Liquid-Liquid Extraction of Vanadium(V) and Niobium(V) with Tris(2-ethylhexyl)phosphate: Mutual Separation of Vanadium(V), Niobium(V), and Tantalum(V), and Analysis of Steel Samples

Abstract

Tris(2-ethylhexyl)phosphate (TEHP) dissolved in toluene is used for selective extraction of vanadium(V) and niobium(V) from hydrochloric and hydrobromic acid solution. Vanadium is determined spectrophotometrically after backextraction from TEHP, whereas unstripped niobium is determined in the TEHP phase with thiocyanate. The probable extractable species is VOCl₃·2TEHP or NbOCl₃·2TEHP/NbOBr₃·2TEHP. The method permits mutual separation of vanadium(V), niobium(V), and tantalum(V), and provides analysis of vanadium and niobium in alloys with a high degree of accuracy and precision.     

Influence of preparation method on the performance of vanadia-niobia catalysts for the oxidative dehydrogenation of propane

The influence of various preparation methods on the performance of V-Nb-0 catalysts has been investigated. It was found that the activity and selectivity of a vanadium site depend on the nature of the neighbouring atoms. Vanadium neighbours provide activity, while niobium neighbours provide selectivity. Careful preparation of these catalysts ensures a homogeneous distribution and good mixing of the vanadium and niobium. It was also found that the vanadium becomes mobile upon reduction and this results in better distribution of vanadium in used catalysts.     

In situ TPR/TPO-Raman studies of dispersed and nano-scaled mixed V-Nb oxides on alumina

Various catalysts containing niobium and vanadium oxides supported on alumina were prepared by wet impregnation via aqueous solution using several precursors. The total loading of V and Nb oxides were below their dispersion limit on alumina. Vanadyl sulfate, ammonium metavanadate and ammonium niobate(V) oxalate were the precursors for supported vanadia and niobia. The reduction/oxidation properties were studied by conventional TPR/TPO and TPR/TPO-Raman. Surface vanadium oxide species tend to increase their polymerization degree upon TPR/TPO cycles. A broad weak feature near 900 cm⁻¹ appears associated to V³⁺–O–Al³⁺ bond vibration in the reduced vanadia-alumina catalysts. Niobia appears to retard vanadia reduction. Regarding supported niobia, a fraction of surface niobia is significantly more reducible than surface vanadia and another fraction is significantly less reducible. The more reducible niobia appears associated to an incipient Nb–Al–O phase that may account for a fluorescence background observed in the Raman spectra. The less reducible niobia phases appears associated to dispersed niobium oxide species on alumina. Niobium has an effect on vanadia reduction profiles in VNb/Al₂O₃ system.     

Niobiosilica Materials as Attractive Supports for Sb–V–O Catalysts

Since niobium species have been described as being able to increase the catalytic properties of the Sb?CV?CO catalytic system, the main objective of the present paper is to design a non ordered-mesoporous Nb-containing material useful to be used as a support for this kind of catalysts. Such a material has been used as support for Sb?CV?CO active phases and the catalysts have been characterized and tested for the propane ammoxidation reaction. For comparative purposes, and in order to evaluate the role of niobium species, the study has been also performed with a support without niobium. The results have shown how the incorporation of niobium species into the support matrix with the procedure described here leads to the formation of a very promising catalytic support. The Nb species incorporated into the support cooperate with vanadium species of the SbVOx active phase increasing its performance for nitrile insertion into propane. Since Nb is a common additive that improves the catalytic behavior of different catalytic systems, the mesoporous Nb-containing support described in the present paper could be useful for other catalysts and/or catalytic processes.     

Oxidation of organosulfur compounds by hydrogen peroxide in the presence of niobium and vanadium peroxo complexes

New niobium(V) peroxo complexes containing aspargine and Schiff base ligands were synthesized, and their structures were solved by IR, NMR, and mass spectrometric methods. They were found to be catalytically active for the peroxidation of methyl phenyl sulfide and benzothiophene to the corresponding sulfoxide and sulfones. It was shown that vanadium(V) peroxo complexes with the same ligands are less active in the oxidation of methyl phenyl sulfide than the niobium complexes.     

Electrodeposition of refractory carbide coatings from fluoride melts

Experimental studies relevant to the electrodeposition of the carbides of vanadium, niobium, titanium, and zirconium are reported. These focus on choices of suitable metal precursors, their solubility and reducibility. The state of knowledge in the field is summarized.     

Recent topics of research and development of catalysis by niobium and tantalum oxides

Current topics of catalysts containing niobium and tantalum, especially in the field of solid acid catalysis and selective oxidation of hydrocarbons are reviewed. Hydrated niobium oxide and hydrated tantalum oxide are highly acidic. Hydrated niobium oxide is active for the hydration of ethene to ethanol, and Nb–W mixed metal oxide is more active for the reaction. Acid properties of tantalum oxide are changed by being supported on SiO₂. Ta oxide/SiO₂, prepared by the chemical reaction between tantalum alkoxide and surface hydroxyl groups of SiO₂, is active and selective for the gas phase Beckmann rearrangement of cyclohexanoneoxime to caprolactam. Niobium oxide and tantalum oxide easily react with many other oxides to form mixed metal oxide phases with complex structure. Mixed metal oxide catalysts, containing molybdenum, vanadium, certain elements together with niobium are active for the selective oxidation of hydrocarbons. Especially, the selective oxidation of propane by such mixed metal oxide catalysts has been paid attention. Additionally, recent progress of environmental catalysts, promoted by niobium and tantalum compounds, namely catalysts for the pollution abatement is reviewed.     

Formation of Zircon from Zirconium Dioxide and Silicon Dioxide in the Presence of Vanadium Pentoxide

The high-temperature formation of zircon from zirconium dioxide and silicon dioxide in the presence of vanadium pentoxide was studied. A reaction between zirconium dioxide and vanadium pentoxide appeared to take place at about 730°C. That reaction product then reacted with silicon dioxide to form zircon. The experiments suggest that such zircon contains a few per cent of tetravalent vanadium in solid solution and has a light blue color. It appeared that the end product under equilibrium conditions would be pure zirconium silicate since vanadium pentoxide or tetroxide was liberated under prolonged heating. Zircon also formed from silicon dioxide and zirconium dioxide in the presence of niobium or tantalum pentoxide.     

A convenient, general synthesis of carbide nanofibres via templated reactions on carbon nanotubes in molten salt media

Carbide nanofibres were synthesized by reaction of various transition metals with carbon nanotubes using a molten LiCl-KCl-KF salt system as a reaction medium. Metal sources included titanium, zirconium, hafnium, vanadium, niobium and tantalum powders. Multi-walled carbon nanotubes were used both as a carbon source and also as a template for the preparation of titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide and tantalum carbide nanofibres. Generally, the carbide products were characterized by scanning electron microscopy, transmission electron microscopy, selected-area electron diffraction and electron energy loss spectroscopy. The polycrystalline carbide nanofibres produced in these reactions have a similar morphology to that of their multi-walled carbon nanotube precursors. However, when using titanium mixed with titanium dioxide as a titanium source, both polycrystalline and straight, single crystal titanium carbide nanofibres are formed.     

Molecular design of supported niobium oxide catalysts

The current investigation demonstrates that it is possible to molecularly design supported niobium oxide catalysts with the assistance of molecular characterization methods such as Raman spectroscopy. The formation and location of the surface niobium oxide species are controlled by the surface hydroxyl chemistry, and the surface niobium oxide species are located in the outermost layer of the catalysts as an overlayer. The catalyst composition is a critical parameter since it affects the presence of different niobium oxide species (several different surface species and crystalline phases), and the reactivity also varies somewhat with surface niobium oxide coverage. The preparation method is not a critical parameter since it does not appear to influence the structure or reactivity of the surface niobium oxide species. However, for silica supported niobium oxide catalysts the preparation method does affect the amount of niobium oxide that can be dispersed as a two-dimensional overlayer. Calcination temperature is an important parameter that controls the activation and deactivation of the supported niobium oxide catalysts, but calcination temperature is not critical if moderate temperatures, 400–500°C, are used. The specific oxide support is a critical parameter since it dramatically affects the reactivity of the surface niobium oxide species and determines if the surface niobium oxide site is active for redox or acid catalysis. Thus, the critical parameters that affect the catalytic properties of the supported niobium oxide catalysts are the specific oxide support and catalyst composition.     

Inhibition of field crystallization of anodic niobium oxide by incorporation of silicon species

The present work demonstrates effective inhibition of field crystallization of amorphous anodic niobium oxide by incorporation of silicon species from substrate. The field crystallization, detrimental for capacitor application of niobium, occurs during anodizing of magnetron sputtered niobium at 100 V in 0.1 mol dm⁻³ ammonium pentaborate electrolyte at 333 K, while amorphous structure of the anodic oxide is totally retained during anodizing of magnetron sputtered Nb–12 at%Si. Even after prior thermal treatment in air, which accelerates field crystallization of anodic oxide on niobium, no crystallization occurs on the Nb–12 at%Si. Through examination of the crystallization behaviours of anodic films formed on a thin Nb–12 at%Si layer superimposed on a niobium layer as well as on a thin niobium layer superimposed on an Nb–12 at%Si layer, it has been confirmed that air-formed oxide or thermal oxide becomes a nucleation site for crystallization. Modification of the air-formed or thermal oxide by incorporation of silicon species inhibits the nucleation of crystalline oxide. The modification, however, does not influence the growth of crystalline oxide. The growth is suppressed by continuous incorporation of silicon species into anodic film from the substrate during anodizing.     

Effect of Modifiers on the Reactivity of Cr2O3/Al2O3 and Cr2O3/TiO2 Catalysts for the Oxidative Dehydrogenation of Propane

Chromium oxide supported on alumina and titania supports was modified with oxides of sodium, vanadium and molybdenum. The modified and unmodified chromium oxide catalysts were characterized by several techniques. The presence of surface chromium oxide and surface molybdenum and vanadium oxide species was detected in the unmodified and molybdenum and vanadium oxide modified supported chromium oxide catalysts. The reducibility (T_max and H/Cr ratio) of the surface chromium species was not affected for the vanadium and molybdenum oxide modified catalysts; however, the reducibility changed noticeably for sodium modified supported chromium oxide catalysts. Studies of the reactivity of the ODH of propane revealed the effect of modifiers on the reactivity properties of the surface chromium oxide species. The activity and propene selectivity decreased for sodium modified supported chromium oxide catalysts. However, the activity increased for vanadium oxide modified catalysts and was similar for molybdenum oxide modified catalysts irrespective of the support. The propene selectivity was higher for molybdenum oxide modified chromium oxide catalysts. However, the propene selectivity for vanadium oxide modified catalysts depends on the support since it appears that the inherent selectivity of the surface vanadium oxide species is reflected.     

介孔磷酸盐分子筛上钒物种的引入方式及其对丙烷氧化脱氢 催化性能的影响

以溶剂挥发诱导自组装法(evaporation–induced self–assembly，EISA)合成的有序磷酸盐介孔分子筛Na_0.1Zr_0.9PO为载体，分别采用掺杂和浸渍两种方式引入过渡金属钒作为活性物种，制备了一系列不同钒含量的催化剂样品。通过小角X射线衍射、N₂吸附-脱附和透射电镜表征了所制备样品的孔道结构，采用Raman光谱着重研究了不同方式引入的钒物种在Na_0.1Zr_0.9PO上的存在状态，并将催化剂上钒物种的存在状态与其在丙烷氧化脱氢反应中的催化性能相关联，探讨在介孔磷酸盐分子筛上构筑丙烷氧化脱氢活性位的合适方法。研究结果表明：掺杂方式引入的钒物种不仅可以同时以孤立态和聚集态存在，并且当钒含量高于8%时仍能保持高度分散状态，不容易出现导致催化性能下降的结晶态V₂O₅，与浸渍负载相比，本文采用掺杂方式制备的钒基催化剂样品普遍显示出更好的丙烷氧化脱氢活性和更高的丙烯选择性。此外，以碱金属Na掺杂的介孔磷酸盐分子筛Na_0.1Zr_0.9PO作为钒基催化剂的载体，虽然丙烷氧化脱氢反应的活性受到一定程度的抑制，但却可以使丙烯的选择性有所提升。     

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.     

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.     

Synthesis of V‐MCM‐41 Catalysts and Their Application in CO2‐Assisted Isobutane Dehydrogenation

A series of V‐MCM‐41 were in situ synthesized. The textual properties and vanadium species were systematically characterized. The results showed that the catalysts could still maintain a mesoporous structure and high specific surface area. The vanadium species were highly dispersed on the surface, with the coexistence of polymeric vanadium species. Isobutane dehydrogenation was performed by employing CO₂ as a soft oxidant. The results revealed an almost linear relationship between the activity and surface vanadium sites. Isolated vanadium species were more active for isobutane dehydrogenation. The isobutane dehydrogenation reaction in the presence of CO₂ could proceed simultaneously through oxidative dehydrogenation and non‐oxidative dehydrogenation followed by the reverse water gas shift reaction.     

Influence of the Content and Distribution of Vanadium in the M1 Phase of the MoVTe(Sb)NbO Catalysts on their Catalytic Properties in Light Alkanes Oxidation

Phase-pure MoVTe(Sb)NbO mixed oxides, with an M1 structure, and various compositions were prepared, characterized and tested as catalysts for the oxidative dehydrogenation of ethane, in order to study the influence of vanadium content and its distribution over the crystallographic sites on the catalytic properties of these oxides. A linear variation in catalytic activity was observed, as a function of the total vanadium content. This property, which has already been demonstrated for propane oxidation, is shown to remain unaffected by the alkane reaction, the nature of the propene α-dehydrogenation elements (Te or Sb), the presence or absence of niobium. The use of XPS to study the surface composition of the catalysts allowed a direct proportionality to be established between the rate of ethane conversion and the V⁵⁺ surface content, thus explaining the first correlation observed with bulk V content. This result also emphasizes the fact that a maximum level of intrinsic catalytic activity can be found, and that high vanadium content might be detrimental to this activity, or to the stability of the catalysts. Finally, crystallographic data found in the literature are used to further interpret and discuss these results.     

Promotional Effect of Iron for the Nitridation of Niobium Oxide to Niobium Nitride

Supported NbN catalysts were prepared under a N₂–H₂ gas stream by the addition of Fe species to Nb/SiO₂. The nitriding process was monitored by in situ XAFS measurements. Fe K-edge XAFS and Nb K-edge in situ XAFS measurements revealed that Fe species in close proximity to niobium oxide can effectively induce nitridation of the niobium oxide with the nitriding rate being dependent upon the dispersion of Fe species. It was concluded that the dispersed Fe species close to niobium effectively assisted the nitridation of niobium oxide into NbN. The nitriding degree can be expressed by the coordination number of Nb–N.     

Al2O3或SiO2负载钒氧化物催化剂的紫外-拉曼光谱比较研究

用柠檬酸络合助溶的等体积浸渍法制备了氧化铝和氧化硅负载的系列钒氧化物催化剂，使用紫外-拉曼光谱对催化剂的结构进行了表征。结果表明，负载钒氧化物的结构与钒的负载量和载体类型有关，在低钒负载量时以隔离的钒氧物种为主；在高负载量时，钒氧化物在γ-Al₂O₃载体上以聚合的钒氧物种和V₂O₅共存，在SiO₂载体上主要以隔离的钒氧物种和V₂O₅形态为主，并有少量聚合的钒氧物种。     

Vanadium to dubnium: from confusion through clarity to complexity

The tangled history of the discovery and naming of the three elements vanadium, niobium and tantalum some 200 years ago is reviewed. Similar controversies attended the much more recent synthesis and naming of the heaviest element of the group, dubnium. Many lessons can be learned from these disputes which are still very relevant today. There follows a brief summary of the physical, chemical and biochemical properties of the elements and an assessment of their current significance.