Vanadium Species Research Articles

Effective abatement of naphthalene from flue gas by V-W/Ti catalyst: Study of vanadium species and reaction mechanism

The removal of naphthalene is important but deficient, so that the available V-W/Ti catalysts (1.0 wt% V2O5/TiO2) were prepared for its efficient abatement in this work. Especially, influences of different existence status of vanadium species on naphthalene elimination were investigated via changing the pH value of precursor solution. With the increase of precursor solution acidity, more highly polymeric vanadium species were formed on the catalyst surface. The redox capability was enhanced markedly as a consequence of the stronger electron transfer between V/W and Ti that induced more surface active oxygen and V5+, whereas the catalytic activity was obviously boosted and almost 90 % conversion of naphthalene was achieved at 293 °C. Moreover, the weaker chemisorption between naphthalene and V-W/Ti catalyst allowed the deeper conversion to COx. GC–MS manifested that naphthalene seemed to be an organic component that was difficult to be totally degraded. Naphthalene oxidation was in the following pathway of naphthalene → 1,4-naphthoquinone → phthalic anhydride → phthalates → benzene → benzoquinone → maleic anhydride → COx/H2O. The opening of aromatic ring in phthalic anhydride and benzene ring in benzene were proven to be the rate-controlling step based on in-situ DRIFTS results. The key of naphthalene oxidation was the complete degradation of various intermediates.

Thermodynamic simulation of stepwise precipitation of NH4VO3 and NaHCO3 from carbonating Na3VO4 solution

Thermodynamic simulation was conducted to design a new process of stepwise precipitating NH4VO3 and NaHCO3 from regulating the CO2 carbonation of Na3VO4 solution. Firstly, a new V(V) speciation model for the aqueous solution containing vanadate and carbonate is established by using the Bromley−Zemaitis activity coefficient model. Subsequently, thermodynamic equilibrium calculations are conducted to clarify the behavior of vanadium, carbon, sodium, and impurity species in atmospheric or high-pressure carbonation. To ensure the purity and recovery of vanadium products, Na3VO4 solution is initially carbonated to the pH of 9.3−9.4, followed by precipitating NH4VO3 by adding (NH4)2CO3. After vanadium precipitation, the solution is deeply carbonated to the final pH of 7.3−7.5 to precipitate NaHCO3, and the remaining solution is recycled to dissolve Na3VO4 crystals. Finally, verification experiments demonstrate that 99.1% of vanadium and 91.4% of sodium in the solution are recovered in the form of NH4VO3 and NaHCO3, respectively.

Enhancing the selectivity of light olefins through synergistic VOx/ZSM-5 composite in the oxidative cracking of hexane

Oxidative-aided cracking of n-hexane is studied in a gas-phase oxygen-free environment over VOx/ZSM-5. The catalysts were prepared by impregnation of VOx on ZSM-5. Characterization of the prepared samples using XRD, SEM, and BET showed smooth, fine, highly crystalline, and highly dispersed VOx on ZSM-5. Raman spectroscopy revealed the presence of isolated moieties on the 1.5 and 2.5 % vanadia loading while a small number of polyvanadate species are detected on the 5 % VOx sample. TPR confirmed the ZSM-5 support contains highly reducible vanadia species. The amount of VOx loading also affected the activity and product distribution. The olefin and COx selectivities are affected by reaction time/temperature and amount/availability of lattice oxygen. VOx/ZSM-5(1.5) showed 99.9 % n-hexane conversion and 91.39 olefin selectivity at 575 °C and 25 s time-on-stream. This superior performance is attributed to the intermittent release of oxygen, optimum acidity, microporosity, and mesoporosity.

Strategically Modulating Proton Activity and Electric Double Layer Adsorption for Innovative All-Vanadium Aqueous Mn2+/Proton Hybrid Batteries.

Aqueous Mn-ion batteries (MIBs) exhibit a promising development potential due to their cost-effectiveness, high safety, and potential for high energy density. However, the development of MIBs is hindered by the lack of electrode materials capable of storing Mn2+ ions due to acidic manganese salt electrolytes and large ion radius. Herein, the tunnel-type structure of monoclinic VO2 nanorods to effectively store Mn2+ ions via a reversible (de)insertion chemistry for the first time is reported. Utilizing exhaustive in situ/ex situ multi-scale characterization techniques and theoretical calculations, the co-insertion process of Mn2+/proton is revealed, elucidating the capacity decay mechanism wherein high proton activity leads to irreversible dissolution loss of vanadium species. Further, the Grotthuss transfer mechanism of protons is broken via a hydrogen bond reconstruction strategy while achieving the modulation of the electric double-layer structure, which effectively suppresses the electrode interface proton activity. Consequently, the VO2 demonstrates excellent electrochemical performance at both ambient temperatures and -20°C, especially maintaining a high capacity of 162mAhg-1 at 5Ag-1 after a record-breaking 20000 cycles. Notably, the all-vanadium symmetric pouch cells are successfully assembled for the first time based on the "rocking-chair" Mn2+/proton hybrid mechanism, demonstrating the practical application potential.

Modulating the Electronic Structure of Cobalt-Vanadium Bimetal Catalysts for High-Stable Anion Exchange Membrane Water Electrolyzer.

Modulating the electronic structure of catalysts to effectively couple the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is essential for developing high-efficiency anion exchange membrane water electrolyzer (AEMWE). Herein, a coral-like nanoarray composed of nanosheets through the synergistic layering effect of cobalt and the 1D guiding of vanadium is synthesized, which promotes extensive contact between the active sites and electrolyte. The HER and OER activities can be enhanced by modulating the electronic structure through nitridation and phosphorization, respectively, enhancing the strength of metal-H bond to optimize hydrogen adsorption and facilitating the proton transfer to improve the transformation of oxygen-containing intermediates. Resultantly, the AEMWE achieves a current density of 500 mA cm-2 at 1.76 V for 1000 h in 1.0 M KOH at 70°C. The energy consumption is 4.21 kWh Nm-3 with the producing hydrogen cost of $0.93 per kg H2. Operando synchrotron radiation and Bode phase angle analyses reveal that during the high-energy consumed OER, the dissolution of vanadium species transforms distorted Co-O octahedral into regular octahedral structures, accompanied by a shortening of the Co-Co bond length. This structural evolution facilitates the formation of oxygen intermediates, thus accelerating the reaction kinetics.

Modulation Excitation Spectroscopy: A Powerful Tool to Elucidate Active Species and Sites in Catalytic Reactions.

ConspectusA rational design of catalysts requires a knowledge of the active species and sites. Often, catalyst surfaces are dominated by spectators, which do not participate in the reaction, while the catalytically active species and sites are hidden. Modulation-excitation spectroscopy (MES) allows discrimination between active and spectator species by applying a concentration modulation, which is translated into the active (that is, actively responding) species by phase-sensitive detection (PSD).While MES has been known for a while, its combination with infrared spectroscopy (IR-MES) has been applied to the detailed mechanistic analysis of a wide range of supported metal and metal oxide catalysts only recently, used for catalytic reactions such as CO2 hydrogenation, water-gas shift, and CO and selective oxidation. The applicability of IR-MES is not limited to catalysis but has started to expand into other areas of research (e.g., gas sensing).In the context of renewable energy, CO2 hydrogenation has been a matter of intense mechanistic debate, despite its great importance for synthesis gas production and further processing to fuels and chemicals. Applying IR-MES to supported Cu and Au catalysts enabled us to discriminate between redox and associative mechanisms. While CO2 hydrogenation to CO and water follows an associative pathway with sequential H2 activation via hydrides and formation of carbon- and oxygen-containing intermediates, such as carbonates and formates, the reverse reaction, that is, the water-gas shift reaction, was shown to proceed via a redox mechanism including oxygen vacancy formation followed by reoxidation of the catalyst by CO2.Recent IR-MES studies on (supported) metal oxides have provided direct spectroscopic insight into the catalytically active sites during the selective oxidation of alkanes and alcohols. By further expanding the potential of IR-MES by transient isotopic exchange experiments, we were able to resolve the nuclearity-dependent vanadium and adsorbate dynamics of supported vanadia catalysts during oxidative dehydrogenation, highlighting the intimate interplay between the surface vanadia species and the support. The strong influence of the support material (ceria and titania) on the sequence of reaction steps provides an explanation for the different catalytic performance. Based on these mechanistic insights, the rational design of improved catalysts has been possible.Expanding the application of IR-MES to the area of gas sensing, as recently demonstrated for doped SnO2, provides access to enhanced mechanistic insight, including previously undetected surface species. Methodical challenges arising from background features associated with semiconductor metal oxides have been successfully tackled, supporting further expansion of IR-MES in the gas sensing community. Mechanistically, the application of IR-MES allows identification of the actively participating OH groups and adsorbed species (e.g., alkoxy, CO, carbonate) and monitoring of reaction sequences based on their temporal behavior, providing a level of understanding typically not accessible by steady-state methods.As outlined above, the combination of MES/PSD with IR spectroscopy constitutes a powerful approach for the identification of catalytically active species and sites, which is essential for a profound mechanistic understanding of surface reactions, greatly facilitating the rational design of catalysts and other functional materials.

Three-dimensional thermal-electrochemical-hydrodynamic numerical study of vanadium redox flow battery with different flow fields and non-homogeneously compressed electrode

This paper presents a concise 3D numerical study of Vanadium Redox Flow Batteries (VRFBs) with different flow field designs and non-homogeneously compressed electrodes. The model integrates mass, momentum, charge, and energy transport equations, including reaction kinetics for vanadium species. Four flow field designs (conventional, parallel, serpentine, and interdigitated) are evaluated for heat distribution uniformity. The model accounts for non-uniform electrode properties due to compression. Numerical results are validated against experimental data, exploring the impact of operating parameters such as current density, flow rate, and temperature on thermal behavior. The study also compares heat generated by electrochemical reactions, ohmic losses, and chemical activation across different flow fields. The findings revealed the highest temperature gradient and non-uniformity (in terms of temperature) with conventional designs followed by interdigitated, parallel and serpentine. Importantly, the study consistently highlights elevated temperatures in the discharge condition across all configurations. This emphasizes the need for precise temperature control to prevent VO₂+ precipitation. These insights from VRFB optimization efforts are thoroughly presented in this paper.

Transparent vanadium doped titania-silica films: Structural characterization and self-cleaning properties

Vanadium is one of the most promising dopants for titanium dioxide, as it has different oxidation states and comparable atomic sizes to titanium cation. In this article, vanadium-modified TiO2 was prepared at low temperatures and immobilized on glass for self-cleaning and superhydrophilic purposes. The synthesis was carried out at 80 °C under reflux for 48 hours and only 150 °C was required for complete immobilization on the glass surface using silica binder, which in turn formed 120 nm thick films. Such multilayered (3) films showed enhanced transparency in the visible region of the spectrum and exhibited strong superhydrophilic properties (water contact angle, WCA < 5°) even when not illuminated. Vanadium was present in interstitial regions, while the unbound vanadium formed V2O5 nanoparticles at higher concentrations. The presence of vanadium did not improve the photocatalytic properties for the degradation of fatty layers composed of stearic acid, which could be attributed to reduced migration of electrons and holes due to the trapping effects of vanadium species in such samples.

SBA-15 Type Mesoporous Silica Modified with Vanadium as a Catalyst for Oxidative and Extractive Oxidative Desulfurization Processes.

One of the current challenges is the reduction of sulfur emitted into the atmosphere, usually in the form of sulfur oxides generated by fossil fuel combustion. To achieve this goal, the sulfur content should be reduced in fuel. In this context, vanadium-containing materials based on SBA-15 mesoporous silica supports and two different sources of vanadium were prepared, characterized, and applied as catalysts for oxidative desulfurization (CODS) and extractive oxidative desulfurization processes (ECODSs). The novelty of this work was the comparative study of vanadium-containing materials in two desulfurization systems. The properties of the catalysts, the concentration and state of vanadium species, and their role in the catalytic process were examined by low-temperature nitrogen physisorption, XRD, UV-Vis, XPS, and chemisorption of pyridine combined with FTIR spectroscopy. The catalytic performance of the material prepared using ammonium metavanadate was superior to that of the catalyst obtained using vanadium(IV) oxide sulfate, which was explained by a higher concentration of vanadium species on the surface of the support and their lower oxidation state in the former. Both types of catalysts showed high activity and stability in the ECODS process.

Full Selectivity Control over the Catalytic Hydrogenation of Nitroaromatics Into Six Products

AbstractA full selectivity control over the catalytic hydrogenation of nitroaromatics leads to the production of six possible products, i.e., nitroso, hydroxylamine, azoxy, azo, hydrazo or aniline compounds, which has however not been achieved in the field of heterogeneous catalysis. Currently, there is no sufficient evidence to support that the catalytic hydrogenation of nitroaromatics with the use of heterogeneous metal catalysts would follow the Haber's mechanistic scheme based on electrochemical reduction. We now demonstrate in this work that it is possible to fully control the catalytic hydrogenation of nitroaromatics into their all six products using a single catalytic system under various conditions. Employing SnO2‐supported Pt nanoparticles facilitated by the surface coordination of ethylenediamine and vanadium species enabled this unprecedented selectivity control. Through systematic investigation into the controlled production of all products and their chemical reactivities, we have constructed a detailed reaction network for the catalytic hydrogenation of nitroaromatics. Crucially, using oxygen‐isolated characterization techniques is essential for identifying unstable compounds such as nitroso, hydroxylamine, hydrazo compounds. The insights gained from this research offer invaluable guidance for selectively transforming nitroaromatics into a wide array of functional N‐containing compounds, both advancing fundamental understanding and fostering practical applications in various fields.

Full Selectivity Control over the Catalytic Hydrogenation of Nitroaromatics Into Six Products.

A full selectivity control over the catalytic hydrogenation of nitroaromatics leads to the production of six possible products, i.e., nitroso, hydroxylamine, azoxy, azo, hydrazo or aniline compounds, which has however not been achieved in the field of heterogeneous catalysis. Currently, there is no sufficient evidence to support that the catalytic hydrogenation of nitroaromatics with the use of heterogeneous metal catalysts would follow the Haber's mechanistic scheme based on electrochemical reduction. We now demonstrate in this work that it is possible to fully control the catalytic hydrogenation of nitroaromatics into their all six products using a single catalytic system under various conditions. Employing SnO2-supported Pt nanoparticles facilitated by the surface coordination of ethylenediamine and vanadium species enabled this unprecedented selectivity control. Through systematic investigation into the controlled production of all products and their chemical reactivities, we have constructed a detailed reaction network for the catalytic hydrogenation of nitroaromatics. Crucially, using oxygen-isolated characterization techniques is essential for identifying unstable compounds such as nitroso, hydroxylamine, hydrazo compounds. The insights gained from this research offer invaluable guidance for selectively transforming nitroaromatics into a wide array of functional N-containing compounds, both advancing fundamental understanding and fostering practical applications in various fields.

VO Supported on Functionalized CNTs for Oxidative Conversion of Furfural to Maleic Anhydride

Commercial non-functionalized (CNTs) and functionalized carbon nanotubes (CNT-COOH and CNT-NH2) were used as supports to synthesize vanadium-supported catalysts to be used in the gas phase partial oxidation of furfural towards maleic anhydride (MA). The CNTs and the VO2-V2O5/CNTs, so-called VO/CNT catalysts, were characterized by AAS, TGA, XRD, N2 adsorption isotherms at −196 °C, Raman, NH3-TPD and XPS. The surface area values, TGA and XRD results indicate that the larger thermal stability and larger dispersion of vanadium species is reached for the VO/CNT-NH2 catalyst. XPS indicates presence of surface VO2 and V2O5 species for the non-functionalized (CNT) and functionalized (CNT-COOH and CNT-NH2) catalysts, with a large interaction of the functional group with the surface vanadium species only for the VO/CNT-NH2 catalyst. The catalytic activity, evaluated in the range 305 °C to 350 °C, indicates that CO, CO2 and MA yield (%) and MA productivity are associated to the redox properties of the vanadium species, the oxygen exchange ability of the support and the vanadium–support interaction. For the reaction temperatures between 320 °C and 335 °C, the maximum MA yield (%) is found in the functionalized VO/CNT-COOH and VO/CNT-NH2 catalysts. This behavior is attributed to a decreased oxidation capability of the CNT with the functionalization. In addition, VO/CNT-NH2 is the more active and selective catalyst for MA productivity at 305 °C and 320 °C, which is related to the greater interaction of the surface vanadium species with the -NH2 group, which enhances the redox properties and stabilization of the VO2 and V2O5 surface active sites. Recycling at 350 °C resulted in 100% furfural conversion for all catalysts and a similar MA yield (%) compared to the fresh catalyst, indicating no loss of surface active sites.

Liquid-liquid extraction equilibrium study of vanadium(V) from nitrate medium by technical grade D2EHPA dissolved in kerosene

The extraction behaviour of vanadium (V) from nitric acid solutions was studied using technical grade D2EHPA in kerosene as an extractant. The effects of aqueous pH, the concentration of vanadium (V) and nitrate ion in the aqueous phase, and the concentration of D2EHPA in the organic phase were investigated. The extraction equilibration time was 30 min. Metal ion dependencies appeared non-ideal due to the non-constancy of the aqueous phase acidity and the equilibrium extractant concentration. Two types of extraction mechanisms originated from the study of pH dependency. The study conceded that the extraction of vanadium (V) occurred via ion exchange or chelation type of extraction when the pH(eq) &lt;2.50. On the other hand, the solvated ion-pair extraction mechanism occurs when the pH(eq) was above 2.50. The extractant dependencies showed that vanadium (V) species were extracted by one molecule of D2EHPA. The salting-out effect was observed from the effect of nitrate ion concentration. The effect of various types of diluents on vanadium (V) extraction with technical grade D2EHPA was studied; kerosene appeared to be a suitable diluent. The temperature dependence data revealed that the system was exothermic with the ΔH value of -12.34 kJ/mol. The loading capacity was 6.11 g vanadium (V) per 100 g extractant. The H2SO4 (0.5 mol/L) was the right stripping agent for the extracted species.

The nature of synergy effects between VOx and TiO2 in low temperature NH3-SCR reaction

In this study, we investigated the low-temperature activity of selective catalytic reduction of NO by NH3 (NH3-SCR) with the effect of different vanadium oxide (VOx) loading in the VOx/TiO2 catalyst. By calculating the specific rate of activity, it was found that the fastest specific rate of activity was achieved when the loading of V2O5 reached 10 wt%, and the nitrogen oxides (NOx) conversion of the above optimal catalyst reached over 80 % in the temperature range of 180–465 °C. The effects of preparation method, calcination temperature, and support on the aggregation state of the vanadium species and the SCR activity of the catalyst were also investigated on the basis of the ideal ratio. Combining the activity and characterization results, it is found that the impregnation method and calcination at 410 °C are more favorable for the moderate dispersion of the vanadium species on the TiO2 surface, producing more highly reactive polymorphic VOx, which is more readily dispersed on the surface of the TiO2 support and interacts more strongly with the TiO2. The interaction between the two can promote the transfer of electrons, resulting in the production of more active O species and low-valent vanadium. The aforementioned species can enhance the catalyst's low- temperature denitrification activity.

Surface anchoring requirements for vanadia clusters on titanium oxide surfaces and their impact on activity for oxidative dehydrogenation of ethanol

Titanium oxide site requirements for the anchoring of catalytically active forms of dispersed vanadia species are investigated. Using a series of oxygen-modified titanium nitride materials, we systematically modify the available vanadia-anchoring moieties on the titanium-bearing support surface. This strategy in turn results in a very narrow size distribution of well-dispersed vanadia clusters anchored on the support. This synthesis technique ensures that only highly dispersed vanadia is present on the catalyst surface even at nominal monolayer coverages. A deeper insight into the catalytic behavior for ethanol partial oxidation of the active vanadia species is obtained by comparing intrinsic kinetic and thermodynamic parameters of kinetically relevant reaction steps (heat of ethanol adsorption, hydrogen abstraction activation energy, and the energetics of catalyst reoxidation). It is found that these parameters are dependent on the relative amount of oxygen in the titanium-bearing support and the resulting distribution of vanadia species, which validates the premise of a potential participation of lattice oxygen atoms of the titania support into the catalytic activity of active vanadia species.

V2O5/TiO2 Catalyst for Catalytic Glucose Oxidation to Formic Acid in Batch Reactor: Vanadium Species Nature and Reaction Conditions Optimization

V2O5/TiO2 Catalyst for Catalytic Glucose Oxidation to Formic Acid in Batch Reactor: Vanadium Species Nature and Reaction Conditions Optimization

Vanadium speciation using magnetic multi-walled carbon nanotubes coated with ion-imprinted polymer and electrothermal atomic absorption spectrometry

ABSTRACT For selective extraction of vanadium (V) from water and food samples, ion-imprinted polymer was synthesised on magnetic multi-walled carbon nanotubes. For this purpose, the complex of V(V)-8-hydroxyquinoline, 4-vinylpyridine, ethylene glycol dimethacrylate, and magnetic multi-walled carbon nanotubes were used as the template of V(V), functional monomer, cross-linker, and the core, respectively. The prepared sorbent was characterised by FTIR spectroscopy, scanning electron microscopy, X-ray diffraction, energy-dispersion X-ray, and vibrating sample magnetometer. The extracted vanadium (V) was assessed by electrothermal atomic absorption spectrometry. The total vanadium in the solution was extracted and determined after oxidation of V(IV) to V(V) by hydrogen peroxide. Under optimised conditions, limits of detection and quantification of 2.9, and 10.0 ng L−1 were obtained, respectively. The maximum capacity of sorbent was 44.1 mg g−1. The method was successfully employed for the extraction and quantification of vanadium species in different water samples and total vanadium in food samples.

Speciation of vanadium and the interacted solid surface of δ-alumina adsorbent in aqueous media in presence of humic acid

Speciation of vanadium elements in the presence of δ-alumina in aqueous media was studied to simulate the environmental impact of soil/sediment–water interacted system. Factors affecting this process are pH, presence of humic acid, and δ-alumina concentrations as an abundant sediment/soil components. Different species of both vanadium and surface of δ-alumina were deduced theoretically using MintaqA2 programme. Due to the effect of pH, the anionic species of vanadium at pH 1–3 is prevailed and changed to cationic species at pH range 6–10 at different levels of alumina. Additionally, based on the effect of alumina concertation, high percent uptake, almost 100% was found at 10.0 g/1 concentration of alumina while at level of 0.2 g/1 alumina, the maximum adsorption of vanadium was become 91%. The effect of humic acid on the speciation behavior of vanadium (V) was also studied and compared with that of vanadium (IV) based on XANES (X-ray absorption near edge structure). Adsorption behaviors were studied at concentration 4.71E-4M for vanadium at 0.1M ionic strength. The mechanism of vanadium adsorption in the presence of alumina under the same working conditions was studied and explained based on TLM (Triple layer model) where the results proved good validation and verification of the practically produced data.

Structure and reactivity of surface vanadia sites in bi-layered supported VOx/AlOx/SiO2 catalysts via solid-state NMR, first-principles calculations, and catalytic studies

By combining multinuclear 1H, 29Si, 27Al and 51V solid-state NMR experimental measurements with reactivity and selectivity data, as well as first-principles calculations, for ternary bi-layered supported VOx/Al2O3/SiO2 catalysts, the structure of the dehydrated surface vanadia species was determined for each combination of supported VOx and AlOx active components. The specific structure of the surface vanadia sites in the ternary bi-layered supported VOx/Al2O3/SiO2 catalyst system have been investigated for the first time.The following vanadia sites are proposed based on the current findings:At low vanadia content, surface VO(OH)(OSi)2 sites form on the alumina-free surface of the SiO2 support in the bi-layered supported VOx/Al2O3/SiO2 catalyst system. In addition, two types of VO(OSi)3 surface species are likely present in this system. On small alumina clusters, weakly bonded surface VO(OH)(OAl)2 sites also form, along with the sites containing mixed Si/Al pods VO(OH)(OAl)(OSi). As the size of alumina clusters increases, strongly bonded VO(OAl)3 centers form, alongside the surface sites containing mixed pods VO(OAl)2(OSi) and VO(OAl)(OSi)2. The content of these sites increases with the loading of vanadia. Comparing supported VOx/SiO2, VOx/Al2O3, and bi-layered VOx/Al2O3/SiO2 catalyst systems revealed differences in catalytic activity due to the presence of new sites with different pods, with OH groups as well as the influence of Al-O-Si bonds on the electronic structure of surface vanadia sites on the alumina clusters. During the formation of dimethyl ether (DME), the turnover frequency (TOFDME) of the catalysts decreases with increasing domain size of the alumina clusters on SiO2. Addition of surface VOx sites, however, slightly decreases the TOFDME with the higher vanadia content weakening the activity of the alumina clusters. When surface VOx exists predominantly as V/Al1 and V/Al2, TOFredox depend on the vanadia content with lower vanadia content resulting in higher the TOFredox values. The 51V NMR spectra show that this decrease in redox TOF value correlates with the appearance of vanadia sites associated with silica pods. The activity of the catalysts was tested in methanol conversion reactions.

Polymeric carriers of vanadyl ions based on copolymers of N-vinylpyrrolidone with vinylimines

In this study, a series of new chelating copolymers containing 20% azomethine groups, poly(N-vinylpyrrolidone-co-vinylsalicylideneimine) (poly[VP-co-VSalI]), poly(N-vinylpyrrolidone-co-vinylpicolinideneimine) (poly[VP-co-VPicI]), poly(N-vinylpyrrolidone-co-vinylpyridoxylideneimine) (poly[VP-co-VPyrI]) with M = 63000 Da and their vanadium(IV) complexes – poly(VP-co-VSalI)-VO, poly(VP-co-VPicI)-VO, poly(VP-co-VPyrI)-VO, were designed and synthesized. These are intended for the delivery and pH-dependent release of vanadium species in the intestine environment. The chelating polymers were obtained from poly(N-vinylpyrrolidone-co-N-vinylamine) (poly[VP-VAm]) by polymer-analogous transformations with the corresponding aldehydes. The vanadium content, determined by ICP-AES and spectrophotometric methods, was 5.36%, 4.99%, and 9.1% of the dry mass for poly(VP-co-VSalI)-VO, poly(VP-co-VPyrI)-VO, and poly(VP-co-VPicI)-VO, respectively. XPS data confirmed that only vanadium(IV) is presented in the complexes. All complexes demonstrated a pH-dependent release of low molecular weight vanadium species, making them promising candidates for the development of vanadium-containing systems for oral administration. These systems protect the main vanadium content in the stomach but can release biologically active ions in the intestine.