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Inorganics
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Vanadium in the Center: Current Chemistry and Utilization of the...
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Vanadium in the Center: Current Chemistry and Utilization of the Versatile Metal

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Coordination Chemistry".

Deadline for manuscript submissions: closed (31 October 2023) | Viewed by 7514

Special Issue Editor

Dr. Lukáš Krivosudský

E-Mail Website
Guest Editor
Deparmtent of inorganic Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, 842 15 Bratislava, Slovakia
Interests: vanadium; vanadates; polyoxometalates; bioinorganic chemistry

Special Issue Information

Dear Colleagues,

Since the discovery of vanadium nearly 200 hundred years ago, the metal has found many applications, mostly in alloys, resulting in the utilization of about 85% of the produced vanadium as ferrovanadium or as a steel additive. Among the compounds of vanadium, V2O5 is a prominent catalyst in sulfuric acid production and other reactions. On the other hand, vanadium forms a vast number of coordination compounds in various oxidation states, and together with polyvanadates and mixed vanadium-containing polyoxometalates they offer applications in distinct areas of chemistry, biology, and materials science. Vanadium is the second most abundant transition metal in seawater, and it has been found in several sea species, such as tunicates, where it is stored in vanadocytes and binds to specialized enzymes known as vanabins. It is assumed that the function of vanadium in biological and catalytic systems is mostly related to its versatile oxidation/reduction processes between the oxidation states II, III, IV, and V. Vanadium is also found in terrestrial species, such as amantina muscaria, where it is present as a vanadium (IV) coordination compound amavadin with a not-yet-elucidated function. These and many other examples have stimulated the utilization of vanadium complexes, polyvanadates, and vanadium-based materials, not only in biological applications but also in materials science and electrochemistry. In this Special Issue, we wish to cover the most recent advances in all these aspects of vanadium chemistry, chemical biology, and materials science, by hosting a mix of original research articles and short critical reviews.

Dr. Lukáš Krivosudský
Guest Editor

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Keywords

  • vanadium
  • vanadates
  • vanadium coordination chemistry
  • vanadium bioinorganic chemistry
  • vanadium organometallic chemistry
  • vanadium-based materials

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Published Papers (4 papers)

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Research

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12 pages, 2434 KiB  
Article
Synthesis of Copper-Substituted Polyoxovanadate and Oxidation of 1-Phenyl Ethanol
by Isshin Yoshida, Ryoji Mitsuhashi, Yuji Kikukawa and Yoshihito Hayashi
Inorganics 2024, 12(2), 61; https://doi.org/10.3390/inorganics12020061 - 19 Feb 2024
Cited by 4 | Viewed by 2092
Abstract
Dicopper-substituted polyoxovanadate [Cu2V16O44(NO3)]5− (Cu2V16) was synthesized through the reaction of [Cu2V8O24]4− and [V4O12]4− in the presence of nitrate salt. From single crystal [...] Read more.
Dicopper-substituted polyoxovanadate [Cu2V16O44(NO3)]5− (Cu2V16) was synthesized through the reaction of [Cu2V8O24]4− and [V4O12]4− in the presence of nitrate salt. From single crystal X-ray analysis, Cu2V16 exhibited the same helical structure as that of nitrate-incorporated polyoxovanadate, [V18O46(NO3)]5− (V18). Both complexes had the same framework with the same guest anion and are considered to be substituted isomers for each other by replacing two Cu2+ ions and two [VO]2+ ions. The incorporated nitrate showed short and long N–O bond lengths (1.14, 1.26 and 1.30 Å) as in the case of V18 (1.09, 1.16 and 1.28 Å). Reflecting the inequivalent bond lengths of the nitrate, the IR spectrum of V18 shows split peaks at 1359 and 1342 cm−1. But the Cu2V16 spectrum showed a single peak due to the presence of nitrate at 1353 cm−1. When the temperature was lowered, the nitrate peak in Cu2V16 was split into two positions at 1354 and 1345 cm−1 when the temperature reached −140 °C. These results indicate that the nitrate incorporated in Cu2V16 rotates relatively easily in the Cu2V16 cavity at room temperature compared to V18. In addition, the oxidation of 1-phenyl ethanol to acetophenone with Cu2V16 smoothly proceeded in comparison with V18. By taking advantage of the same framework in both catalysts, we can deduce the position of potential active sites in the oxidation reaction. We have concluded that the most active site is not on the peripheral of the vanadate framework, but it is reasonable to suggest that the active site is on the substituted copper atoms rather than the polyoxovanadate framework. Full article
(This article belongs to the Special Issue Vanadium in the Center: Current Chemistry and Utilization of the Versatile Metal)
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11 pages, 2379 KiB  
Article
MoO3 Solubility and Chemical Durability of V2O5-Bearing Borosilicate Glass
by Minako Nagata and Toru Sugawara
Inorganics 2023, 11(7), 311; https://doi.org/10.3390/inorganics11070311 - 24 Jul 2023
Cited by 5 | Viewed by 1570
Abstract
In the vitrification of high-level radioactive liquid waste (HLW), the separation of sodium-molybdate melts is a problem because it reduces the chemical durability of the vitrified waste. A glass with both high MoO3 solubility and chemical durability is required for the safe [...] Read more.
In the vitrification of high-level radioactive liquid waste (HLW), the separation of sodium-molybdate melts is a problem because it reduces the chemical durability of the vitrified waste. A glass with both high MoO3 solubility and chemical durability is required for the safe disposal of radioactive waste. In this study, we investigate the effects of vanadium oxide on the phase separation of the molybdenum-rich phase and the water resistance of the resulting glass by phase equilibrium experiments and chemical durability test. Phase equilibrium experiments were performed on SiO2-B2O3-Al2O3-ZnO-CaO-Na2O-LiO2-MoO3 system glasses and on glasses with V2O5 added. The results showed that MoO3 solubility increased when V2O5 was added. The increase in MoO3 solubility in borosilicate melts may be associated with the viscosity-lowering effect of V2O5. Chemical durability tests were performed on borosilicate glass compositions obtained from phase equilibrium experiments. The normalized leaching rates of V2O5-bearing glasses were higher than those of other glasses. This is due to the higher network modifier/network former ratio of the glass tested. The normalized elemental mass loss of glass containing waste components increases with increasing leaching duration. This suggests that the waste component prevents the formation of a gel layer at the reaction front. Full article
(This article belongs to the Special Issue Vanadium in the Center: Current Chemistry and Utilization of the Versatile Metal)
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10 pages, 1014 KiB  
Article
A Self-Consistent Exact Diagonalization Approach to the Ground State Magnetic Properties of the Meridional [V(ddpd)2]3+ Complex
by Miroslav Georgiev, Takvor Baronian and Hassan Chamati
Inorganics 2023, 11(7), 268; https://doi.org/10.3390/inorganics11070268 - 24 Jun 2023
Viewed by 1361
Abstract
The present paper presents a thorough study of the ground state magnetic properties of the spin-one mononuclear nanomagnet mer-[V(ddpd)2][PF6]3, with the V3+ center exhibiting a distorted octahedral coordination. The theoretical analysis is based on [...] Read more.
The present paper presents a thorough study of the ground state magnetic properties of the spin-one mononuclear nanomagnet mer-[V(ddpd)2][PF6]3, with the V3+ center exhibiting a distorted octahedral coordination. The theoretical analysis is based on a multiconfigurational, self-consistent approach that effectively parametrizes the total energy spectrum of the considered coordination complex via exact diagonalization. We provide a comprehensive discussion for the obtained zero-field and field-dependent fine structure of the ground state along with the ensuing crystal field splitting of the 3d orbitals. Furthermore, we report the results for the low-field susceptibility, magnetization and the corresponding reversal dynamics, finding good agreement with the experimental data reported in the literature. The calculations show considerable zero-field splitting and strong field-dependent orbital unquenching underlying the occurrence of a field-induced full profile magnetization reversal barrier. Full article
(This article belongs to the Special Issue Vanadium in the Center: Current Chemistry and Utilization of the Versatile Metal)
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Review

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11 pages, 3173 KiB  
Review
Import and Implications of Vanadium in Live Aspects
by Dieter Rehder
Inorganics 2023, 11(6), 256; https://doi.org/10.3390/inorganics11060256 - 12 Jun 2023
Cited by 8 | Viewed by 1881
Abstract
In Earth’s regions accessible for living organisms (Earth’s crust, crude oil, water sanctuaries and lower atmosphere), vanadium is present in the oxidation states +III and—essentially—+IV (cationic) and +V (cationic and anionic), with the redox interchange and biochemical recycling often monitored by bacteria. Organisms [...] Read more.
In Earth’s regions accessible for living organisms (Earth’s crust, crude oil, water sanctuaries and lower atmosphere), vanadium is present in the oxidation states +III and—essentially—+IV (cationic) and +V (cationic and anionic), with the redox interchange and biochemical recycling often monitored by bacteria. Organisms having available vanadium-containing (bio)molecules with essential functions for life include marine brown algae (haloperoxidases), ascidians and fan worms, as well as terrestrial organisms, viz., nitrogen-fixing bacteria (associated with the roots of legumes), and the fly agaric mushroom. The hypohalite generated by the algal haloperoxidases in turn is involved in the emission of bromoform into the atmosphere. Nitrogen fixation (N2 ε NH4+) is a process of immanent importance for life on our planet. Other bacterial issues include the reduction of vanadate to VO2+. Medicinal applications of vanadium coordination compounds are directed towards the treatment of diabetes mellitus (vanadium complexes with hypoglycemic activity) and cancer—although boundaries are set due to side effects such as oxidative damage elicited by vanadium-induced hyperoxide formation. Physiological actions of vanadium are often invoked due to the structural and physiological similarity between vanadate and phosphate. An additional field of medicinal applications addresses the treatment of cancer, such as leukaemia, malignant melanoma and bone cancer. Full article
(This article belongs to the Special Issue Vanadium in the Center: Current Chemistry and Utilization of the Versatile Metal)
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