IR spectroscopic analysis of isotopic C2-products of the oxidative coupling of CH4+CD4mixture over manganese oxide catalyst

The composition and structure of the product of mixture CH₄+CD₄ oxidative coupling over natural manganese mineral catalyst at 3% and 25% methane conversion in redox mode at 850°C have been determined by IR-Absorption- Reflection spectroscopy technique. At low methane conversion there were ethanes: H₃OCH₃, H₃OCD₃, D₃CCD₃ and ethylenes: H₂CCH₂, H₂CCD₂, D₂CCD₂ only The data obtained showed that the reaction proceeds by gas-phase CH₃, CD₃ radicals coupling and ethane is the primary C₂-product and ethylene is produced by gas-phase conversion of ethane.     

Production of hydrogen via partial oxidation of methanol over Au/TiO2 catalysts

Selective production of hydrogen by partial oxidation of methanol (CH₃OH + (1/2)O₂ → 2H₂ + CO₂) over Au/TiO₂ catalysts, prepared by a deposition–precipitation method, was studied. The catalysts were characterized by XRD, TEM, and XPS analyses. TEM observations show that the Au/TiO₂ catalysts exhibit hemispherical gold particles, which are strongly attached to the metal oxide support at their flat planes. The size of the gold particles decreases from 3.5 to 1.9 nm during preparation of the catalysts with the rise in pH from 6 to 9 and increases from 2.9 to 4.3 nm with the rise in calcination temperature up to 673 K. XPS analyses demonstrate that in uncalcined catalysts gold existed in three different states: i.e., metallic gold (Au⁰), non-metallic gold (Au^δ+) and Au₂O₃, and in catalysts calcined at 573 K only in metallic state. The catalytic activity is strongly dependent on the gold particle size. The catalyst precipitated at pH 8 and uncalcined catalysts show the highest activity for hydrogen generation. The partial pressure of oxygen plays an important role in determining the product distribution. There is no carbon monoxide detected when the O₂/CH₃OH molar ratio in the feed is 0.3. Both hydrogen selectivity and methanol conversion increase with increasing the reaction temperature. The reaction pathway is suggested to consist of consecutive methanol combustion, partial oxidation and steam reforming.     

Characterization of self-standing Ti-containing porous silica thin films and their reactivity for the photocatalytic reduction of CO2 with H2O

Self-standing porous silica thin films with different pore structures were synthesized by a solvent evaporation method and used as photocatalysts for the photocatalytic reduction of CO₂ with H₂O at 323 K. UV irradiation of these Ti-containing porous silica thin films in the presence of CO₂ and H₂O led to the formation of CH₄ and CH₃OH as well as CO and O₂ as minor products. Such thin films having hexagonal pore structure exhibited higher photocatalytic reactivity than the Ti-MCM-41 powder catalyst even with the same pore structure. From FTIR investigations, it was found that these Ti-containing porous silica thin films had different concentrations of surface OH groups and showed different adsorption properties for the H₂O molecules toward the catalyst surface. Furthermore, the concentration of the surface OH groups was found to play a role in the selectivity for the formation of CH₃OH.     

Selective formation of CH3OH in the photocatalytic reduction of CO2 with H2O on titanium oxides highly dispersed within zeolites and mesoporous molecular sieves

Highly dispersed titanium oxide catalysts have been prepared within zeolite cavities as well as in the zeolite framework and utilized as photocatalysts for the reduction of CO₂ with H₂O to produce CH₄ and CH₃OH at 328 K. In situ photoluminescence, ESR, diffuse reflectance absorption and XAFS investigations indicate that the titanium oxide species are highly dispersed within the zeolite cavities and framework and exist in tetrahedral coordination. The charge transfer excited state of the highly dispersed titanium oxide species play a significant role in the reduction of CO₂ with H₂O with a high selectivity for the formation of CH₃OH, while the catalysts involving the aggregated octahedrally coordinated titanium oxide species show a high selectivity to produce CH₄, being similar to reactions on the powdered TiO₂ catalysts. Ti-mesoporous molecular sieves exhibit high photocatalytic reactivity for the formation of CH₃OH, its reactivity being much higher than the powdered TiO₂ catalysts. The addition of Pt onto the highly dispersed titanium oxide catalysts promotes the charge separation which leads to an increase in the formation of CH₄ in place of CH₃OH formation.     

NO reduction by CH4 in the presence of O2 over La2O3 supported on Al2O3

Dispersing La₂O₃ on δ- or γ-Al₂O₃ significantly enhances the rate of NO reduction by CH₄ in 1% O₂, compared to unsupported La₂O₃. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La₂O₃ precursor used, the pretreatment, and the La₂O₃ loading. The most active family of catalysts consisted of La₂O₃ on γ-Al₂O₃ prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m²) occurred between the addition of one and two theoretical monolayers of La₂O₃ on the γ-Al₂O₃ surface. The best catalyst, 40% La₂O₃/γ-Al₂O₃, had a turnover frequency at 700°C of 0.05 s⁻¹, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La₂O₃/Al₂O₃ catalysts exhibited stable activity under high conversion conditions as well as high CH₄ selectivity (CH₄ + NO vs. CH₄ + O₂). The addition of Sr to a 20% La₂O₃/γ-Al₂O₃ sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO⁼₄ to the latter Sr-promoted La₂O₃/Al₂O₃ catalyst decreased activity although sulfate increased the activity of Sr-promoted La₂O₃. Dispersing La₂O₃ on SiO₂ produced catalysts with extremely low specific activities, and rates were even lower than with pure La₂O₃. This is presumably due to water sensitivity and silicate formation. The La₂O₃/Al₂O₃ catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications.     

Relative rates of various steps of NO–CH4–O2 reaction catalyzed by Pd/H-ZSM-5

Reaction mechanism of the reduction of nitrogen monoxide by methane in an oxygen excess atmosphere (NO–CH₄–O₂ reaction) catalyzed by Pd/H-ZSM-5 has been studied at 623–703 K in the absence of water vapor, in comparison with the mechanism for Co-ZSM-5. Kinetic isotope effect for the N₂ formation in NO–CH₄–O₂ vs. NO–CD₄–O₂ reactions was 1.65 at 673 K and decreased with a decrease in the reaction temperature. In addition, H–D isotopic exchange took place significantly in NO–(CH₄+CD₄)–O₂ reaction. These results are in marked contrast with the case of Co-ZSM-5, for which the C–H dissociation of methane is the only rate-determining step, and show that the C–H dissociation is slow but not the only rate-determining step in the case of Pd/H-ZSM-5.

A reaction scheme was proposed, in which the relative rates of the three steps ((i)–(iii) below) vary depending on the reaction conditions.

Further, in contrast to Co-ZSM-5, NO_x–CH₄–O₂ reaction was much slower than CH₄–O₂ reaction for Pd/H-ZSM-5; the presence of NO_x retards the reaction of CH₄ over the latter catalyst, while it accelerates the reaction over the former. It is suggested that CH₄ is activated directly by the Pd atoms in the case of Pd/H-ZSM-5, but by NO₂ strongly adsorbed on Co ion for Co-ZSM-5. The reaction order of the NO–CH₄–O₂ reaction with respect to NO pressure was consistent with this mechanism; 1.05 for Pd/H-ZSM-5 and 0.11 for Co-ZSM-5.     

PERMEATION THROUGH KAPTON® POLYIMIDE AT ELEVATED TEMPERATURES

The permeabilities of CH₄, CO₂, CH₃OH, H₂O, O₂, and CO through films of Kapton® polyimide were measured at temperatures of 50, 100, 150, 200, and 250°C and pressures below 1 atm. Apparent activation energies for the permeation of the pure components ranged from 31.6kJ mol^-1 for CH₄ to nearly 0 for H₂O under the conditions studied. The ideal permselectivity for methanol relative to methane decreased from over 100 to under 10 as the temperature was increased from 50 to 250°C.     

Comparison of catalytic activity and selectivity of Pd/(OSC + Al2O3) and (Pd + OSC)/Al2O3 catalysts

The effect of the Pd addition method into the fresh Pd/(OSC + Al₂O₃) and (Pd + OSC)/Al₂O₃ catalysts (OSC material = Ce_xZr_1−xO₂ mixed oxides) was investigated in this study. The CO + NO and CO + NO + O₂ model reactions were studied over fresh and aged catalysts. The differences in the fresh catalysts were insignificant compared to the aged catalysts. During the CO + NO reaction, only small differences were observed in the behaviour of the fresh catalysts. The light-off temperature of CO was about 20 °C lower for the fresh Pd/(OSC + Al₂O₃) catalyst than for the fresh (Pd + OSC)/Al₂O₃ catalyst during the CO + NO + O₂ reaction. For the aged catalysts lower NO reduction and CO oxidation activities were observed, as expected. Pd on OSC-containing alumina was more active than Pd on OSC material after the agings. The activity decline is due to a decrease in the number of active sites on the surface, which was observed as a larger Pd particle size for aged catalysts than for fresh catalysts. In addition, the oxygen storage capacity of the aged Pd/(OSC + Al₂O₃) catalyst was higher than that of the (Pd + OSC)/Al₂O₃ catalyst.     

Methanol partial oxidation on carbon-supported Pt and Pd catalysts

Different Pt and Pd catalysts supported on an activated carbon were prepared by using different metal precursors. Prepared catalysts were pretreated at 400 °C under different atmospheres to decompose the precursor compound and reduce the metal. After pretreatments, the supported catalysts were characterized by H₂ chemisorption, X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy to know their metal dispersion, particle size, distribution and oxidation state. Afterwards, the catalysts were tested in methanol partial oxidation with two different O₂/CH₃OH molar ratios. Results obtained in this reaction were compared with those obtained for methanol decomposition in inert atmosphere. For Pt catalysts, there was an increase in methanol conversion and hydrogen production and a decrease in carbon monoxide production under oxidizing conditions. Both methanol conversion and partial oxidation reactions appear to be sensitive to Pt particle structure in the particle size range studied. Results obtained under oxidizing conditions differed between Pd and Pt catalysts. Finally, catalytic activity in methanol partial oxidation was more affected by Pt than Pd particle size in the size range studied.     

Regeneration of S-poisoned Pd/Al2O3 catalysts for the combustion of methane

Regeneration of S-poisoned Pd/Al₂O₃ catalysts for the abatement of methane emissions from natural gas vehicles was addressed in this work.

Investigations were devoted to determine the temperature threshold allowing for catalyst reactivation under different CH₄ containing atmospheres. Under lean combustion conditions in the presence of excess O₂, partial regeneration took place only above 750 °C after decomposition of stable sulphate species adsorbed on the support. Short CH₄-reducing, O₂-free pulses led to partial catalyst reactivation already at 550 °C and to practically complete regeneration at 600 °C. Also in this case reactivation was associated with SO₂ release due to the decomposition of stable support sulphates likely promoted by CH₄ activation onto the reduced metallic Pd surface. Rich combustion pulses with CH₄/O₂ = 2 were equally effective to CH₄-reducing pulses in catalyst regeneration.

These results suggest that a regeneration strategy based on periodical natural gas pulses fed to the catalyst by a by-pass line might be efficient in limiting the effects of S-poisoning of palladium catalysts for the abatement of CH₄ emissions from natural gas engine.     

贵金属催化剂用于低浓度甲烷的去除

制备不同负载量的Pd基和Pt基催化剂,建立催化剂活性评价装置,考察贵金属Pd和Pt负载量对甲烷转化率的影响,结果表明,甲烷转化率最高的Pd和Pt负载质量分数分别为1.25%和2%,相同负载质量分数0.1%时,Pd基催化剂的甲烷转化率优于Pt基催化剂。催化剂的BET比表面积大小不能反映催化剂的催化活性,二者之间无线性关系。     

Carbon formation and its influence on ethanol steam reforming over Ni/Al2O3 catalysts

Ethanol steam reforming was studied over Ni/Al₂O₃ catalysts. The effect of support (- and γ-Al₂O₃), metal loading and a comparison between conventional H₂ reduction with an activation method employing a CH₄/O₂ mixture was investigated. The properties of catalysts were studied by N₂ physisorption, X-ray diffraction (XRD) and temperature programmed reduction (TPR). After activity tests, the catalysts were analyzed by scanning electron microscopy (SEM) and thermogravimetric analysis (TG/DTA). Ni supported on γ-Al₂O₃ was more active for H₂ production than the catalyst supported on -Al₂O₃. Metal loading did not affect the catalytic performance. The alternative activation method with CH₄/O₂ mixture affected differently the activity and stability of the Ni/γ-Al₂O₃ and the Ni/-Al₂O₃ catalyst. This activation method increased significantly the stability of Ni/-Al₂O₃ compared to H₂ reduction. SEM and TG/DTA analysis indicate the formation of filamentous carbon during the CH₄/O₂ activation step, which is associated with the increasing catalyst activity and stability. The effect of temperature on the type of carbon formed was investigated; indicating that filamentous coke increased activity while encapsulating coke promoted deactivation. A discussion about carbon formation and the influence on the activity is presented.     

Structure and methanol activation: niobia promoted Pt/Al2O3 catalysts

Distinction between geometric and ligand effects has been studied by the infrared study of CO chemisorption on four catalyst samples modified by niobia. According to earlier studies the metal-support interface plays a crucial role in the CH₃OH + D₂ reaction. Platinum and niobia content, oxidative-reductive treatment and chloride content has a great influence of the niobia decorating Pt surface. High temperature reduction does not effect niobia-free sample, while niobia addition decreases the bridged/linear ratio of the adsorbed CO, especially in the SMSI state. Simultaneously the peak positions are shifting towards higher frequencies. Both geometric effect of decoration and ligand effect are observed.

The observed effect has been further supported by XRD data for the platinum crystallite sizes and a quantitative parameter for the characterization of SMSI is proposed     

Lean reduction of NO by C3H6 over Ag/alumina derived from Al2O3, AlOOH and Al(OH)3

The effectiveness of Ag/Al₂O₃ catalyst depends greatly on the alumina source used for preparation. A series of alumina-supported catalysts derived from AlOOH, Al₂O₃, and Al(OH)₃ was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible (UV–vis) spectroscopy, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, O₂, NO + O₂-temperature programmed desorption (TPD), H₂-temperature programmed reduction (TPR), thermal gravimetric analysis (TGA) and activity test, with a focus on the correlation between their redox properties and catalytic behavior towards C₃H₆-selective catalytic reduction (SCR) of NO reaction. The best SCR activity along with a moderated C₃H₆ conversion was achieved over Ag/Al₂O₃ (I) employing AlOOH source. The high density of Ag–O–Al species in Ag/Al₂O₃ (I) is deemed to be crucial for NO selective reduction into N₂. By contrast, a high C₃H₆ conversion simultaneously with a moderate N₂ yield was observed over Ag/Al₂O₃ (II) prepared from a γ-Al₂O₃ source. The larger particles of Ag_mO (m > 2) crystallites were believed to facilitate the propene oxidation therefore leading to a scarcity of reductant for SCR of NO. An amorphous Ag/Al₂O₃ (III) was obtained via employing a Al(OH)₃ source and 500 °C calcination exhibiting a poor SCR performance similar to that for Ag-free Al₂O₃ (I). A subsequent calcination of Ag/Al₂O₃ (III) at 800 °C led to the generation of Ag/Al₂O₃ (IV) catalyst yielding a significant enhancement in both N₂ yield and C₃H₆ conversion, which was attributed to the appearance of γ-phase structure and an increase in surface area. Further thermo treatment at 950 °C for the preparation of Ag/Al₂O₃ (V) accelerated the sintering of Ag clusters resulting in a severe unselective combustion, which competes with SCR of NO reaction. In view of the transient studies, the redox properties of the prepared catalysts were investigated showing an oxidation capability of Ag/Al₂O₃ (II and V) > Ag/Al₂O₃ (IV) > Ag/Al₂O₃ (I) > Ag/Al₂O₃ (III) and Al₂O₃ (I). The formation of nitrate species is an important step for the deNO_x process, which can be promoted by increasing O₂ feed concentration as evidenced by NO + O₂-TPD study for Ag/Al₂O₃ (I), achieving a better catalytic performance.     

CO oxidation over promoted Pt catalysts

A study of CO oxidation by O₂ over Pt catalysts, promoted by MnO_x and CoO_x, is described. The activities of Pt/SiO₂, Pt/MnO_x/SiO₂ and Pt/CoO_x/SiO₂ are compared with commercial Pt/Al₂O₃, Pt/Rh/Al₂O₃ and Pt/CeO_x/Al₂O₃ catalysts. Since these catalysts differ in dispersion and weight loading of platinum, the turnover frequencies are also compared. The following order in activity in CO oxidation after a reductive pretreatment is found: Pt/CoO_x/SiO₂ > Pt/MnO_x/SiO₂, Pt/CeO_x/Al₂O₃ > Pt/Al₂O₃, Pt/Rh/Al₂O₃, Pt/SiO₂. Over Pt/CoO_x/SiO₂ CO is already oxidised at room temperature. Possible models to account for the high activity of Pt/CoO_x/SiO₂ in the CO/O₂ reaction are presented and discussed. Partially reduced metal oxides are necessary to increase the activity of the Pt/CoO_x/SiO₂, Pt/MnO_x/SiO₂ or Pt/CeO_x/Al₂O₃ catalysts. It was shown that mild ageing treatments did not affect the activity of the Pt/CoO_x/SiO₂ catalyst in CO oxidation.     

Effect of Rh loading on the performance of Rh/Al2O3 for methane partial oxidation to synthesis gas

Catalytic performance for partial oxidation of methane (POM) to synthesis gas was studied over the Rh/Al₂O₃ catalysts with Rh loadings between 0.1 and 3 wt%. It was found that the ignition temperature of POM reaction increased with the decreasing of the Rh loadings in the catalysts. For the POM reaction over the catalysts with high (≥1 wt%) Rh loadings, steady-state reactivity was observed. For the reaction over the catalysts with low (≤0.25 wt%) Rh loadings, however, oscillations in CH₄ and reaction products (CO, H₂, and CO₂) were observed. Comparative studies using H₂-TPR, O₂-TPD and high temperature in situ Raman spectroscopy techniques were carried out in order to elucidate the relation between the redox property of the Rh species in the Rh/Al₂O₃ with different Rh loadings and the performance of the catalysts for the reaction. Three kinds of oxidized rhodium species, i.e. the rhodium oxide species insignificantly affected by the support (RhO_x), that intimately interacting with the Al₂O₃ surface (RhⁱO_x) and the Rh(AlO₂)_y species formed by diffusion of rhodium oxides in to sublayers of Al₂O₃ [C.P. Hwang, C.T. Yeh, Q.M. Zhu, Catal. Today, 51 (1999) 93.], were identified by H₂-TPR and O₂-TPD experiments. Among them, the first two species can be easily reduced by H₂ at temperature below 350 °C, while the last one can only be reduced by H₂ at temperature above 500 °C. The ignition temperatures of POM reaction over the catalysts are closely related to the temperature at which most of the RhO_x and RhⁱO_x species can be reduced by CH₄ in the reaction mixture. Compared to the Rh/Al₂O₃ with high Rh loadings, the catalysts with low Rh loadings contain more RhⁱO_x species which possess stronger RhO bond strength and are more difficult to be reduced than RhO_x by the reaction mixture. Higher temperature is therefore required to ignite the POM reaction over the catalysts with lower Rh loadings. The oscillation during the POM reaction over the Rh/Al₂O₃ with low Rh loadings can be related to the behaviour of Rh(AlO₂)_y species in the catalyst switching cyclically from the oxidized state to the reduced state during the reaction.     

Complete oxidation of methane at low temperature over Pt and Pd catalysts for the abatement of lean-burn natural gas fuelled vehicles emissions: influence of water and sulphur containing compounds

The catalytic activity of fresh Pd and Pt catalysts supported on γ-alumina in the complete oxidation of CH₄ traces under lean-burn conditions was studied in the presence or the absence of water or H₂S. Steam-aged catalysts were also studied in order to simulate long-term ageing in real lean-burn natural gas fuelled vehicles (NGVs) exhaust conditions. Without water or H₂S added to the feed, Pd catalysts exhibit a superior catalytic activity in methane oxidation compared to Pt ones, whatever the catalysts were fresh or aged. The addition of 10 vol.% water vapour to the feed strongly affects the activity of the fresh Pd catalyst, thus being only slightly more efficient than the fresh Pt one. H₂S has a strong poisoning effect on the catalytic activity of Pd catalysts, while Pt catalysts are more resistant. The fresh H₂S-poisoned Pd/Al₂O₃ catalyst was studied by TPD in O₂/He. Poisoning species decompose above 873 K as SO₂ and O₂ in relative concentrations consistent with the decomposition of surface sulphate species. However, a treatment in O₂/He at temperatures as high as 923 K does not allow the complete regeneration of the catalytic activity of H₂S-poisoned Pd/Al₂O₃. A mechanism involving the poisoning of PdO by sulphate species is proposed. Different diffusion processes by which these sulphate species can migrate back and forth between PdO and the support, depending on the experimental conditions, are suggested.     

A comparative study of Ag/Al2O3 and Cu/Al2O3 catalysts for the selective catalytic reduction of NO by C3H6

The selective catalytic reduction (SCR) of NO by C₃H₆ in excess oxygen was evaluated and compared over Ag/Al₂O₃ and Cu/Al₂O₃ catalysts. Ag/Al₂O₃ showed a high activity for NO reduction. However, Cu/Al₂O₃ showed a high activity for C₃H₆ oxidation. The partial oxidation of C₃H₆ gave surface enolic species and acetate species on the Ag/Al₂O₃, but only an acetate species was clearly observed on the Cu/Al₂O₃. The enolic species is a more active intermediate towards NO + O₂ to yield—NCO species than the acetate species on the Ag/Al₂O₃ catalyst. The Ag and Cu metal loadings and phase changes on Al₂O₃ support can affect the activity and selectivity of Ag/Al₂O₃ and Cu/Al₂O₃ catalysts, but the formation of enolic species is the main reason why the activity of the Ag/Al₂O₃ catalyst for NO reduction is higher than that of the Cu/Al₂O₃ catalyst.     

锆基双金属氧化物催化剂硫中毒的研究

在工业二氧化碳加氢制甲醇过程中,硫化氢气体的引入将对该过程中使用的催化剂活性及稳定性带来负面的影响。基于此,采用微反应合成法成功制备了InZrO_x和ZnZrO_x锆基催化剂,并研究了在二氧化碳加氢反应中,硫化氢气体对锆基催化剂的结构性质及其催化性能的影响规律。结果表明,在T=573 K、p=3.0 MPa和GHSV=18 000 mL/(g_cat·h)条件下,仅通入二氧化碳/氢气反应气时,InZrO_x和ZnZrO_x催化剂的二氧化碳转化率和甲醇选择性分别为7.2%、9.3%和93%、92%。在二氧化碳/氢气原料气中通入体积分数为5×10^-3硫化氢气体时,InZrO_x和ZnZrO_x催化剂的二氧化碳转化率和甲醇选择性都降为0,这主要是因为硫化氢气体占据了氧空位,导致锆基双金属氧化物催化剂硫中毒失活。当停止通硫化氢气体时,InZrO_x和ZnZrO_x催化剂的二氧化碳转化率和甲醇选择...     

Physico-chemical properties of V-Sb-oxide systems and their catalytic behaviour in oxidative dehydrogenation of light paraffins

Catalysts prepared as bulk VSb_0.1O_x and supported V₂O₅/Al₂O₃, V₂O₅-Sb₂O₃/Al₂O₃ and Sb₂O₃/Al₂O₃ (containing 0.5, 1 or 2 theoretical monolayers of V₂O₅ or Sb₂O₃) were tested in the oxidative dehydrogenation of iso-butane at 550°C in i-C₄H₁₀:O₂:He=20:10:70 gas mixture. Fresh and used catalysts were characterised by BET, XRD and XPS. Reactivity and thermochemistry of active oxygen taking part in the redox cycle with ethane and hydrogene were studied using in situ differential scanning calorimetry. Temperature-programmed desorption of O₂ in He flow was also investigated and in situ DRIFT was applied to investigate surface species of the catalysts in flows of i-C₄H₁₀, O₂ and i-C₄H₁₀/O₂ mixture. Supported VSb_yO_x catalysts are more active and selective than bulk one. V-only supported catalysts display a high efficiency due to the high reactivity of VOX-species. In bulk catalyst, the surface is enriched with antimony. In supported samples, the surfaces V/Sb are close to the calculated ones. In the presence of antimony, the amount of active oxygen species and their reactivity in redox transformation is improved. The rates of vanadium reduction and reoxidation are also higher. Compared to V-only catalysts, supported V-Sb-catalysts display a lower coking activity and higher on-stream stability.