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.     

Deposition and characterisation of vanadium oxide thin films: Linking single crystal and supported catalyst

Thin films can make a useful link between single crystal and supported vanadium oxide. The deposition of vanadium oxide thin films with physical vapour deposition techniques ensures clean and highly controllable synthesis. The resulting material is easily accessed with surface sensitive techniques. On flat TiO₂ anatase substrates, XPS–XPD and UPS indicated that the vanadia deposition was epitaxial, and fully oxidised if performed in situ. A step closer to typical industrial catalysts was achieved by sputter deposition onto sub-millimetre inert particles. In addition to surface characterisation, these model particle catalysts allow use in reactors for catalytic testing under relevant process conditions. On both silica and titania supports, sputter deposited vanadia of varying thickness proved to be equally well dispersed. Oxidative dehydrogenation (ODH) activity was higher over vanadia/titania (anatase) than over vanadia/silica, demonstrating the synergetic interaction between anatase and vanadia. Highest activity in alkane ODH was observed for vanadia a few monolayers thick, supported on titania-coated particles.     

On the intrinsic activity of vanadium centres in the oxidative dehydrogenation of propane over V–Ca–O and V–Mg–O catalysts

The performance of V–Ca–O catalysts for the oxidative dehydrogenation of propane has been studied for the first time, being compared with that of similar V–Mg–O catalysts, and their differences are interpreted in terms of their physico-chemical properties. The VCaO catalyst showed the same initial selectivity to propene as the most selective VMgO composition, but it decreased faster with increasing propane conversion. Vanadium species present in the catalyst surface were different for the two supports: isolated V⁵⁺ tetrahedra on CaO and magnesium orthovanadate and pyrovanadate on MgO. The intrinsic activity of isolated vanadium centres in the surface of the V–Ca–O catalyst was more than one order of magnitude higher than that of dimeric or polymeric tetahedral species in the magnesium-containing catalysts. This revised version was published online in August 2006 with corrections to the Cover Date.     

Selective catalytic reduction of NO with NH3 over Nb2O5-promoted V2O5/TiO2 catalysts

In contrast to previous claims, the addition of niobia to catalysts containing vanadia supported on titania resulted in much enhanced activity for low-temperature SCR of NO with NH₃ only at low vanadia loadings. Niobia promoted catalysts could also be demonstrated to show higher selectivities to N2, especially at high temperatures and low vanadia loading. This enhancement of the activity cannot be explained only on the basis of the observation that niobia stabilized the surface area of the catalyst: calculations of the activation energy suggest that a different mechanism of the reaction may be at work at low vanadia loadings.     

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.     

Vanadia/silica model catalyst: AFM and XPS investigation of morphological and chemical changes occurring upon exposure to different gas atmospheres

A model vanadia/silica interface has been prepared by vapour deposition of vanadium-oxy-triisopropoxide onto the native oxide layer of a silicon wafer. The VO _x /SiO₂/Si model system has been used to investigate the morphological and chemical changes occurring with vanadia/silica catalysts when they are exposed to different gas atmospheres. Atomic force microscopy and X-ray photoelectron spectroscopy have been used to follow these changes. The studies show that exposure of the vanadia/silica interface to conditions prevailing during the selective reduction of NO by NH₃ results in temperature dependent morphological changes, while the oxidation states of the vanadia species reflected by the ratio V(III)/V(V) change only little during the surface reconstruction.     

Monitoring Aging and Deactivation of Emission Abatement Catalysts for Selective Catalytic Reduction of NOx

Titania/vanadia, zeolite, and noble metal catalysts are utilized for selective catalytic reduction (SCR) of NO _x using ammonia as the reductant in different temperature ranges. Studies of aging have been carried out to probe deactivation rates and mechanisms. Periodic laboratory testing of samples of NO _x reduction catalysts from multi-layer reactors, such as those utilized at electric power plants, allows prediction of catalyst life-times. Testing has been carried out under protocol conditions with monolith, plate-type, and pelleted catalysts so that relative NO reduction rates can be compared, with or without the presence of SO₂. The catalysts were analyzed by surface analysis techniques, including electron microscopy and X-ray photoelectron spectroscopy, to probe surface morphology, loss of active components, presence of poisons, and blocking of pores and active sites by ammonium bisulfate to determine the dominant mode(s) of gradual deactivation.     

Theoretical Insight into the Nature of Ammonia Adsorption on Vanadia-Based Catalysts for SCR Reaction

Density functional theory (DFT) calculations were carried out on monomeric and oligomeric vanadium oxide clusters to probe the factors leading to the formation of NH₄ species from the adsorption of ammonia. The interaction of ammonia with monomeric vanadium oxide clusters leads to the formation of hydrogen-bonded NH₃ species, with energy changes for ammonia adsorption near -50 kJ/mol. The interaction of ammonia with oligomeric vanadium oxide clusters leads to the formation of bidentate NH_4 species, where the ammonium cation is coordinated between two V=O groups on adjacent vanadium cations. The energy change for ammonia adsorption in this mode is near -100 kJ/mol. Adsorption of ammonia as NH₄ species was not observed when the oligomeric vanadium oxide clusters were reduced by addition of hydrogen atoms, i.e., in clusters where the formal oxidation state of the vanadium cations was 4+. Based on our findings, a model for the generation of Brönsted acidity through the interaction of vanadium oxide oligomers with the titanium oxide support is proposed.     

Long-term stability of the V2O5/Al2O3 catalyst for the selective reduction of nitrogen oxides

Changes of the V₂O₅/Al₃O₃ catalyst aged for up to 10 years under real conditions of the selective catalytic reduction of NO _x by ammonia (SCR) at the tail gases of the nitric acid plant were characterized by⁵¹V NMR spectroscopy, porosimetry, temperature programmed reduction (TPR) and catalytic activity measurements. The catalytic activity and the redox properties of the catalyst were found intact. Only small variations of the ratio of the octahedral and tetrahedral vanadia species were documented by⁵¹V NMR on aged catalyst.     

Optimization of V2O5–MgO/TiO2 catalyst for the oxidative dehydrogenation of propane effect of magnesia loading and preparation procedure

The effect of magnesia loading and preparation procedure of vanadia on titania catalysts on the physicochemical characteristics and the performance in propane oxidative dehydrogenation were investigated. A series of magnesia promoted vanadia catalyst (5 wt% V₂O₅) with varying amounts of MgO (1.9--10 wt%) were synthesized by synchronous and sequential deposition on titania support. The catalysts were characterized using several techniques (BET, XRD, H₂-TPR and NH₃)-TPD). Both MgO loading and preparation procedure affect the catalyst surface properties and the behavior in the oxidative dehydrogenation of propane. Magnesia addition results in drastic increase in propene selectivity, while the effect on activity is negative. The activity is inversely related with the magnesia loading. Deposition of V₂O₅ on previously prepared MgO/TiO₂ presents a beneficial effect in the activity of the sample. The role of acidity and reducibility is explored. There is no correlation between reducibility and activity of the catalysts, whereas the acidity seems to influence the catalytic performance. Catalyst containing 5 wt% V₂O₅ and 1.9 wt% MgO prepared by sequential deposition of V₂O₅ on already doped with MgO titania exhibits the most interesting results.