Spanish-Mexican scientistAndrés Manuel del Río discovered compounds of vanadium in 1801 by analyzing a newlead-bearing mineral he called "brown lead". Though he initially presumed its qualities were due to the presence of a new element, he was later erroneously convinced by French chemistHippolyte Victor Collet-Descotils that the element was justchromium. Then in 1830,Nils Gabriel Sefström generatedchlorides of vanadium, thus proving there was a new element, and named it "vanadium" after the Scandinavian goddess of beauty and fertility,Vanadís (Freyja). The name was based on the wide range of colors found in vanadium compounds. Del Río's lead mineral was ultimately namedvanadinite for its vanadium content. In 1867,Henry Enfield Roscoe obtained the pure element.
Large amounts of vanadiumions are found in a few organisms, possibly as atoxin. The oxide and some other salts of vanadium have moderate toxicity. Particularly in the ocean, vanadium is used by some life forms as an active center ofenzymes, such as thevanadium bromoperoxidase of some oceanalgae.
Vanadium wasdiscovered in Mexico in 1801 by the Spanish mineralogistAndrés Manuel del Río. Del Río extracted the element from a sample of Mexican "brown lead" ore, later namedvanadinite. He found that its salts exhibit a wide variety of colors, and as a result, he named the elementpanchromium (Greek: παγχρώμιο "all colors"). Later, del Río renamed the elementerythronium (Greek: ερυθρός "red") because most of the salts turned red upon heating. In 1805, French chemistHippolyte Victor Collet-Descotils, backed by del Río's friend BaronAlexander von Humboldt, incorrectly declared that del Río's new element was an impure sample ofchromium. Del Río accepted Collet-Descotils' statement and retracted his claim.[9]
In 1831 Swedish chemistNils Gabriel Sefström rediscovered the element in a new oxide he found while working withiron ores. Later that year,Friedrich Wöhler confirmed that this element was identical to that found by del Río and hence confirmed del Río's earlier work.[10] Sefström chose a name beginning with V, which had not yet been assigned to any element. He called the elementvanadium afterOld NorseVanadís (another name for theNorseVanir goddessFreyja, whose attributes include beauty and fertility), because of the many beautifully coloredchemical compounds it produces.[10] On learning of Wöhler's findings, del Río began to passionately argue that his old claim be recognized, but the element kept the namevanadium.[11] In 1831, the geologistGeorge William Featherstonhaugh suggested that vanadium should be renamed "rionium" after del Río, but this suggestion was not followed.[12]
As vanadium is usually found combined with other elements, the isolation of vanadium metal was difficult.[13] In 1831,Berzelius reported the production of the metal, butHenry Enfield Roscoe showed that Berzelius had produced the nitride,vanadium nitride (VN). Roscoe eventually produced the metal in 1867 by reduction ofvanadium(II) chloride, VCl2, withhydrogen.[14] In 1927, pure vanadium was produced by reducingvanadium pentoxide withcalcium.[15]
The first large-scale industrial use of vanadium was in thesteel alloy chassis of theFord Model T, inspired by French race cars. Vanadium steel allowed reduced weight while increasingtensile strength (c. 1905).[16] For the first decade of the 20th century, most vanadium ore were mined by theAmerican Vanadium Company from theMinas Ragra in Peru. Later, the demand for uranium rose, leading to increased mining of that metal's ores. One major uranium ore wascarnotite, which also contains vanadium. Thus, vanadium became available as a by-product of uranium production. Eventually, uranium mining began to supply a large share of the demand for vanadium.[17][18]
Naturally occurring vanadium is composed of one stableisotope,51V, and one radioactive isotope,50V. The latter has ahalf-life of 2.71×1017 years and a natural abundance of 0.25%.51V has anuclear spin of7⁄2, which is useful forNMR spectroscopy.[25] Twenty-four artificialradioisotopes have been characterized, ranging inmass number from 40 to 65. The most stable of these isotopes are49V with a half-life of 330 days, and48V with a half-life of 16.0 days. The remainingradioactive isotopes have half-lives shorter than an hour, most below 10 seconds. At least four isotopes havemetastable excited states.[26]Electron capture is the maindecay mode for isotopes lighter than51V. For the heavier ones, the most common mode isbeta decay.[27] The electron capture reactions lead to the formation of element 22 (titanium) isotopes, while beta decay leads to element 24 (chromium) isotopes.
From left: [V(H2O)6]2+ (lilac), [V(H2O)6]3+ (green), [VO(H2O)5]2+ (blue) and [VO(H2O)5]3+ (yellow)
The chemistry of vanadium is noteworthy for the accessibility of the four adjacentoxidation states 2–5. In anaqueous solution, vanadium formsmetal aquo complexes of which the colors are lilac [V(H2O)6]2+, green [V(H2O)6]3+, blue [VO(H2O)5]2+, yellow-orange oxides [VO(H2O)5]3+, the formula for which depends on pH. Vanadium(II) compounds are reducing agents, and vanadium(V) compounds are oxidizing agents. Vanadium(IV) compounds often exist asvanadyl derivatives, which contain the VO2+ center.[23]
Ammonium vanadate(V) (NH4VO3) can be successively reduced with elementalzinc to obtain the different colors of vanadium in these four oxidation states. Lower oxidation states occur in compounds such asV(CO)6,[V(CO) 6]− and substituted derivatives.[23]
Vanadium pentoxide is a commercially important catalyst for the production of sulfuric acid, a reaction that exploits the ability of vanadium oxides to undergo redox reactions.[23]
Thevanadium redox battery utilizes all four oxidation states: one electrode uses the +5/+4 couple and the other uses the +3/+2 couple. Conversion of these oxidation states is illustrated by the reduction of a strongly acidic solution of a vanadium(V) compound with zinc dust or amalgam. The initial yellow color characteristic of the pervanadyl ion [VO2(H2O)4]+ is replaced by the blue color of [VO(H2O)5]2+, followed by the green color of [V(H2O)6]3+ and then the violet color of [V(H2O)6]2+.[23] Another potential vanadium battery based on VB2 uses multiple oxidation state to allow for 11 electrons to be released per VB2, giving it higher energy capacity by order of compared to Li-ion and gasoline per unit volume.[28] VB2 batteries can be further enhanced as air batteries, allowing for even higher energy density and lower weight than lithium battery or gasoline, even though recharging remains a challenge.[28]
In an aqueous solution, vanadium(V) forms an extensive family ofoxyanions as established by51V NMR spectroscopy.[25] The interrelationships in this family are described by thepredominance diagram, which shows at least 11 species, depending on pH and concentration.[29] The tetrahedral orthovanadate ion,VO3− 4, is the principal species present at pH 12–14. Similar in size and charge to phosphorus(V), vanadium(V) also parallels its chemistry and crystallography.Orthovanadate VO3− 4 is used inprotein crystallography[30] to study thebiochemistry of phosphate.[31] Besides that, this anion also has been shown to interact with the activity of some specific enzymes.[32][33] The tetrathiovanadate [VS4]3− is analogous to the orthovanadate ion.[34]
At lower pH values, the monomer [HVO4]2− and dimer [V2O7]4− are formed, with the monomer predominant at a vanadium concentration of less than c. 10−2M (pV > 2, where pV is equal to the minus value of the logarithm of the total vanadium concentration/M). The formation of the divanadate ion is analogous to the formation of thedichromate ion.[35][36] As the pH is reduced, further protonation and condensation topolyvanadates occur: at pH 4–6 [H2VO4]− is predominant at pV greater than ca. 4, while at higher concentrations trimers and tetramers are formed.[37] Between pH 2–4decavanadate predominates, its formation from orthovanadate is represented by this condensation reaction:
10 [VO4]3− + 24 H+ → [V10O28]6− + 12 H2O
Vanadium crystal
In decavanadate, each V(V) center is surrounded by six oxideligands.[23] Vanadic acid, H3VO4, exists only at very low concentrations because protonation of the tetrahedral species [H2VO4]− results in the preferential formation of the octahedral [VO2(H2O)4]+ species.[38] In strongly acidic solutions, pH < 2, [VO2(H2O)4]+ is the predominant species, while the oxide V2O5 precipitates from solution at high concentrations. The oxide is formally theacid anhydride of vanadic acid. The structures of manyvanadate compounds have been determined by X-ray crystallography.
ThePourbaix diagram for vanadium in water, which shows theredox potentials between various vanadium species in different oxidation states[39]
Vanadium(V) forms various peroxo complexes, most notably in the active site of the vanadium-containingbromoperoxidase enzymes. The species VO(O2)(H2O)4+ is stable in acidic solutions. In alkaline solutions, species with 2, 3 and 4 peroxide groups are known; the last forms violet salts with the formula M3V(O2)4 nH2O (M= Li, Na, etc.), in which the vanadium has an 8-coordinate dodecahedral structure.[40][41]
Twelve binaryhalides, compounds with the formula VXn (n=2..5), are known.[42] VI4, VCl5, VBr5, and VI5 do not exist or are extremely unstable. In combination with other reagents,VCl4 is used as a catalyst for the polymerization ofdienes. Like all binary halides, those of vanadium areLewis acidic, especially those of V(IV) and V(V).[42] Many of the halides form octahedral complexes with the formula VXnL6−n (X= halide; L= other ligand).
Many vanadiumoxyhalides (formula VOmXn) are known.[43] The oxytrichloride and oxytrifluoride (VOCl3 andVOF3) are the most widely studied. Akin to POCl3, they are volatile,[44] adopt tetrahedral structures in the gas phase, and are Lewis acidic.[45]
Complexes of vanadium(II) and (III) are reducing, while those of V(IV) and V(V) are oxidants. The vanadium ion is rather large and some complexes achieve coordination numbers greater than 6, as is the case in [V(CN)7]4−. Oxovanadium(V) also forms 7 coordinate coordination complexes with tetradentate ligands and peroxides and these complexes are used for oxidative brominations and thioether oxidations. The coordination chemistry of V4+ is dominated by thevanadyl center, VO2+, which binds four other ligands strongly and one weakly (the one trans to the vanadyl center). An example isvanadyl acetylacetonate (V(O)(O2C5H7)2). In this complex, the vanadium is 5-coordinate, distorted square pyramidal, meaning that a sixth ligand, such as pyridine, may be attached, though theassociation constant of this process is small. Many 5-coordinate vanadyl complexes have a trigonal bipyramidal geometry, such as VOCl2(NMe3)2.[46] The coordination chemistry of V5+ is dominated by the relatively stable dioxovanadium coordination complexes[47] which are often formed by aerial oxidation of the vanadium(IV) precursors indicating the stability of the +5 oxidation state and ease of interconversion between the +4 and +5 states.[48]
The organometallic chemistry of vanadium is well–developed.Vanadocene dichloride is a versatile starting reagent and has applications in organic chemistry.[49]Vanadium carbonyl, V(CO)6, is a rare example of a paramagneticmetal carbonyl. Reduction yields V(CO)− 6 (isoelectronic withCr(CO)6), which may be further reduced with sodium in liquid ammonia to yield V(CO)3− 5 (isoelectronic with Fe(CO)5).[50][51]
Metallic vanadium is rare in nature (known asnative vanadium),[52][53] having been found among fumaroles of theColima Volcano, but vanadium compounds occur naturally in about 65 differentminerals.
Vanadium began to be used in the manufacture of special steels in 1896. At that time, very few deposits of vanadium ores were known. Between 1899 and 1906, the main deposits exploited were the mines of Santa Marta de los Barros (Badajoz), Spain.Vanadinite was extracted from these mines.[54] At the beginning of the 20th century, a large deposit of vanadium ore was discovered near Junín,Cerro de Pasco,Peru (now theMinas Ragra vanadium mine).[55][56][57] For several years thispatrónite (VS4)[58] deposit was an economically significant source for vanadium ore. In 1920 roughly two-thirds of the worldwide production was supplied by the mine in Peru.[59] With the production of uranium in the 1910s and 1920s fromcarnotite (K2(UO2)2(VO4)2·3H2O) vanadium became available as a side product of uranium production.Vanadinite (Pb5(VO4)3Cl) and other vanadium bearing minerals are only mined in exceptional cases. With the rising demand, much of the world's vanadium production is now sourced from vanadium-bearingmagnetite found inultramaficgabbro bodies. If thistitanomagnetite is used to produce iron, most of the vanadium goes to theslag and is extracted from it.[60][57]
Vanadium is mined mostly inChina,South Africa and easternRussia. In 2022 these three countries mined more than 96% of the 100,000tons of produced vanadium, with China providing 70%.[61]
Fumaroles of Colima are known of being vanadium-rich, depositing other vanadium minerals, that include shcherbinaite (V2O5) andcolimaite (K3VS4).[62][63][64]
Vanadium is also present inbauxite and deposits ofcrude oil,coal,oil shale, andtar sands. In crude oil, concentrations up to 1200 ppm have been reported. When such oil products are burned, traces of vanadium may causecorrosion in engines and boilers.[65] An estimated 110,000 tons of vanadium per year are released into the atmosphere by burningfossil fuels.[66]Black shales are also a potential source of vanadium. During WWII some vanadium was extracted fromalum shales in the south of Sweden.[67]
In the universe, thecosmic abundance of vanadium is 0.0001%, making the element nearly as common ascopper orzinc.[68] Vanadium is the 19th most abundant element in the crust.[69] It is detectedspectroscopically in light from theSun and sometimes in the light from otherstars.[70] Thevanadyl ion is also abundant inseawater, having an average concentration of 30 nM (1.5 mg/m3).[68] Somemineral watersprings also contain the ion in high concentrations. For example, springs nearMount Fuji contain as much as 54 μg perliter.[68]
Vanadium production trendVacuum sublimed vanadiumdendritic crystals (99.9%)
Vanadium metal is obtained by a multistep process that begins with roasting crushed ore withNaCl orNa2CO3 at about 850 °C to givesodium metavanadate (NaVO3). An aqueous extract of this solid is acidified to produce "red cake", a polyvanadate salt, which is reduced withcalcium metal. As an alternative for small-scale production, vanadium pentoxide is reduced withhydrogen ormagnesium. Many other methods are also used, in all of which vanadium is produced as abyproduct of other processes.[71] Purification of vanadium is possible by thecrystal bar process developed byAnton Eduard van Arkel andJan Hendrik de Boer in 1925. It involves the formation of the metal iodide, in this examplevanadium(III) iodide, and the subsequent decomposition to yield pure metal:[72]
2 V + 3 I2 ⇌ 2 VI3
Ferrovanadium chunks
Most vanadium is used as asteel alloy calledferrovanadium. Ferrovanadium is produced directly by reducing a mixture of vanadium oxide, iron oxides and iron in an electric furnace. The vanadium ends up inpig iron produced from vanadium-bearing magnetite. Depending on the ore used, the slag contains up to 25% of vanadium.[71]
Approximately 85% of the vanadium produced is used asferrovanadium or as asteel additive.[71] The considerable increase of strength in steel containing small amounts of vanadium was discovered in the early 20th century. Vanadium forms stable nitrides and carbides, resulting in a significant increase in the strength of steel.[73] From that time on, vanadium steel was used for applications inaxles, bicycle frames,crankshafts, gears, and other critical components. There are two groups of vanadium steel alloys. Vanadium high-carbon steel alloys contain 0.15–0.25% vanadium, andhigh-speed tool steels (HSS) have a vanadium content of 1–5%. For high-speed tool steels, a hardness aboveHRC 60 can be achieved. HSS steel is used insurgical instruments andtools.[74]Powder-metallurgic alloys contain up to 18% percent vanadium. The high content of vanadium carbides in those alloys increases wear resistance significantly. One application for those alloys is tools and knives.[75]
Vanadium stabilizes the beta form of titanium and increases the strength and temperature stability of titanium. Mixed withaluminium intitanium alloys, it is used injet engines, high-speed airframes anddental implants. The most common alloy for seamless tubing isTitanium 3/2.5 containing 2.5% vanadium, the titanium alloy of choice in the aerospace, defense, and bicycle industries.[76] Another common alloy, primarily produced in sheets, isTitanium 6AL-4V, a titanium alloy with 6% aluminium and 4% vanadium.[77]
Several vanadium alloys showsuperconducting behavior. The firstA15 phase superconductor was a vanadium compound, V3Si, which was discovered in 1952.[78]Vanadium-gallium tape is used insuperconducting magnets (17.5teslas or 175,000gauss). The structure of the superconducting A15 phase of V3Ga is similar to that of the more commonNb3Sn andNb3Ti.[79]
It has been found that a small amount, 40 to 270 ppm, of vanadium inWootz steel significantly improved the strength of the product, and gave it the distinctive patterning. The source of the vanadium in the original Wootz steel ingots remains unknown.[80]
Vanadium can be used as a substitute for molybdenum in armor steel, though the alloy produced is far more brittle and prone tospalling on non-penetrating impacts.[81] The Third Reich was one of the most prominent users of such alloys, in armored vehicles likeTiger II orJagdtiger.[82]
The catalyst is regenerated by oxidation with air:
4 VO2 + O2 → 2 V2O5
Similar oxidations are used in the production ofmaleic anhydride:
C4H10 + 3.5 O2 → C4H2O3 + 4 H2O
Phthalic anhydride and several other bulk organic compounds are produced similarly. Thesegreen chemistry processes convert inexpensive feedstocks to highly functionalized, versatile intermediates.[85][86]
Vanadium is an important component of mixed metal oxide catalysts used in the oxidation of propane and propylene toacrolein, acrylic acid or the ammoxidation of propylene toacrylonitrile.[87]
Thevanadium redox battery, a type offlow battery, is an electrochemical cell consisting of aqueous vanadium ions in different oxidation states.[88][89] Batteries of this type were first proposed in the 1930s and developed commercially from the 1980s onwards. Cells use +5 and +2 formal oxidization state ions.Vanadium redox batteries are used commercially forgrid energy storage.[90]
Vanadate can be used for protecting steel against rust and corrosion byconversion coating.[91] Vanadium foil is used incladding titanium to steel because it is compatible with both iron and titanium.[92] The moderatethermal neutron-capture cross-section and the short half-life of the isotopes produced by neutron capture makes vanadium a suitable material for the inner structure of afusion reactor.[93][94]
Vanadium can be added in small quantities < 5% toLFP battery cathodes to increase ionic conductivity.[95]
Vanadium is essential totunicates, where it is stored in the highly acidifiedvacuoles of certain blood cell types, designatedvanadocytes.Vanabins (vanadium-binding proteins) have been identified in the cytoplasm of such cells. The concentration of vanadium in the blood ofascidian tunicates is as much as ten million times higher[specify][102][103] than the surrounding seawater, which normally contains 1 to 2 μg/L.[104][105] The function of this vanadium concentration system and these vanadium-bearing proteins is still unknown, but the vanadocytes are later deposited just under the outer surface of the tunic, where they may deterpredation.[106]
Amanita muscaria and related species of macrofungi accumulate vanadium (up to 500 mg/kg in dry weight). Vanadium is present in thecoordination complexamavadin[107] in fungal fruit-bodies. The biological importance of the accumulation is unknown.[108][109] Toxic orperoxidase enzyme functions have been suggested.[110]
Deficiencies in vanadium result in reduced growth in rats.[111] The U.S. Institute of Medicine has not confirmed that vanadium is an essential nutrient for humans, so neither a Recommended Dietary Intake nor an Adequate Intake have been established. Dietary intake is estimated at 6 to 18 μg/day, with less than 5% absorbed. TheTolerable Upper Intake Level (UL) of dietary vanadium, beyond which adverse effects may occur, is set at 1.8 mg/day.[112]
Vanadyl sulfate as a dietary supplement has been researched as a means of increasing insulin sensitivity or otherwise improving glycemic control in people who are diabetic. Some of the trials had significant treatment effects but were deemed as being of poor study quality. The amounts of vanadium used in these trials (30 to 150 mg) far exceeded the safe upper limit.[113][114] The conclusion of the systemic review was "There is no rigorous evidence that oral vanadium supplementation improves glycaemic control in type 2 diabetes. The routine use of vanadium for this purpose cannot be recommended."[113]
All vanadium compounds should be considered toxic.[117] TetravalentVOSO4 has been reported to be at least 5 times more toxic than trivalent V2O3.[118] The USOccupational Safety and Health Administration (OSHA) has set an exposure limit of 0.05 mg/m3 for vanadium pentoxide dust and 0.1 mg/m3 for vanadium pentoxide fumes in workplace air for an 8-hour workday, 40-hour work week.[119] The USNational Institute for Occupational Safety and Health (NIOSH) has recommended that 35 mg/m3 of vanadium be considered immediately dangerous to life and health, that is, likely to cause permanent health problems or death.[119]
Vanadium compounds are poorly absorbed through the gastrointestinal system. Inhalation of vanadium and vanadium compounds results primarily in adverse effects on the respiratory system.[120][121][122] Quantitative data are, however, insufficient to derive a subchronic or chronic inhalation reference dose. Other effects have been reported after oral or inhalation exposures on blood parameters,[123][124] liver,[125] neurological development,[126] and other organs[127] in rats.
There is little evidence that vanadium or vanadium compounds are reproductive toxins orteratogens. Vanadium pentoxide was reported to be carcinogenic in male rats and in male and female mice by inhalation in an NTP study,[121] although the interpretation of the results has been disputed a few years after the report.[128] The carcinogenicity of vanadium has not been determined by theUnited States Environmental Protection Agency.[129]
Vanadium traces indiesel fuels are the main fuel component inhigh temperature corrosion. During combustion, vanadium oxidizes and reacts with sodium and sulfur, yieldingvanadate compounds with melting points as low as 530 °C (986 °F), which attack thepassivation layer on steel and render it susceptible to corrosion. The solid vanadium compounds also abrade engine components.[130][131]
^abcArblaster, John W. (2018).Selected Values of the Crystallographic Properties of Elements. Materials Park, Ohio: ASM International.ISBN978-1-62708-155-9.
^V(–3) is known inV(CO)3−5; seeJohn E. Ellis (2006). "Adventures with Substances Containing Metals in Negative Oxidation States".Inorganic Chemistry.45 (8).doi:10.1021/ic052110i.
^V(0) is known inV(CO)6; seeJohn E. Ellis (2006). "Adventures with Substances Containing Metals in Negative Oxidation States".Inorganic Chemistry.45 (8).doi:10.1021/ic052110i.
^Weast, Robert (1984).CRC, Handbook of Chemistry and Physics. Boca Raton, Florida: Chemical Rubber Company Publishing. pp. E110.ISBN0-8493-0464-4.
^Cintas, Pedro (12 November 2004). "The Road to Chemical Names and Eponyms: Discovery, Priority, and Credit".Angewandte Chemie International Edition.43 (44):5888–5894.doi:10.1002/anie.200330074.PMID15376297.
^abcdefgHolleman, Arnold F.; Wiberg, Egon; Wiberg, Nils (1985). "Vanadium".Lehrbuch der Anorganischen Chemie (in German) (91–100 ed.). Walter de Gruyter. pp. 1071–1075.ISBN978-3-11-007511-3.
^Crans, Debbie C.; Simone, Carmen M. (9 July 1991). "Nonreductive interaction of vanadate with an enzyme containing a thiol group in the active site: glycerol-3-phosphate dehydrogenase".Biochemistry.30 (27):6734–6741.doi:10.1021/bi00241a015.PMID2065057.
^Jung, Sabrina (2018).Speciation of molybdenum- and vanadium-based polyoxometalate species in aqueous medium and gas-phase and its consequences for M1 structured MoV oxide synthesis (Thesis).doi:10.14279/depositonce-7254.
^Al-Kharafi, F.M.; Badawy, W.A. (January 1997). "Electrochemical behaviour of vanadium in aqueous solutions of different pH".Electrochimica Acta.42 (4):579–586.doi:10.1016/S0013-4686(96)00202-2.
^Flesch, Gerald D.; Svec, Harry J. (1 August 1975). "Thermochemistry of vanadium oxytrichloride and vanadium oxytrifluoride by mass spectrometry".Inorganic Chemistry.14 (8):1817–1822.doi:10.1021/ic50150a015.
^Iqbal, Javed; Bhatia, Beena; Nayyar, Naresh K. (March 1994). "Transition Metal-Promoted Free-Radical Reactions in Organic Synthesis: The Formation of Carbon-Carbon Bonds".Chemical Reviews.94 (2):519–564.doi:10.1021/cr00026a008.
^Geiser, Jan Nicholas (2019).Development of an improved state-of-charge sensor for the all-vanadium redox flow battery (Thesis).doi:10.22028/D291-29229.
^Nica, Simona; Rudolph, Manfred; Görls, Helmar; Plass, Winfried (April 2007). "Structural characterization and electrochemical behavior of oxovanadium(V) complexes with N-salicylidene hydrazides".Inorganica Chimica Acta.360 (5):1743–1752.doi:10.1016/j.ica.2006.09.018.
^Wilkinson, G.; Birmingham, J. M. (September 1954). "Bis-cyclopentadienyl Compounds of Ti, Zr, V, Nb and Ta".Journal of the American Chemical Society.76 (17):4281–4284.Bibcode:1954JAChS..76.4281W.doi:10.1021/ja01646a008.
^Bellard, S.; Rubinson, K. A.; Sheldrick, G. M. (15 February 1979). "Crystal and molecular structure of vanadium hexacarbonyl".Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry.35 (2):271–274.Bibcode:1979AcCrB..35..271B.doi:10.1107/S0567740879003332.
^Elschenbroich, C.; Salzer A. (1992).Organometallics: A Concise Introduction. Wiley-VCH.ISBN978-3-527-28165-7.
^Calvo Rebollar, Miguel (2019).Construyendo la Tabla Periódica [Building the Periodic Table] (in Spanish). Zaragoza, Spain: Prames. pp. 161–165.ISBN978-84-8321-908-9.
^Ostrooumov, M., and Taran, Y., 2015. Discovery of Native Vanadium, a New Mineral from the Colima Volcano, State of Colima (Mexico). Revista de la Sociedad Española de Mineralogía 20, 109-110
^Dyni, John R. (2006). "Geology and resources of some world oil-shale deposits".Scientific Investigations Report. p. 22.doi:10.3133/sir29955294.S2CID19814608.
^abcRehder, Dieter (2008).Bioinorganic Vanadium Chemistry. Inorganic Chemistry (1st ed.). Hamburg, Germany: John Wiley & Sons, Ltd. pp. 5 & 9–10.doi:10.1002/9780470994429.ISBN978-0-470-06509-9.
^Carlson, O. N.; Owen, C. V. (1961). "Preparation of High-Purity Vanadium Metalb by the Iodide Refining Process".Journal of the Electrochemical Society.108 (1): 88.doi:10.1149/1.2428019.
^Rohrmann, B. (1985). "Vanadium in South Africa (Metal Review Series no. 2)".Journal of the Southern African Institute of Mining and Metallurgy.85 (5):141–150.hdl:10520/AJA0038223X_1959.
^Langeslay, Ryan R.; Kaphan, David M.; Marshall, Christopher L.; Stair, Peter C.; Sattelberger, Alfred P.; Delferro, Massimiliano (8 October 2018). "Catalytic Applications of Vanadium: A Mechanistic Perspective".Chemical Reviews.119 (4):2128–2191.doi:10.1021/acs.chemrev.8b00245.OSTI1509906.PMID30296048.S2CID52943647.
^Eriksen, K.M.; Karydis, D.A.; Boghosian, S.; Fehrmann, R. (August 1995). "Deactivation and Compound Formation in Sulfuric-Acid Catalysts and Model Systems".Journal of Catalysis.155 (1):32–42.doi:10.1006/jcat.1995.1185.
^Abon, Michel; Volta, Jean-Claude (September 1997). "Vanadium phosphorus oxides for n-butane oxidation to maleic anhydride".Applied Catalysis A: General.157 (1–2):173–193.doi:10.1016/S0926-860X(97)00016-1.
^Fierro, J. G. L., ed. (2006).Metal Oxides, Chemistry and Applications. CRC Press. pp. 415–455.ISBN978-0-8247-2371-2.
^Joerissen, Ludwig; Garche, Juergen; Fabjan, Ch.; Tomazic, G. (March 2004). "Possible use of vanadium redox-flow batteries for energy storage in small grids and stand-alone photovoltaic systems".Journal of Power Sources.127 (1–2):98–104.Bibcode:2004JPS...127...98J.doi:10.1016/j.jpowsour.2003.09.066.
^Li, Liyu; Kim, Soowhan; Wang, Wei; Vijayakumar, M.; Nie, Zimin; Chen, Baowei; Zhang, Jianlu; Xia, Guanguang; Hu, Jianzhi; Graff, Gordon; Liu, Jun; Yang, Zhenguo (May 2011). "A Stable Vanadium Redox-Flow Battery with High Energy Density for Large-Scale Energy Storage".Advanced Energy Materials.1 (3):394–400.Bibcode:2011AdEnM...1..394L.doi:10.1002/aenm.201100008.S2CID33277301.
^Guan, H.; Buchheit, R. G. (1 March 2004). "Corrosion Protection of Aluminum Alloy 2024-T3 by Vanadate Conversion Coatings".Corrosion.60 (3):284–296.doi:10.5006/1.3287733.
^Lositskii, N. T.; Grigor'ev, A. A.; Khitrova, G. V. (December 1966). "Welding of chemical equipment made from two-layer sheet with titanium protective layer (review of foreign literature)".Chemical and Petroleum Engineering.2 (12):854–856.Bibcode:1966CPE.....2..854L.doi:10.1007/BF01146317.S2CID108903737.
^Saıdi, M.Y.; Barker, J.; Huang, H.; Swoyer, J.L.; Adamson, G. (1 June 2003), "Performance characteristics of lithium vanadium phosphate as a cathode material for lithium-ion batteries",Journal of Power Sources,119–121:266–272,Bibcode:2003JPS...119..266S,doi:10.1016/S0378-7753(03)00245-3 Selected papers presented at the 11th International Meeting on Lithium Batteries
^Sigel, Astrid; Sigel, Helmut, eds. (1995).Vanadium and Its Role in Life. Metal Ions in Biological Systems. Vol. 31. CRC.ISBN978-0-8247-9383-8.
^Gribble, Gordon W. (1999). "The diversity of naturally occurring organobromine compounds".Chemical Society Reviews.28 (5):335–346.doi:10.1039/a900201d.
^Butler, Alison; Carter-Franklin, Jayme N. (2004). "The role of vanadium bromoperoxidase in the biosynthesis of halogenated marine natural products".Natural Product Reports.21 (1):180–188.doi:10.1039/b302337k.PMID15039842.
^Robson, R. L.; Eady, R. R.; Richardson, T. H.; Miller, R. W.; Hawkins, M.; Postgate, J. R. (1986). "The alternative nitrogenase of Azotobacter chroococcum is a vanadium enzyme".Nature.322 (6077):388–390.Bibcode:1986Natur.322..388R.doi:10.1038/322388a0.S2CID4368841.
^Smith, M. J. (1989). "Vanadium biochemistry: The unknown role of vanadium-containing cells in ascidians (sea squirts)".Experientia.45 (5):452–7.doi:10.1007/BF01952027.PMID2656286.S2CID43534732.
^MacAra, Ian G.; McLeod, G. C.; Kustin, Kenneth (1979). "Tunichromes and metal ion accumulation in tunicate blood cells".Comparative Biochemistry and Physiology B.63 (3):299–302.doi:10.1016/0305-0491(79)90252-9.
^Weiss, H.; Guttman, M. A.; Korkisch, J.; Steffan, I. (1977). "Comparison of methods for the determination of vanadium in sea-water".Talanta.24 (8):509–11.doi:10.1016/0039-9140(77)80035-0.PMID18962130.
^Ruppert, Edward E.; Fox, Richard, S.; Barnes, Robert D. (2004).Invertebrate Zoology (7th ed.). Cengage Learning. p. 947.ISBN978-81-315-0104-7.{{cite book}}: CS1 maint: multiple names: authors list (link)
^Kneifel, Helmut; Bayer, Ernst (June 1973). "Determination of the Structure of the Vanadium Compound, Amavadine, from Fly Agaric".Angewandte Chemie International Edition in English.12 (6): 508.doi:10.1002/anie.197305081.
^Falandysz, J.; Kunito, T.; Kubota, R.; Lipka, K.; Mazur, A.; Falandysz, Justyna J.; Tanabe, S. (31 August 2007). "Selected elements in fly agaric Amanita muscaria".Journal of Environmental Science and Health, Part A.42 (11):1615–1623.Bibcode:2007JESHA..42.1615F.doi:10.1080/10934520701517853.PMID17849303.S2CID26185534.
^da Silva, José A.L.; Fraústo da Silva, João J.R.; Pombeiro, Armando J.L. (August 2013). "Amavadin, a vanadium natural complex: Its role and applications".Coordination Chemistry Reviews.257 (15–16):2388–2400.doi:10.1016/j.ccr.2013.03.010.
^abSmith, D.M.; Pickering, R.M.; Lewith, G.T. (31 January 2008). "A systematic review of vanadium oral supplements for glycaemic control in type 2 diabetes mellitus".QJM.101 (5):351–358.doi:10.1093/qjmed/hcn003.PMID18319296.
^"Vanadium (vanadyl sulfate). Monograph".Altern Med Rev.14 (2):177–80. 2009.PMID19594227.
^Roschin, A. V. (1967). "Toksikologiia soedineniĭ vanadiia, primeneniaemykh v sovremennoĭ promyshlennosti" [Toxicology of vanadium compounds used in modern industry].Gigiena i Sanitariia (Water Res.) (in Russian).32 (6):26–32.PMID5605589.
^Wörle-Knirsch, Jörg M.; Kern, Katrin; Schleh, Carsten; Adelhelm, Christel; Feldmann, Claus & Krug, Harald F. (2007). "Nanoparticulate Vanadium Oxide Potentiated Vanadium Toxicity in Human Lung Cells".Environmental Science and Technology.41 (1):331–336.Bibcode:2007EnST...41..331W.doi:10.1021/es061140x.PMID17265967.
^Ścibior, A.; Zaporowska, H.; Ostrowski, J. (2006). "Selected haematological and biochemical parameters of blood in rats after subchronic administration of vanadium and/or magnesium in drinking water".Archives of Environmental Contamination and Toxicology.51 (2):287–295.Bibcode:2006ArECT..51..287S.doi:10.1007/s00244-005-0126-4.PMID16783625.S2CID43805930.
^González-Villalva, Adriana; Fortoul, Teresa I; Avila-Costa, Maria Rosa; Piñón-Zarate, Gabriela; Rodriguez-Lara, Vianey; Martínez-Levy, Gabriela; Rojas-Lemus, Marcela; Bizarro-Nevarez, Patricia; Díaz-Bech, Patricia; Mussali-Galante, Patricia; Colin-Barenque, Laura (April 2006). "Thrombocytosis induced in mice after subacute and subchronic V2O5 inhalation".Toxicology and Industrial Health.22 (3):113–116.Bibcode:2006ToxIH..22..113G.doi:10.1191/0748233706th250oa.PMID16716040.S2CID9986509.
^Opreskos, Dennis M. (1991)."Toxicity Summary for Vanadium". Oak Ridge National Laboratory.Archived from the original on 6 October 2021. Retrieved8 November 2008.
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