fe-MCM-41 > Sn-MCM-41, which were related to the coordination of the metal ions.     

Highly Active La1−x K x CoO3 Perovskite-type Complex Oxide Catalysts for the Simultaneous Removal of Diesel Soot and Nitrogen Oxides Under Loose Contact Conditions

The nanometric La_1?x K _x CoO₃ (x = 0–0.30) perovskite-type oxides were prepared by a citric acid-ligated method. The catalysts were characterized by means of XRD, IR, BET, XPS and SEM. The catalytic activity for the simultaneous removal of soot and nitrogen oxides was evaluated by a technique of the temperature-programmed oxidation reaction. In the LaCoO₃ catalyst, the partial substitution of La³⁺ at A-site by alkali metal K⁺ enhanced the catalytic activity for the oxidation of soot particle and reduction of NO _x . The La_0.70K_0.30CoO₃ oxides are good candidate catalysts for the simultaneous removal of soot particle and NO _x . The combustion temperatures for soot particles over the La_0.70K_0.30CoO₃ catalyst are in the range from 289 to 461 °C, the selectivity of CO₂ is 98.4% and the conversion of NO to N₂ is 34.6% under loose contact conditions. The possible reasons that can lead to the activity enhancement for the K-substitution samples compared to the unsubstituted sample (LaCoO₃) were given. The particle size has a large effect on its catalytic performance for the simultaneous removal of diesel soot and nitrogen oxides.     

The control of catalytic performance of rutile-type Sn/V/Nb/Sb mixed oxides, catalysts for propane ammoxidation to acrylonitrile

This paper describes the effect of the composition of rutile-type Sn/V/Nb/Sb mixed oxides catalysts on the catalytic performance in the gas-phase ammoxidation of propane to acrylonitrile. The variation in the atomic ratio between components in catalysts is the key for the control of activity and selectivity. In samples with atomic composition Sn/V/Nb/Sb 1/0.2/1/x (0 ≤ x ≤ 5) and 1/0.2/y/3 (0 ≤ y ≤ 3) several compounds formed, i.e., SnO₂, Sb/Nb mixed oxide, Sb₆O₁₃ and non-stoichiometric rutile-type V/Nb/Sb/O; the latter segregated preferentially at the surface of the catalyst. Tin oxide provided the rutile matrix for the dispersion of the mixed oxides. The main role of Sb was shown to generate mixed oxides containing specific sites for the allylic ammoxidation of propylene intermediately formed. The presence of Nb enhanced the activity and selectivity of these sites.     

Formation of catalytic active sites in copper and manganese modified SBA-15 mesoporous silica

A series of copper and manganese oxides modified SBA-15 mesoporous silicas with different composition was prepared by incipient wetness impregnation with the corresponding nitrate precursors and compared with the analogous materials supported on conventional SiO₂. Nitrogen physisorption, XDR, FTIR, UV–Vis and temperature programmed reduction with hydrogen were used for samples characterization. Their catalytic activity was tested in ethyl acetate oxidation and methanol decomposition. The ordered porous structure of the support facilitates the interaction between different metal oxide nanoparticles and increases their dispersion due to the formation of mixed oxide phase. The ethyl acetate oxidation on SBA-15 binary materials is suppressed due to the lower accessibility of the metal oxide particles, located deeply into the micro-meso pores of the support. The reaction medium which forms during the methanol decomposition provides the reduction/decomposition transformations with the mixed oxide phase. The final phase composition of finely dispersed Cu/CuO and MnO_x particles stabilizes in a highly dispersed state into the porous matrix of SBA-15 support and increases the catalytic activity in methanol decomposition due to the appearance of synergistic effect between them.     

Highly ordered crystalline mesoporous metal oxides for hydrogen peroxide decomposition

Highly ordered mesoporous metal oxides (meso-MO _x ) such as CeO₂, Co₃O₄, Cr₂O₃, Mn₂O₃, NiO, RuO₂, SnO₂ and TiO₂ were successfully synthesized using mesoporous silica KIT-6 as a hard template via the nano-replication method. The physicochemical properties of as-prepared meso-MO _x were characterized by scanning electron microscopy, X-ray diffraction, N₂ adsorption–desorption and temperature programmed techniques. Their catalytic behavior toward H₂O₂ decomposition was investigated and compared with the corresponding bulk metal oxides (bulk-MO _x ) synthesized by the conventional precipitation method. These meso-MO _x materials exhibited much higher catalytic activities than their bulk counterparts. In particular, meso-Mn₂O₃ and meso-RuO₂ showed high activities, while meso-SnO₂ resulted in no activity toward H₂O₂ decomposition. The overall conversion of H₂O₂ followed a general order: Mn₂O₃ > RuO₂ > Co₃O₄ > CeO₂ > NiO > Cr₂O₃ > TiO₂ > SnO₂.     

Selective Reduction of NO with CO Over Titania Supported Transition Metal Oxide Catalysts

A series of transition metal oxides promoted titania catalysts (MO _x /TiO₂; M = Cr, Mn, Fe, Ni, Cu) were prepared by wet impregnation method using dilute solutions of metal nitrate precursors. The catalytic activity of these materials was evaluated for the selective catalytic reduction (SCR) of NO with CO as reductant in the presence of excess oxygen (2 vol.%). Among various promoted oxides, the MnO _x /TiO₂ system showed very promising catalytic activity for NO + CO reaction, giving higher than 90% NO conversion over a wide temperature window and at high space velocity (GHSV) of 50,000 h⁻¹. It is remarkable to note that the catalytic activity increased with oxygen, up to 4 vol.%, under these conditions leading primarily to nitrogen. Our TPR studies revealed the presence of mixed oxidation states of manganese on the catalyst surface. Characterization results indicated that the surface manganese oxide phase and the redox properties of the catalyst play an important role in final catalytic activity.     

Catalytic combustion of soot on metal oxides and their supported metal chlorides

Gravimetric temperature programmed oxidation was used to study the combustion of a soot mixed with various metal oxides and their supported metal chloride catalysts. It is found that the catalytic effect of metal oxide on soot combustion varies depending on property of oxides. CuO and Cr₂O₃ are better catalysts. Addition of some chloride salts (FeCl₃, NaCl and KCl) increases the catalytic activity and KCl exhibits the highest promoting effect by reducing the T_max for about 200 °C. Metal chlorides can also show a synergistic effect on soot combustion. FeCl₃–KCl/CuO can reduce the T_max of carbon oxidation from 780 to 500 °C. Investigation also demonstrates that FeCl₃–KCl/CuO is effective for NO reduction at low temperatures.     

Catalytic combustion of methane over mixed oxides derived from Co-Mg/Al ternary hydrotalcites

Co_xMg_3 − x /Al composite oxides (xCoMAO-800) were prepared by calcination of Co_xMg_3 − x/Al hydrotalcites (x = 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, respectively) at 800 °C. The materials were characterized using XRD, TG-DSC, N₂ adsorption-desorption and TPR. The methane catalytic combustion over the xCoMAO-800 was assessed in a fixed bed micro-reactor. The results revealed that cobalt can be homogenously dispersed into the matrices of the hydrotalcites and determines the structure, specific surface areas and porosity of the derived xCoMAO-800 oxide catalysts. The thermal stability and homogeneity of the hydrotalcites markedly depends on the cobalt concentration in the hydrotalcites. The Co-based hydrotalcite-derived oxides exhibit good activity in the catalytic combustion of methane. The catalytic activity over the xCoMAO-800 oxides enhances with increasing x up to 1.5, but subsequently decreases dramatically as cobalt loadings are further increased. The 1.5CoMAO-800 catalyst shows the best methane combustion activity, igniting methane at 450 °C and completing methane combustion around 600 °C. The catalytic combustion activity over the xCoMAO-800 oxides are closely related to the strong Co-Mg/Al interaction within the mixed oxides according to the TG-DSC, TPR and activity characteristics.     

Novel Y2O3 Doped MnO x Binary Metal Oxides for NO x Storage at Low Temperature in Lean Burn Condition

MnO _x -Y₂O₃ binary metal oxide catalysts are synthesized by a constant-pH co-precipitation method, their ability of NO _x storage capacity and absorbing process were investigated. The pure MnO _x and Y₂O₃ calcined at 500 °C for 4 h in static air are both of body-centre structure, while the binary metal oxides containing Mn and Y are mainly of amorphous phase. The adulteration of Y₂O₃ can remarkably improve the specific surface areas of the catalysts, which probably result of the enhancement on NO storage capacity and catalytic oxidation ability of NO at 100 °C. The XPS results indicate that both Mn and Y have 3+ chemical states in the binary oxides. FT-IR spectra could be beneficial to explain the NO storage process on the binary metal oxide: NO can be adsorbed on the MnO _x and Y₂O₃ sites as nitrates and nitrites, respectively, and then the nitrites on Y₂O₃ site are shifted to Mn₂O₃ site and then is oxidized to nitrates. As a result, the NO storage capacity is enhanced due to the adulteration of Y₂O₃, finally the NO _x are adsorbed on the Mn₂O₃ site as nitrate species.