Vanadium oxide supported on mesoporous Al2O3: Preparation, characterization and reactivity

The application of different techniques (diffuse reflectance-UV–vis, ⁵¹V NMR, FT-IR of adsorbed pyridine and TPR-H₂) in the characterization of vanadia supported on mesoporous Al₂O₃ catalysts shows that the nature of the vanadium species depends on the V-loading. At V-content lower than 15 wt.% of V-atoms (30% of the theoretical monolayer), vanadium is mainly in a tetrahedral environment. Higher V-contents in the catalyst leads to the formation of octahedral V⁵⁺ species and V₂O₅-like species. Both XRD and textural results indicate that the mesoporous structure of the support is mostly maintained after the vanadium incorporation, and therefore high surface areas were obtained on the final catalysts. Al₂O₃-suppported vanadia catalysts are active and selective in the oxidative dehydrogenation of ethane, although the catalytic behavior depends on the V-loading. High rates of formation of ethylene per unit mass of catalyst per unit time have also been observed as a consequence of the high dispersion of V-atoms on the surface of the support.     

The effect of the nature of vanadium species on benzene total oxidation

The nature of the vanadium species present on V₂O₅/Al₂O₃ catalysts was investigated by using solid state ⁵¹V NMR, diffuse reflectance spectroscopy (DRS), X-ray diffraction (XRD) and temperature programmed reduction (TPR). ⁵¹V NMR and DRS analyses indicated the presence of V⁵⁺ in tetrahedral symmetry at low vanadium loading. A surface polymeric vanadium species and/or the bulk crystalline V₂O₅ were mainly observed at high vanadium loading as also detected by XRD. The positions of the absorption edges determined through the UV–VIS spectra allowed distinguishing between various tetrahedral symmetries. After TPR, the average oxidation state of vanadium depended on the vanadium content. The nature of vanadium species was related to the catalyst behavior on the benzene oxidation reaction. The catalysts containing high vanadium content were more active suggesting that a high amount of V⁴⁺ is responsible for the higher activity.     

Alumina-supported catalysts for propane oxidative dehydrogenation from mixed VXM(6−X)O19 (M=W, Mo) hexametalate precursors

γ-Al₂O₃ supported vanadium oxides were modified by tungsten and molybdenum oxides in order to improve dispersion and selectivity towards olefins in propane oxidative dehydrogenation (ODH). Both vanadium–tungsten and vanadium–molybdenum catalysts were obtained by adsorption of mixed isopolyanions (VW₅O₁₉⁵⁻, V₂W₄O₁₉⁴⁻, VMo₅O₁₉⁵⁻ and V₂Mo₄O₁₉⁴⁻) from aqueous solutions. The isopolyanion solutions were characterized by UV-Vis and ⁵¹V NMR spectroscopy. Vanadium, vanadium–tungsten and vanadium–molybdenum precursors and catalysts were also characterized by UV-Vis (diffuse reflectance) and solid state ⁵¹V NMR spectroscopy. An improved selectivity to propene in the presence of tungsten and molybdenum in VO_x/γ-Al₂O₃ was observed and attributed to dilution of vanadium by tungsten or molybdenum oxides on the γ-Al₂O₃ surface.     

TiO2-SiO2 and V2O5/TiO2-SiO2 catalyst: Physico-chemical characteristics and catalytic behavior in selective catalytic reduction of NO by NH3

TiO₂-SiO₂ with various compositions prepared by the coprecipitation method and vanadia loaded on TiO₂-SiO₂ were investigated with respect to their physico-chemical characteristics and catalytic behavior in SCR of NO by NH₃ and in the undesired oxidation of SO₂ to SO₃, using BET, XRD, XPS, NH₃-TPD, acidity measurement by the titration method and activity test. TiO₂-SiO₂, compared with pure TiO₂, exhibits a remarkably stronger acidity, a higher BET surface area, a lower crystallinity of anatase titania and results in allowing a good thermal stability and a higher vanadia dispersion on the support up to high loadings of 15 wt% V₂O₅. The SCR activity and N₂ selectivity are found to be more excellent over vanadia loaded on TiO₂-SiO₂ with 10–20 mol% of SiO₂ than over that on pure TiO₂, and this is considered to be associated with highly dispersed vanadia on the supports and large amounts of NH₃ adsorbed on the catalysts. With increasing SiO₂ content, the remarkable activity decrease in the oxidation of SO₂ to SO₃, favorable for industrial SCR catalysts, was also observed, strongly depending on the existence of vanadium species of the oxidation state close to V⁴⁺ on TiO₂-SiO₂, while V⁵⁺ exists on TiO₂, according to XPS. It is concluded that vanadia loaded on Ti-rich TiO₂-SiO₂ with low SiO₂ content is suitable as SCR catalysts for sulfur-containing exhaust gases due to showing not only the excellent de-NO_x activity but also the low SO₂ oxidation performance.     

Surface characteristics and activity in selective oxidation of o-xylene of supported V2O5 catalysts prepared by standard impregnation and atomic layer deposition

Alumina-, silica-, and titania-supported vanadium oxide systems with V₂O₅ loadings ranging from 3 to 12 wt.%, corresponding to 0.02–0.09 V/(Al,Si,Ti) atomic ratios, were prepared by atomic layer deposition (ALD) and compared with the corresponding impregnated catalysts. The surface acidic properties of the supports and catalysts were investigated using ammonia adsorption microcalorimetry to determine the number and strength of the surface acid sites. Deposition of V₂O₅ on alumina and titania supports gave rise to catalysts with lower amounts of acid sites than the respective supports, while for the samples prepared on silica, an increase of the number of acid sites was observed after V₂O₅ deposition. As a common trend, the surface acid strength was greater for the ALD catalysts than for the impregnated ones, suggesting a stronger interaction of the VO species with the support centers, which act as electron attractor centers creating Lewis-like vanadium species. Redox cycles were performed, involving temperature programmed reduction (TPR) analyses separated by an oxidation treatment (TPO). The results evidenced the good reversibility of the redox behavior of the vanadium centers in every case, while significant differences were observed when comparing the temperatures of reduction (T_max). Lower T_max values were observed for the better dispersed vanadia catalysts. After reduction, the V centers had a final formal average oxidation state corresponding to +3 or less (+2.5 to +2). The reactivity of the vanadia systems was examined by measuring their performance for the oxidation of o-xylene to phthalic anhydride. Activity tests indicated the superior selectivity of the V₂O₅ systems based on the more acidic supports (Al₂O₃ and TiO₂). The nature of the support governed the activity, and the more concentrated catalysts gave rise to improved selectivity to phthalic anhydride.     

Ammoxidation of 3-picoline over V2O5/TiO2 (anatase) system I. Relationship between ammoxidation activity and oxidation state of vanadium

A series of titania (anatase)-supported vanadia catalysts ranging in V₂O₅ content from 0.4 to 9.9 mol% was prepared by wet impregnation technique, characterized by BET surface area measurement and X-ray diffraction, and evaluated for ammoxidation of 3-picoline. The average oxidation number of vanadium in the fresh and used catalysts was determined by titrimetric methods. The ammoxidation activity and the average oxidation number were observed to increase with vanadia loading up to 3.4 mol% in the catalyst which corresponds to a monolayer coverage. The phase transformation of anatase to rutile after the reaction was observed at a V₂O₅ loading of 5.9 mol%. The slow decrease of ammoxidation activity beyond 3.4 mol% V₂O₅ was attributed to the coverage of active monomeric VO_x species on the support by bulk vanadia and by other oxides, and also to compound formation with ammonia.     

Solid-state V NMR for characterization of vanadium-containing systems

This overview paper includes both published and original data of the current state of the field of ⁵¹V NMR in solid-state chemistry. Advantages and shortcomings of different NMR techniques in their applications to vanadium are discussed on the examples of their application to various vanadia based systems (including individual highly crystalline compounds, solid solutions, glasses, catalysts). New correlations between local structure of vanadium atoms and NMR parameters allowing to discriminate at least seven different types of vanadium sites (tetrahedral sites of Q⁰, Q¹ and Q² types; trigonal pyramids of 3=1 and 3=2 (V₂O₅ like) types; tetragonal pyramids of 4=1, 4=2 types) are proposed. It is demonstrated that competent combination of different NMR approaches permits now not only to describe different vanadium sites in highly crystalline and amorphous materials, but also to insight into the structural aspects of disorder in crystallinity as well as to reveal the behavior of different functional groups at elevated temperatures. The influence of low valence vanadium atoms on ⁵¹V NMR spectra is also discussed.     

Characterization and catalytic activity of Pd/V2O5/Al2O3 catalysts on benzene total oxidation

The role of vanadium oxide and palladium on the benzene oxidation reaction over Pd/V₂O₅/Al₂O₃ catalysts was investigated. The Pd/V₂O₅/Al₂O₃ catalysts were more active than V₂O₅/Al₂O₃ and Pd/Al₂O₃ catalysts. The increase of vanadium oxide content decreased the Pd dispersion and increased the benzene conversion. A strong Pd particle size effect on benzene oxidation reaction was observed. Although the catalysts containing high amount of V⁴⁺ species were more active, the Pd particle size effect was responsible for the higher activity.     

A comparative study of the partial oxidation of methane to formaldehyde on bulk and silica supported MoO3 and V2O5 catalysts

The mechanism of the partial oxidation of methane to formaldehyde with O₂ has been investigated on bulk and differently loaded silica supported (4–7 wt%) MoO₃ and (5–50 wt%) V₂O₅ catalysts at 600–650°C in a pulse reactor connected to a quadrupole mass spectrometer. The reaction rate and product distribution in the presence and in the absence of gas-phase O₂ have been evaluated. On bare SiO₂, low and medium loaded silica supported MoO₃ and V₂O₅ catalysts the reaction proceeds via a concerted mechanism involving the activation of gas-phase oxygen on the reduced sites of the catalyst surface as proved by the direct correlation between catalytic activity and density of reduced sites evaluated in steady-state conditions, while on highly loaded catalysts as well as on bulk MoO₃ and V₂O₅ the reaction rate drops dramatically and the reaction pathway via redox mechanism becomes predominant. The results indicate that the surface mechanism is essentially more effective than the redox mechanism enabling also a higher selectivity to HCHO.     

Selective oxidation of propylene to acrolein over supported V2O5/Nb2O5 catalysts: An in situ Raman, IR, TPSR and kinetic study

The vapor-phase selective oxidation of propylene (H₂CCHCH₃) to acrolein (H₂CCHCHO) was investigated over supported V₂O₅/Nb₂O₅ catalysts. The catalysts were synthesized by incipient wetness impregnation of V-isopropoxide/isopropanol solutions and calcination at 450 °C. The catalytic active vanadia component was shown by in situ Raman spectroscopy to be 100% dispersed as surface VO_x species on the Nb₂O₅ support in the sub-monolayer region (<8.4 V/nm²). Surface allyl species (H₂CCHCH_2*) were observed with in situ FT-IR to be the most abundant reaction intermediates. The acrolein formation kinetics and selectivity were strongly dependent on the surface VO_x coverage. Two surface VO_x sites were found to participate in the selective oxidation of propylene to acrolein. The reaction kinetics followed a Langmuir–Hinshelwood mechanism with first-order in propylene and half-order in O₂ partial pressures. C₃H₆-TPSR spectroscopy studies also revealed that the lattice oxygen from the catalyst was not capable of selectively oxidizing propylene to acrolein and that the presence of gas phase molecular O₂ was critical for maintaining the surface VO_x species in the fully oxidized state. The catalytic active site for this selective oxidation reaction involves the bridging VONb support bond.     

Thermal behaviour, redox properties, and catalytic performance of alkali-promoted V2O5 catalysts in the selective oxidation of p-methoxytoluene: a comparative study

Alkali-promoted V₂O₅ catalysts M–V₂O₅ (M=Li, K, Cs) were synthesised by impregnation of V₂O₅ with alkali sulphate solution. Pure V₂O₅ was used for comparison. X-ray diffraction, spectroscopic (FTIR), and thermoanalytical methods (STA/MS) have been used to characterise the phase composition, the adsorption properties, and the reducibility of the catalysts. The catalytic performance was proved using the oxidation of p-methoxytoluene (PMT) to p-methoxybenzaldehyde (PMBA) as test reaction. The surface acidity is lowered, but the reducibility is enhanced with increasing size and basic properties of the alkali cation. This leads to an increased adduct (PMT) adsorption and decreased product (PMBA) adsorption in the order V₂O₅2O₅K–V₂O₅2O₅. Consequently, the catalytic performance is improved in the same way. The formation of bronze phases at relative low temperatures in the case of K– and Cs–V₂O₅ stabilise V⁴⁺ oxidation state and improve the redox properties and consequently the catalytic results. The admixture of the non-reactive pyridine enhances the aldehyde selectivity by further lowering of the surface acidity. Additionally, pyridinium cations generated during catalytic reaction and incorporated into the formed alkali bronze phases stabilise these structures.     

Reactivity of V2O5&z.sbnd;WO3TiO2 de-NOx catalysts by transient methods

The reactivity of ternary V₂O₅&z.sbnd;WO₃TiO₂ de-NO_xing catalysts with compositions similar to those of commercial catalysts (WO₃ ca. 9% w/w, V₂O₅ < 2% w/w) is investigated by transient techniques (temperature programmed desorption, TPD; temperature programmed surface reaction, TPSR; and temperature programmed reaction, TPR). The results indicate that the reactivity of the ternary catalysts in the SCR reaction increases on increasing the vanadia loading, and that the ternary catalysts are more active than the corresponding binary vanadia-titania samples with the same V₂O₅ loading. Indeed the SCR reaction is monitored at lower temperatures and high NO conversions are also preserved at high temperatures. TPSR and TPR data show that at low temperatures the SCR reaction occurs via a redox mechanism that involves at first the participation of the catalyst lattice oxygen and then the reoxidation of the reduced sites by gas-phase oxygen. Based on TPSR and TPR data, the higher reactivity of the ternary catalysts has been related to their superior redox properties, in line with previous chemico-physical characterisation studies. The catalyst redox properties thus appear as a key-factor in controlling the reactivity of V₂O₅&z.sbnd;WO₃TiO₂ de-NO_xing catalysts at low temperatures. The results also show that at high temperatures the surface acidity plays an important role in the adsorption and activation of ammonia.     

Synergistic catalysis of carbon black oxidation by Pt with MoO3 or V2O5

A series of SiO₂-supported MoO₃, V₂O₅, and Pt catalysts were prepared for the study of model soot oxidation with simulated diesel exhaust gas. Composite samples of Pt with the metal oxides demonstrated higher oxidation activities than the single-component SiO₂-supported MoO₃, V₂O₅ or Pt catalysts in the absence of SO₂ in the reactant gas. Based on the effects of NO₂ on carbon oxidation, a synergistic reaction mechanism was suggested to explain the effects of combining Pt with the oxides: Pt catalyzes the oxidation of NO with gas phase O₂ to NO₂, while MoO₃ and V₂O₅ catalyze the oxidation of carbon with NO₂. Finally, the effects of SO₂ on the carbon oxidation reaction were examined and discussed.     

Characteristics of V2O5 supported on sulfated TiO2 for selective catalytic reduction of NO by NH3

V₂O₅ supported on sulfated TiO₂ catalyst was investigated by using Raman and infrared spectroscopies to examine the surface structure of vanadia and the hydroxyl groups of titania along with the sulfate species on the catalyst surface. The surface structure of vanadia plays a critical role, particularly for the reduction of NO by NH₃. The polymeric vanadate species on the catalyst surface is the active reaction site for this reaction system. The surface sulfate species enhanced the formation of the polymeric vanadate by reducing the available surface area of the catalyst. The formation of the polymeric vanadate species on the catalyst surface also depends on the number of hydroxyl groups on the support. Both the sulfate and the vanadate species strongly interacted with the hydroxyl groups on titania. The fewer the number of the hydroxyl sites on the catalyst surface became by increasing the calcination temperatures, the more the polymeric vanadate species formed. A model was proposed to elucidate the progressive alteration of the surface structure of vanadia by the amounts of V₂O₅ loadings and the sulfate species on the catalyst surface.     

SO2 resistant antimony promoted V2O5/TiO2 catalyst for NH3-SCR of NOx at low temperatures

To get the low temperature sulfur resistant V₂O₅/TiO₂ catalysts quantum chemical calculation study was carried out. After selecting suitable promoters (Se, Sb, Cu, S, B, Bi, Pb and P), respective metal promoted V₂O₅/TiO₂ catalysts were prepared by impregnation method and characterized by X-ray diffraction (XRD) and Brunner Emmett Teller surface area (BET-SA). Se, Sb, Cu, S promoted V₂O₅/TiO₂ catalysts showed high catalytic activity for NH₃ selective catalytic reduction (NH₃-SCR) of NO_x carried at temperatures between 150 and 400 °C. The conversion efficiency followed in the order of Se > Sb > S > V₂O₅/TiO₂ > Cu but Se was excluded because of its high vapor pressure. An optimal 2 wt% ‘Sb’ loading was found over V₂O₅/TiO₂ for maximum NO_x conversion, which also showed high resistance to SO₂ in presence of water when compared to other metal promoters. In situ electrical conductivity measurement was carried out for Sb(2%)/V₂O₅/TiO₂ and compared with commercial W(10%)V₂O₅/TiO₂ catalyst. High electrical conductivity difference (ΔG) for Sb(2%)/V₂O₅/TiO₂ catalyst with temperature was observed. SO₂ deactivation experiments were carried out for Sb(2%)/V₂O₅/TiO₂ and W(10%)/V₂O₅/TiO₂ at a temperature of 230 °C for 90 h, resulted Sb(2%)/V₂O₅/TiO₂ was efficient catalyst. BET-SA, X-ray photoelectron spectroscopy (XPS) and carbon, hydrogen, nitrogen and sulfur (CHNS) elemental analysis of spent catalysts well proved the presence of high ammonium sulfate salts over W(10%)/V₂O₅/TiO₂ than Sb(2%)/V₂O₅/TiO₂ catalyst.     

Effects of microwaves on selective oxidation of toluene to benzoic acid over a V2O5/TiO2 system

Two series of catalysts, V₂O₅/TiO₂ and modified V₂O₅/TiO₂, were prepared with a conventional impregnation method. They were tested in the selective oxidation of toluene to benzoic acid under microwave irradiation. The reaction conditions were optimized over V₂O₅/TiO₂. It was found that in the microwave catalytic process the optimum reactor bed temperature of the titled reaction decreases to 500 K (600 K in the conventional process). The modification of V₂O₅/TiO₂ with MoO₃, WO₃, Nb₂O₅ or Ta₂O₅, which has no negative influence on the reaction in the conventional catalytic process, can greatly promote the catalytic activities in the microwave process, leading to a high yield of benzoic acid (41%). The effects of microwave electromagnetic field on the catalysts are discussed.     

Characterization by solid state V NMR spectroscopy

The fresh catalyst V₂O₅–WO₃/TiO₂ and catalyst used in SCR for 9000 h have been studied by the solid state ⁵¹V NMR spectroscopy in static and MAS conditions. According to ⁵¹V NMR in both samples the majority of vanadium sites are in a distorted octahedral environment similar to that in V₂O₅. There is a strong interaction between vanadium oxide and the support, but the concentration of vanadium atoms strongly bound to the surface is very small and can be detected only in MAS NMR experiments or after removing the excess of V₂O₅. There is no influence of WO₃ additives on the structure of the particles of V₂O₅, whereas the influence on the structure of strongly bounded V cannot be excluded. Combination of static (wide line) and MAS NMR techniques permit the characterization of not only the structure of the vanadium species but also small changes in their local environment. Hence these experiments show that there are some distortions of the local environment of vanadium sites of the vanadium oxide particles compared with the polycrystalline V₂O₅; treatment by SCR increases these distortions.     

Deactivation patterns of Mo/Al2O3, Ni–Mo/Al2O3 and Ni–MoP/Al2O3 catalysts in atmospheric residue hydrodesulphurization

In the present work, a comparative study on the deactivation behavior of three types of industrial hydrotreating catalysts, namely, Mo/Al₂O₃, Ni–Mo/Al₂O₃ and Ni–MoP/Al₂O₃, that are used to promote primarily hydrodemetallization (HDM), hydrodesulphurization (HDS) and hydrodesulphurization + hydrodenitrogenation (HDS/HDN) reactions, respectively, in the first, second and third reactor of commercial atmospheric residue desulfurization (ARDS) units was carried out. The main objective of the study was to contribute to a better understanding of the relationship between catalyst type and catalyst deactivation patterns. The used catalysts from these experiments were fully characterized to determine the extent and the cause of deactivation. Special emphasis was paid to understanding the nature of the coke and metal deposition on the used catalysts by applying chemical analysis and various advanced analytical techniques, such as solid-state carbon-13 nuclear magnetic resonance spectroscopy (¹³C NMR), temperature-programmed oxidation (TPO), electron probe micro-analysis (EPMA), and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The results are discussed scientifically based on the physico–chemical properties of the three catalysts.     

Selective photo-oxidation of various hydrocarbons in the liquid phase over V2O5/Al2O3

More than 0.22 mmol of isolated VO₄ species of V₂O₅/Al₂O₃ exhibited the highest evolution of the partial oxidation products (alcohol and ketone) in the oxidation of cyclohexane and cyclopentane. The conversion of cyclohexane and the selectivity of the partial oxidation products were achieved to be 0.49% and 85% over 0.8 g of 3.5 wt.% V₂O₅/Al₂O₃, respectively, where the K/A ratio was 6.2. In addition, V₂O₅/Al₂O₃ can selectively oxidize various hydrocarbons in the liquid phase by the one-step oxygen atom insertion to CH bond. The order of priority was tertiary carbon > secondary carbon > primary carbon > benzene ring.     

Factors controlling the selectivity of V2O5 supported catalysts in the oxidative dehydrogenation of propane

The surface properties of a series of V₂O₅ catalysts supported on different oxides (Al₂O₃, H–Na/Y zeolite, MgO, SiO₂, TiO₂ and ZrO₂) were investigated by transmission electron microscopy and FTIR spectroscopy augmented by CO and NH₃ adsorption. In the case of the V₂O₅/SiO₂ system TEM images evidenced the presence of V₂O₅ crystallites, whereas such segregated phase was not observed for the other samples. VO_x species resulted widely spread on the surface of Al₂O₃, H–Na/Y zeolite, MgO and SiO₂, whereas on TiO₂ and ZrO₂ they are assembled in a layer covering almost completely the support. Furthermore, evidences for the presence in this layer of V–OH Brønsted acid sites close to the active centres were found. It is proposed that propene molecules primarily produced by oxydehydrogenation of propane can be adsorbed on this acid centres and then undergo an overoxidation by reaction with redox centres in the neighbourhood. This features could account for the low selectivity of V₂O₅/TiO₂ and V₂O₅/ZrO₂ catalysts.