Vanadia/titania catalysts for gas phase partial toluene oxidation: Spectroscopic characterisation and transient kinetics study

Formation of vanadia species during the calcination of ball milled mixture of V₂O₅ with TiO₂ was studied by Raman spectroscopy in situ and at ambient conditions. It is found that calcination in air leads to fast (1–3 h) spreading of vanadia over TiO₂ followed by a slower process leading to the formation of a monolayer vanadia. The calcinated catalyst showed higher activity during toluene oxidation than the uncalcinated one, but the selectivity towards C₇-oxygenated products (benzaldehyde and benzoic acid) remains unchanged. The activity of the catalysts is ascribed to the formation of vanadia species in the monolayer. The details of the parallel–consecutive reaction scheme of toluene oxidation are presented from steady-state and transient kinetics studies. Different oxygen species seem to participate in the deep and partial oxidation of toluene. Coke formation was observed during the reaction presenting an average composition C_2nH_1.1n. The amount of coke on the catalyst was not dependent on the calcination step and the vanadium content in the catalyst. Coke formation was seen to be responsible for the deactivation of the catalyst.     

Transient kinetics of toluene partial oxidation over V/Ti oxide catalysts

Transient kinetics in the toluene oxidation over V/Ti oxide catalysts prepared by grafting and impregnation have been compared. V⁴⁺ cations are supposed to be the sites for the formation of electrophilic oxygen species participating in deep oxidation. Another oxygen species (probably nucleophilic) present on the oxidised catalyst surface are responsible for benzaldehyde formation. Selectivity of 80–100% can be obtained during the initial period of the reaction on the grafted catalysts in the presence of gaseous oxygen and during the interaction of toluene (without O₂ in the mixture) with partially reduced catalysts.     

Deactivation kinetics of V/Ti-oxide in toluene partial oxidation

Deactivation kinetics of a V/Ti-oxide catalyst was studied in partial oxidation of toluene to benzaldehyde (BA) and benzoic acid (BAc) at 523–573 K. The catalyst consisted of 0.37 monolayer of VO_x species and after oxidative pre-treatment contained isolated monomeric and polymeric metavanadate-like vanadia species under dehydrated conditions as was shown by FT Raman spectroscopy. Under the reaction conditions via in situ DRIFTS fast formation of adsorbed carboxylate and benzoate species was observed accompanied by disappearance of the band of the monomeric species (2038 cm⁻¹) (polymeric species were not controlled). Slow accumulation of maleic anhydride, coupling products and/or BAc on the surface caused deactivation of the catalyst during the reaction. Temperature-programmed oxidation (TPO) after the reaction showed formation of high amounts of CO, CO₂ and water. Rate constants for the steps of the toluene oxidation were derived via mathematical modelling of reaction kinetics at low conversion and constant oxygen/toluene ratio of 20:1. The model allows predicting deactivation dynamics, steady-state rates and selectivity. The highest rate constant was found for the transformation of BA into BAc explaining a low BA yield in the reaction.     

Selective catalytic reduction of nitric oxide over vanadia grafted on titania. Influence of vanadia loading on structural and catalytic properties of catalysts

The selective catalytic reduction (SCR) of NO by NH₃ has been studied over vanadia/ titania catalysts prepared by selective immobilization of vanadyl alkoxide species on two structurally different titania supports. The loading of vanadia was varied from 1.8 to 7.5 ,mol V⁵⁺ per m² surface area. Comparative kinetic measurements at 150 °C show that the NO turnover frequencies increase by more than an order of magnitude when the vanadia loading is increased from 1.8 to 3 mol V⁵⁺/m². In the region of lower SCR activity, i.e. at lower coverages ( 2 mol V⁵⁺/m²), small clusters and ribbons of vanadia are detected in the Raman spectra, whereas at loadings where maximum NO turnovers are achieved ( 3 mol V⁵⁺/m²) the prevalent vanadia species are well-developed two-dimensional vanadia layers bound to titania.     

Atomic layer deposition and surface characterization of highly dispersed titania/silica-supported vanadia catalysts

The atomic layer deposition (ALD) method using surface-saturating gas–solid reactions was applied to modify a highly dispersed titania/silica support with submonolayer amounts of vanadia. The surface properties and acidity of the V₂O₅/TiO₂/SiO₂ materials were examined relatively to the corresponding silica and titania supported samples. The surface area, porosity and amorphous nature of the support were not affected by vanadia, which was present in the form of highly dispersed isolated species on titania/silica, as detected by Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Microcalorimetry measurements showed that the vanadia species interacted with both the titania overlayer and the silica surface, confirming the observed V–O–Ti bonding Raman features. The surface reactivity towards ammonia was strongly enhanced by the modification, as probed by adsorption microcalorimetry and XPS. The superiority of the ALD method for the preparation of bilayered vanadia/titania/silica catalysts was demonstrated by examining for comparison a series of aqueous-phase impregnated catalysts.     

Possible effects of site isolation in antimony oxide-modified vanadia/titania catalysts for selective oxidation of o-xylene

Titania-supported vanadia catalysts were modified by addition of antimony oxide for application in o-xylene selective oxidation to phthalic anhydride. It was shown that active and selective catalysts can be prepared by ball-milling mixtures of powders of TiO₂, V₂O₅and Sb₂O₃followed by calcination. X-ray photoelectron spectroscopy proves the formation of highly dispersed overlayers of vanadium oxide and antimony oxide, in which V⁵⁺is partially reduced to lower oxidation states and Sb³⁺is partially oxidized to Sb⁵⁺. Antimony oxide segregated into the outermost surface layers. It is therefore inferred that the presence of the antimony oxide modifier spatially separates V–O species and leads to site isolation which may be responsible for the positive effect of the modifier for the catalyst's selectivity.     

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.     

Partial oxidation of methane over ruthenium catalysts

The catalytic partial oxidation of methane with oxygen to produce synthesis gas was studied under a wide range of conditions over supported ruthenium catalysts. The microreador results demonstrated the high activity of ruthenium catalysts for this reaction. A catalyst having as little as 0.015% (w/w) Ru on Al₂O₃ gave a higher synthesis gas selectivity than a catalyst having 5% Ni on SiO₂. XANES measurements for fresh and used catalyst samples confirmed that ruthenium is reduced from ruthenium dioxide to ruthenium metal early during the experiments. Ruthenium metal is thus the active element for the methane partial oxidation reaction.     

NO reduction with NH3 over chromia–vanadia catalysts supported on TiO2: an in situ Raman spectroscopic study

In situ Raman spectroscopy was used for studying the ternary 2% CrO₃–6% V₂O₅/TiO₂ catalyst, for which a synergistic effect between vanadia and chromia leads to enhanced catalytic performance for the selective catalytic reduction (SCR) of NO with NH₃. The structural properties of this catalyst were studied under NH₃/NO/O₂/N₂/SO₂/H₂O atmospheres at temperatures up to 400 °C and major structural interactions between the surface chromia and vanadia species are observed. The effects of oxygen, ammonia, water vapor and sulfur dioxide presence on the in situ Raman spectra are presented and discussed.     

In situ IR,Raman, and UV-Vis DRS spectroscopy of supported vanadium oxide catalysts during methanol oxidation

The application of in situ Raman, IR, and UV-Vis DRS spectroscopies during steady-state methanol oxidation has demonstrated that the molecular structures of surface vanadium oxide species supported on metal oxides are very sensitive to the coordination and H-bonding effects of adsorbed methoxy surface species. Specifically, a decrease in the intensity of spectral bands associated with the fully oxidized surface (V⁵⁺) vanadia active phase occurred in all three studied spectroscopies during methanol oxidation. The terminal V = O (∼1030 cm⁻¹) and bridging V–O–V (∼900–940 cm⁻¹) vibrational bands also shifted toward lower frequency, while the in situ UV-Vis DRS spectra exhibited shifts in the surface V⁵⁺ LMCT band (>25,000 cm⁻¹) to higher edge energies. The magnitude of these distortions correlates with the concentration of adsorbed methoxy intermediates and is most severe at lower temperatures and higher methanol partial pressures, where the surface methoxy concentrations are greatest. Conversely, spectral changes caused by actual reductions in surface vanadia (V⁵⁺) species to reduced phases (V³⁺/V⁴⁺) would have been more severe at higher temperatures. Moreover, the catalyst (vanadia/silica) exhibiting the greatest shift in UV-Vis DRS edge energy did not exhibit any bands from reduced V³⁺/V⁴⁺ phases in the d–d transition region (10,000–30,000 cm⁻¹), even though d–d transitions were detected in vanadia/alumina and vanadia/zirconia catalysts. Therefore, V⁵⁺ spectral signals are generally not representative of the percent vanadia reduction during the methanol oxidation redox cycle, although estimates made from the high temperature, low methoxy surface coverage IR spectra suggest that the catalyst surfaces remain mostly oxidized during steady-state methanol oxidation (15–25% vanadia reduction). Finally, adsorbed surface methoxy intermediate species were easily detected with in situ IR spectroscopy during methanol oxidation in the C–H stretching region (2800–3000 cm⁻¹) for all studied catalysts, the vibrations occurring at different frequencies depending on the specific metal oxide upon which they chemisorb. However, methoxy bands were only found in a few cases using in situ Raman spectroscopy due to the sensitivity of the Raman scattering cross-sections to the specific substrate onto which the surface methoxy species are adsorbed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Characterization of surface species on V/SiO2 and V,Na/SiO2 and their role in the partial oxidation of methane to formaldehyde

Silica-supported vanadium (1–8 wt%) and vanadium (5 wt%)-sodium (0.4 wt%) catalysts have been characterized by laser Raman spectroscopy, temperature-programmed reduction, X-ray photoelectron spectroscopy, NO + NH₃ rectangular pulses and oxygen chemisorption. The presence of different vanadium species was correlated with activity and selectivity during the methane partial oxidation reaction. The pre-impregnation of the silica support with sodium favors vanadium dispersion, but strongly diminishes V=O concentration due to the formation of orthovanadate-like compounds. As a result of these modifications, methane conversion is strongly inhibited while formaldehyde decomposition is favored.     

Partial oxidation of methane to synthesis gas over Rh-hexaaluminate-based catalysts

The partial oxidation of methane to synthesis gas over catalysts consisting of Rh supported on hexaaluminates (BaAl₁₂O₁₉, CaAl₁₂O₁₉ and SrAl₁₂O₁₉) was investigated at atmospheric pressure and high reactant dilution in order to compare their performances within the kinetic-controlling regime. Comparison with the results obtained over a commercial Rh/-Al₂O₃ system indicates that hexaaluminate catalysts are active and selective in this reaction. Despite of the higher surface area of the support, hexaaluminate-supported catalysts were found less stable, active and selective than an -Al₂O₃-supported catalyst.     

Partial oxidation of13C-labeled ethylene in methane over Ca/Ni/K catalysts

The relative reactivity of ethane and ethylene compared to methane over the Ca/Ni/K catalyst was determined. The reactivities are in the order of ethylene > ethane methane. The catalyst was also studied using temperature-programmed reaction, desorption and decomposition.     

The effect of potassium on the selective oxidation ofn-butane and ethane over Al2O3-supported vanadia catalysts

The catalytic properties of undoped and K-doped (K/V atomic ratio of 0.5) Al₂O₃-supported vanadia catalysts (4.5 wt% of V₂O₅) for the oxidation ofn-butane and ethane were studied. Isolated tetrahedral V⁵⁺ species are mainly observed in both undoped and K-doped samples. The incorporation of potassium decreases both the reducibility of surface vanadium species and the number of surface acid sites. Potassium-free vanadium catalysts show a high selectivity during the oxidative dehydrogenation (ODH) of ethane but a low selectivity during the ODH ofn-butane. However, the presence of potassium on the vanadium catalysts strongly influences their catalytic properties, increasing the selectivity to C₄-olefins fromn-butane and decreasing the selectivity to ethene from ethane. The role of the acid-base characteristics of catalysts on selectivity to ODH reactions is proposed.On leave from the Department of Industrial Chemistry and Materials, V. le Risorgimento 4, 40136 Bologna, Italy.     

Catalytic performance of vanadyl pyrophosphate in the partial oxidation of toluene to benzaldehyde

Vanadyl pyrophosphate catalysts were generated by dehydrating VOHPO₄·(1/2)H₂O at different temperatures and duration of the dehydration procedure. The as-synthesised materials were characterised by X-ray diffractometry, FTIR spectroscopy and temperature-programmed reduction. The prolongation of the formation period at higher temperatures led to improved crystallinity and lower BET surface areas of the vanadyl pyrophosphate specimens and, additionally, a significantly impeded reducibility of the vanadyl sites was observed. The catalytic performance of the samples was tested in the partial oxidation of toluene to benzaldehyde. The obtained results revealed an increasing benzaldehyde selectivity with improved catalyst crystallinity. In situ FTIR and ESR spectroscopy were used to throw more light on the interaction of the toluene–air feed with the surface of the catalyst. This revised version was published online in July 2006 with corrections to the Cover Date.     

Oxidation of toluene to benzaldehyde over VSb0.8Ti0.2O4 Effect of the operating conditions

In the present work, the kinetic toluene oxidation on VSb_0.8Ti_0.2O₄ based catalyst was studied. A reaction network, which involves three steps: the partial oxidation of toluene to benzaldehyde, a consecutive oxidation of benzaldehyde to carbon oxides and a parallel oxidation of toluene to carbon oxides, was proposed. The kinetic parameters were estimated assuming the redox mechanism proposed by Mars and van Krevelen. The products distribution was strongly affected by the reaction temperature. The adjustment of activation energies for total and partial oxidation of toluene led to the same values. The activation energy for the benzaldehyde oxidation was lower than the one for its formation.     

Wet air oxidation of p-coumaric acid over promoted ceria catalysts

The catalytic wet air oxidation (WAO) of p-coumaric acid (PCA) has been investigated over Fe- and Zn-promoted ceria catalysts. The catalysts have been prepared by the coprecipitation method and have been characterized by X-ray diffraction (XRD), BET surface area, SEM–EDX and temperature programmed reduction (TPR). The oxidation reaction was carried out in a batch reactor under an air pressure of 2 MPa and in the temperature range 353–403 K. Fe-CeO₂ catalysts, with 20–50 mol% of iron, were found more effective than the unpromoted and Zn-promoted ceria catalysts. On the basis of characterization data, it has been suggested that the higher activity of the Fe-promoted catalysts is related to the modification of the structural and redox properties of the ceria oxide catalyst on addition of iron.     

Micellar catalysis for partial oxidation of toluene to benzoic acid in supercritical CO2: effects of fluorinated surfactants

One of the key hindrances on development of solid catalysts containing cobalt species for partial oxidation of organic molecules at mild conditions in conventional liquid phase is the severe metal leaching. The leached soluble Co species with a higher degree of freedom always out-performs those of solid supported Co species in oxidation catalysis. However, the homogeneous Co species concomitantly introduces separation problems. We have recently reported for the first time, a new oxidation catalyst system for the oxidation of organic molecules in supercritical CO₂ using the principle of micellar catalysis. [CF₃(CF₂)₈COO]₂Co·xH₂O (the fluorinated anionic moiety forms aqueous reverse micelles carrying water-soluble Co²⁺ cations in scCO₂) was previously shown to be extremely active for the oxidation of toluene in the presence of sodium bromide in water–CO₂ mixture, giving 98% conversion and 99% selectivity to benzoic acid at 120 °C. In this study, we show that the effects of varying the type of surfactant counterions and the length of the surfactant chains on catalysis. It is found that the use of [CF₃(CF₂)₈COO]₂Mg·yH₂O/Co(II) acetate is as effective as the [CF₃(CF₂)₈COO]₂Co·xH₂O and the fluorinated chain length used has a subtle effect on the catalytic rate measured. It is also demonstrated that this new type of micellar catalyst in scCO₂ can be easily separated via CO₂ depressurisation and be reused without noticeable deactivation.     

Partial oxidation of propylene MoO3/iron tellurite catalysts

The catalytic behaviour of the series Fe₂(TeO₃)₃ + × % MoO₃ (X = 0–30 mol. %) in the oxidation of propylene in the gaseous phase has been studied. It has been found that the addition of Mo0₃ to the iron tellurite activates the reaction towards the partial oxidation to acrolein. From the characterisation of solids it is possible to conclude that the addition of MoO₃ promotes the crystallinity of the iron tellurite. On the other hand, surface studies of the catalysts show that depending on the MoO₃ loading, this component is present in various states which contribute in different ways to the catalytic action. Some explanations for the observed behaviour are proposed.     

Co-Mo催化剂上甲苯气相选择氧化制苯甲醛的研究

制备一系列的负载型Co-Mo-O/Al2O3-USY催化剂,并用于甲苯的气相选择氧化制苯甲醛。结果表明:在空速6000h-1,空气/甲苯摩尔比100,MoO3负载量为10.00%(质量分数),在480℃反应,得到甲苯转化率43.76%,苯甲醛选择性25.97%,苯甲醛收率为11.37%的结果。并用X射线衍射、X射线光电子能谱等测试手段,对催化剂进行结构表征。