Ternary VO-ligand-surface complexes on boehmite and noncrystalline aluminosilicates

Electron spin resonance (ESR) spectroscopy was used to characterize the ligand environment of VO²⁺ absorbed on boehmite and noncrystalline aluminosilicates. Boehmite possessed a relatively low capacity to chemisorb VO²⁺ at discrete sites at low pH, a fact attributed to the chemical inactivity of the dominant (020) surfaces of the mineral. The chemisorbed cation is rigidly bound by one or two surface oxyanions. Chemisorption on allophane produced slightly different ESR parameters for VO²⁺, a possible consequence of the participation of silanol groups in the metal-surface bond. Evidence for ternary surface complexes was seen upon the addition of phosphate to the VO²⁺-surface complexes, with changes occurring in the ESR spectrum of bound VO²⁺. Oxalate also appeared to perturb the ligand environment of sorbed VO²⁺, but other anionic species had little or no effect. The experimental results point to the coadsorption of a vanadyl-phosphate complex, in which both the VO²⁺ and the PO₄³⁻ are chemisorbed to surface Al atoms. The ESR spectra of VO²⁺ in model phosphate compounds are used to establish the effect of PO₄³⁻ coordination with VO²⁺ on the spectral parameters.     

Ternary VO2+-ligand-surface complexes on boehmite and noncrystalline aluminosilicates

Electron spin resonance (ESR) spectroscopy was used to characterize the ligand environment of VO²⁺ absorbed on boehmite and noncrystalline aluminosilicates. Boehmite possessed a relatively low capacity to chemisorb VO²⁺ at discrete sites at low pH, a fact attributed to the chemical inactivity of the dominant (020) surfaces of the mineral. The chemisorbed cation is rigidly bound by one or two surface oxyanions. Chemisorption on allophane produced slightly different ESR parameters for VO²⁺, a possible consequence of the participation of silanol groups in the metal-surface bond. Evidence for ternary surface complexes was seen upon the addition of phosphate to the VO²⁺-surface complexes, with changes occurring in the ESR spectrum of bound VO²⁺. Oxalate also appeared to perturb the ligand environment of sorbed VO²⁺, but other anionic species had little or no effect. The experimental results point to the coadsorption of a vanadyl-phosphate complex, in which both the VO²⁺ and the PO₄³⁻ are chemisorbed to surface Al atoms. The ESR spectra of VO²⁺ in model phosphate compounds are used to establish the effect of PO₄³⁻ coordination with VO²⁺ on the spectral parameters.     

Modified multiwalled carbon nanotubes as an electrode reaction catalyst for an all vanadium redox flow battery

Different modified multiwalled carbon nanotubes (MWCNTs) are prepared by heat treatments in the air and in the H₂SO₄?+?HNO₃ (1:1) mixed acids which are investigated by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, Brunaur–Emmett–Teller, and cyclic voltammetry measurements. The results show the physicochemical properties of MWCNTs change significantly after these different modification processes, especially the electrochemical catalytic activity towards the VO₂ ⁺/VO²⁺ and V³⁺/V²⁺ redox pairs. The MWCNTs treated in the air at 600 °C for 30 min shows better electrochemical performances for the VO₂ ⁺/VO²⁺ redox reactions (58.8 and ?32.4 μA for the oxidation and reduction peaks at 10 mV?s^?1, respectively) than any other samples. Compared with the V³⁺/V²⁺ redox couple, the VO₂ ^+/VO²⁺ redox reactions are more easily affected by the physicochemical property changes of the MWCNTs. The enhanced electrochemical catalytic activity of the modified MWCNTs is not only related to the surface oxygen content, but also to the specific surface area, conductivity and the unique structure variations of the MWCNTs. The investigation demonstrated that the modified MWCNTs have a promising future application in the vanadium redox flow battery.     

Catalytic performance of silica-supported chromium oxide catalysts in ethane dehydrogenation with carbon dioxide

The oxidative dehydrogenation of ethane into ethylene by CO₂ over a series of silica-supported chromium oxide catalysts was investigated. The results showed that the catalysts were effective for the reaction and CO₂ in the feed promoted the catalytic activity. The 5%Cr/SiO₂ catalyst exhibited the excellent performance with 30.7% ethane conversion and 96.5% ethylene selectivity at 700^oC. ESR and UV-DRS were used to probe the active sites and the species with high valent states (Cr⁵⁺ and/or Cr⁶⁺) were found to be important for the reaction.     

Direct Oxidation of Benzene to Phenol by Dioxygen over Nano-vanadium Oxide

Reducing regents, such as ascorbic acid, are needed for vanadium‐containing catalysts to catalyze the direct oxidation of benzene to phenol by dioxygen. Quadrivalent vanadium species, reduced from quinquevalent vanadium species, can activate dioxygen to produce active oxygen species, which is important for the reaction. The key step is to prepare more V⁴⁺‐containing catalysts. Here, VO_X‐C₁₆‐A was prepared in an acidic medium to produce more V⁴⁺ species. The results of XPS and XRD studies confirmed that the vanadium species in VO_X‐C₁₆‐A was mainly V⁴⁺ ions. The results of XRD and electron diffraction patterns revealed that VO_X‐C₁₆‐A consisted of tetragonal VO₂ and monoclinic VO₂. Morphology observations display that the VO_X‐C₁₆‐A is made of nanorod. Investigations into the performances of the catalysts showed that VO_X‐C₁₆‐A was reusable, producing a 1.9% conversion of benzene without reducing agent.     

CO Oxidation Promoted by the Gold Dimer in Au2VO3− and Au2VO4− Clusters

Investigations on the reactivity of atomic clusters have led to the identification of the elementary steps involved in catalytic CO oxidation, a prototypical reaction in heterogeneous catalysis. The atomic oxygen species O^.? and O^2? bonded to early‐transition‐metal oxide clusters have been shown to oxidize CO. This study reports that when an Au₂ dimer is incorporated within the cluster, the molecular oxygen species O₂^2? bonded to vanadium can be activated to oxidize CO under thermal collision conditions. The gold dimer was doped into Au₂VO₄^? cluster ions which then reacted with CO in an ion‐trap reactor to produce Au₂VO₃^? and then Au₂VO₂^?. The dynamic nature of gold in terms of electron storage and release promotes CO oxidation and O? O bond reduction. The oxidation of CO by atomic clusters in this study parallels similar behavior reported for the oxidation of CO by supported gold catalysts.     

Untersuchungen an katalytisch aktiven Oberflächenverbindungen. XIII. Struktur und katalytische Eigenschaften von Molybdän-oxid/SiO2-Katalysatoren

Studies on Catalytically Active Surface Compounds. XIII. Structure and Catalytic Properties of Molybdenum Oxide/SiO₂ Catalysts The catalytic properties of Mo oxide/SiO₂ catalysts in the selective oxidation of methanol to formaldehyde are described. It is shown that, independently on the preparation conditions, all catalysts showed relative high activity and selectivity values which were however, not constant during the reaction time. The high initial activity could be stabilized to a limited extent both by prereduction with methanol (but not with hydrogen) and by decreasing the oxygen concentration of the reaction gas. ESR measurements showed that in dependence on the means of reduction (methanol or hydrogen) two different coordinated Mo⁵⁺ ions were formed. Evidence was given by IR spectroscopy that prereduction in methanol caused the formation of methoxy groups stabilizing catalytically active Mo⁵⁺ ions. UV-Vis, ESCA, and electron microscopic measurements showed however, that further aggregation and formation of microcrystallites of MoO₃ took place during the catalytic reaction which caused the observed decrease of the activity.     

VO<Subscript>x</Subscript>/Zr–SBA-15 catalysts for selective oxidation of ethanol to acetaldehyde

Effect of zirconium presence in the silica framework and content and speciation of vanadium surface oxo-complexes on the catalytic behavior of VO_x/Zr–SBA-15 catalysts in oxidative dehydrogenation of ethanol was investigated. Experimental results bring evidence of successful incorporation of zirconium into ordered mesoporous silica framework with the preservation of ordered mesoporosity by hydrothermal template base synthesis method. The presence of zirconium in the SBA-15 framework increases reducibility of vanadium species and acidity of the catalysts. It is reflected in higher activity of vanadium species expressed as turn-over frequency (e.g., TOF of 20 h^?1 for 5%VO_x/Zr–SBA-15 sample in comparison with TOF of 12 h^?1 for 5%VO_x/SBA-15 sample) and also in significant decrease of selectivity to acetaldehyde (65% in comparison with 90% for mentioned samples) followed by increase in selectivity to ethylene (25% in comparison with 5%). This change in distribution of reaction products is related to stronger acidity character of surface OH groups and inhibition effect of formed water vapours on the oxidative dehydrogenation products (acetaldehyde). Catalytic data also reveal that oligomeric/polymeric tetrahedrally coordinated vanadium species exhibit higher activity in ethanol oxidative dehydrogenation than monomeric complexes. In addition, comparison of the catalytic performance of VO_x/Zr–SBA-15 catalysts with VO_x/SBA-15 catalysts showed that catalytic properties of VO_x/Zr–SBA-15 catalysts can be tuned by incorporation of controlled amount of zirconium into silica framework.     

Effect of Mg/Al atom ratio of support on catalytic performance of Co-Mo/MgO-Al2O3 catalyst for water gas shift reaction

Co-Mo-based catalysts supported on mixed oxide supports MgO-Al₂O₃ with different Mg/Al atom ratios for water gas shift reaction were studied by means of TPR, Raman, XPS and ESR. It was found that the octahedral Mo species in oxidized Co-Mo/MgO(x)-Al₂O₃ catalyst and the contents of Mo⁵⁺, Mo⁴⁺, S²⁻ and S²⁻₂ species in the functioning catalysts increased with increasing the Mg/Al atom ratio of the support under the studied experimental conditions. This is favorable for the formation of the active Co-Mo-S phase of the catalysts. Catalytic performance testing results showed that the catalysts Co-Mo/MgO-Al₂O₃ with the Mg/Al atom ratio of the support in the range of 0.475–0.525 exhibited optimal catalytic activity for the reaction.     

Hydroxyl‐Mediated Non‐oxidative Propane Dehydrogenation over VOx/γ‐Al2O3 Catalysts with Improved Stability

Supported vanadium oxides are one of the most promising alternative catalysts for propane dehydrogenation (PDH) and efforts have been made to improve its catalytic performance. However, unlike Pt‐based catalysts, the nature of the active site and surface structure of the supported vanadium catalysts under reductive reaction conditions still remain elusive. This paper describes the surface structure and the important role of surface‐bound hydroxyl groups on VO_x / γ‐Al₂O₃ catalysts under reaction conditions employing in situ DRIFTS experiments and DFT calculations. It is shown that hydroxyl groups on the VO_x /Al₂O₃ catalyst (V?OH) are produced under H₂ pre‐reduction, and the catalytic performance for PDH is closely connected to the concentration of V?OH species on the catalyst. The hydroxyl groups are found to improve the catalyst that leads to better stability by suppressing the coke deposition.     

Chlorisotopenseparation in einem heterogenen Elektrolytsystem in Abhängigkeit von Konzentration und Gegenion einer Fluoridlösung

Using the ESR method the formation of O^? and O₂^? on silica supported vanadiumphosphorus catalysts has been investigated. Studying catalysts with varying phosphorus contents it was found that the concentration of O^? and O₂^? can be related to the contents of phosphate ions. The admixture of increasing amounts of phosphorus obviously increases the reducibility of the catalysts and stabilizes the square-pyramidical coordination of V⁴⁺ ions. Comparing these results with activity and selectivity of the catalytic butene oxidation to maleic anhydride we point out that both the changed catalytic properties and the formation of oxygen radicals may be influenced by the same structural effects.     

Oxidative Desulfurization Activity of NIT Nitroxide Radical Modified Metallophthalocyanine

In the present study, metallophthalocyanines were modified with NIT nitroxide radicals through chemical bonds to prepare a series of metallophthalocyanines–NIT catalysts (MPcTcCl₈-NIT, M=Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺) applied for oxidative desulfurization of thiophene (T) in model fuel. The MPcTcCl₈-NIT catalysts were characterized by FTIR, UV-Vis, ESR, and XPS spectra. The oxidative desulfurization activity of MPcTcCl₈-NIT catalysts was studied in a biomimetic catalytic system using molecular O₂ as the oxidant. The MPcTcCl₈-NIT catalysts exhibited high catalytic activities for the oxidation of thiophene in model fuel. The desulfurization rate of ZnPcTcCl₈-NIT for thiophene reached to 99.61%, which was 20.53% higher than that of pure ZnPcTcCl₈ (79.08%) under room temperature and natural light. The results demonstrated that MPcTcCl₈-NIT catalysts could achieve more effective desulfurization rate under milder conditions than that of the metallophthalocyanines. The NIT nitroxide radicals also could improve the catalytic activity of metallophthalocyanine based on the synergistic oxidation effect. The stability experiments for ZnPcTcCl₈-NIT showed that the catalyst still had a high desulfurization rate of 92.37% after five times recycling. All these findings indicate that the application of MPcTcCl₈-NIT catalysts provides a potential new way for the desulfurization performance of thiophene in fuel.     

The role of V4+ ions in vanadium oxide catalysts I. Decomposition of 2-propanol

Decomposition of 2-propanol has been studied on vanadium pentoxide with MoO₃ and WO₃ additives. It has been observed that a small amount of the additives increases the dehydration activity of the catalysts, but at 5% or higher concentration, dehydration of 2-propanol decreases. The initial increase followed by a decrease in the dehydration activity with increased amount of additives is due to the change in the rate-determining step. Addition of MoO₃, WO₃, and alkali metal oxides to vanadium pentoxide has similar effects on the V⁴⁺ concentration and catalytic activity. Based on the results of the kinetic and ESR spectral studies, a scheme for the reaction has been proposed. It is concluded that the concentration of V⁴⁺ ion plays the crucial role in these catalysts. Deceased October 1979     

The Influence of Sulfate‐Doping on the Nature of V Sites in VOx/TiO2 Catalysts

EPR, UV/Vis and FTIR spectroscopy as well as thermal analysis (TA/MS) were applied to study the influence of sulfate species present in the anatase support on the specific nature of VO_x species in supported VO_x/TiO₂ catalysts. Those sulfate species modify the local structure of the supported vanadyl species and lead to the formation of two types of VO²⁺ sites instead of only one type being formed on sulfate‐free anatase. EPR and FTIR spectroscopic measurements revealed that a part of the VO²⁺ species are directly bound to the surface sulfate species. By TA/MS it was found that SO₂ is released at lower temperature from VO_x/TiO₂ in comparison to the vanadium‐free support. The direct bonding between sulfate and VO_x species stabilizes the latter on the surface of VO_x/TiO₂ resulting in three effects: 1) a higher V site dispersion in comparison to sulfate‐free TiO₂, 2) a better resistance of surface vanadyls against diffusion into the bulk of the support and 3) a much faster reoxidation of reduced V sites than observed on sulfate‐free TiO₂.     

Understanding the nature of vanadium species supported on activated carbon and its catalytic properties in the aerobic oxidation of aromatic alcohols

Vanadium oxide catalysts supported on activated carbon (V/AC) with V loadings ranging from 1 to 20 wt.% were prepared by a wet-impregnation method. Various physicochemical characterization techniques, including nitrogen physisorption, X-ray diffraction (XRD), Raman spectroscopy, X-ray absorption (XANES and EXAFS), X-ray photoelectron spectroscopy (XPS), and electron spin resonance (ESR), were employed to understand the nature of vanadium species on activated carbon. The results revealed that vanadium oxide mainly existed in a highly dispersed state for 10 wt.% or less vanadium loadings; a large amount of vanadium resulted in aggregated microcrystalline phase. Vanadium species on activated carbon surface showed a similar local coordination structure to that of NH₄VO₃ with a distorted tetrahedral symmetry at low vanadium loadings, whereas octahedral coordination was dominant at high vanadium loadings (>10 wt.%). All V/AC samples showed V⁵⁺ as the major oxidation state. Nevertheless, V⁴⁺ centered in a distorted tetrahedral symmetry could be detected at a vanadium loading greater than 4 wt.%. The catalytic activity for the benzyl alcohol oxidation largely depended on the dispersion, oxidation state, and local coordination of vanadium oxides on activated carbon. Highly dispersed vanadium (5+) species with a distorted tetrahedral coordination were postulated to account for the excellent catalytic performances of V/AC catalysts (TOF = 39.1 h^?1).     

The Effects of M2O3 on Stabilizing Monocopper over the Surface of Cu-ZnO-M2O3 Catalysts for Mathanol Synthesis

The effects of M₃O₃ (M = Al, Sc etc.) in Cu-ZnO-M₂O₃ catalysts on methanol synthesis at low pressure were studied with ESR, XPS and TPR spectroscopy. The results of ESR showed that the generation of monovalent cationic defects was because the valence state and electronic charge on the ZnO lattice lost their balance as M³⁺ doped into ZnO. The induced effect by Sc³⁺ is stronger than that by Al³⁺. The results of XPS and TPR indicated that the amount and stabilization of Cu⁺ on the surface of reduced copper-based catalyst and its catalytic activity were affected by the monovalent cationic defects on the surface of ZnO.     

Characterization and Dehydrogenation Activity of SBA-15 and HMS Supported Chromia Catalysts

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Cu-ETS-10催化NH3选择性还原NOx性能

采用离子交换法制备了Cu-ETS-10钛硅分子筛催化剂,该催化剂对于NH₃选择性催化还原（SCR）NO_x反应具有较高的催化活性、N₂选择性和抗SO₂性能.结果表明,Cu-ETS-10钛硅分子筛具有丰富的微孔结构和较高的比表面积（288-380m²/g）;原子发射光谱、程序升温还原技术和原位红外漫反射等表征结果表明,Cu在Cu-ETS-10钛硅分子筛中具有多种存在形态,其中Cu²⁺物种为Cu-ETS-10的活性中心,其含量随Cu含量的增加而先增后降,与催化活性的变化趋势一致.     

Formation of gels and gel-glasses in the VO2(V2O5)-SiO2 systems

Blue-coloured gels have been prepared in the VO₂-SiO₂ system up to 80 mol% VO₂ by sol-gel technology using TEOS and aqueous solutions of VOSO₄·5H₂O. It is established by means of VIS and ESR spectra that at low temperatures VO²⁺ complexes are formed. An oxidation of V⁴⁺ has taken place with increasing temperature, and V₂O₅ and cristobalite have been separated. Silica gel glasses stable up to 800°C have been obtained from gels containing 1–3 mol% VO₂.