• Title/Summary/Keyword: Vanadyl

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Influence of [VO4]3- Bridges on Magnetic Coupling in Ba2V3O9 Studied by Molecular Orbital Calculations

  • Kang, Dae-Bok
    • Bulletin of the Korean Chemical Society
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    • v.33 no.7
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    • pp.2341-2344
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    • 2012
  • A molecular orbital study is presented of the magnetic coupling in the one-dimensional vanadium oxide $Ba_2V_3O_9$ with a bridge formed by two different types of $VO_4$ tetrahedra. The concept of complementary versus counter-complementary effect has been used to explain the structural origin of the magnetic behavior of the compound. Namely, the observed antiferromagnetic coupling is dominated by the orbital complementarity of the V(1) tetrahedra sharing only one oxygen corner with two adjacent $VO_6$ octahedra. The second type of V(2) tetrahedra does not provide a noticeable contribution to the magnetic coupling due to the orbital counter-complementarity of the bridging ligand.

The Synthesis and the Electrochemical Properties of Al Doped $V_2O_5$ (Al이 도핑된 오산화바나듐의 합성 및 전기화학적 특성)

  • Park, Heai-Ku;Joung, Ok-Young;Lee, Man-Ho
    • Applied Chemistry for Engineering
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    • v.16 no.4
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    • pp.491-495
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    • 2005
  • Vanadium pentoxide xerogels with a doping ratio of $Al/V_2O_5$ ranging from 0.01 to 0.05 were synthesized by doping Al into $V_2O_5$ xerogel via the sol-gel process. By using the synthesized $Al_xV_2O_5$, the $Li/Al_xV_2O_5$ cells were assembled to investigate the chemical and electrochemical properties. Surface morphology of the $Al_xV_2O_5$ xerogel showed an anisotropic corrugated sheet-like matrix, and the interlayer distance was about $11.5{\AA}$. The IR spectra of the $Al_xV_2O_5$ revealed that the doped Al was coordinated to the vanadyl group in $V_2O_5$. The $Al_xV_2O_5$ xerogels showed enhanced reversibility and energy density compared with the $V_2O_5$ xerogel. The specific capacity of the $Al_{0.05}V_2O_5$ xerogel was more than 200 mAh/g at 10 mA/g discharge rate, and cycle efficiency was about 90% after the 31st cycling test between 1.9 V and 3.9 V.

Tracer Study Using $H_2O^{18}$ on the Oxidation of Vanadium (III) by Molecular Oxygen (산소에 의한 바나듐 (III) 이온의 산화반응에 대한 $O^{18}$ 동위원소 연구)

  • Kim, Myeong Ja;Choe, Dong Sik
    • Journal of the Korean Chemical Society
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    • v.18 no.4
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    • pp.259-266
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    • 1974
  • Isotopic experiments using $H_2O^{18}$ on the oxidation of V(III) in acid perchlorate by molecular oxygen were performed in the range pH 1.0 to 3.0. At pH < 2, where a rate equation of the form TEX>$ -\frac{d[V(III)]}{dt}=k_1\frac{[O_2][V(III)]}{[H^+]}$ is adequate, the tracer study clearly indicated that all the product vanadyl ion's ($VO^{2+}$) oxygen originated from the molecular oxygen. At pH > ~2, where a different rate expression of the form $-\frac{d[V(III)]}{dt}=K_2\frac{[O_2][V(III)]^2}{[Ht]^2}$is required, the isotopic experiment showed that half the vanadyl oxygen originated from the molecular oxygen. Considering the results of the isotopic study, a mechanism for the V(Ⅲ)-O2 reaction at pH < ~2, may be suggested as follows: The tracer results at pH > ~2 imply that the rate determining step may be $$ V_2(OH)_2^{4+} + O_2 \rightarrow 2VO^{2+} + H_2O_2$$ followed by $$V_2(OH)_2^{4+} + H_2O_2 \rightarrow 2VO^{2+} + 2H_2O$$ after establishing the equilibria V^{3+} + H_2O \leftrightarrow VOH^{2+} + H^+, and 2VOH^{2+}\leftrightarrow V_2(OH)_2^{4+}$$

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The Photodegradation Effect of Organic Dye for Metal Oxide (Cr2O3, MgO and V2O3) Treated CNT/TiO2 Composites

  • Chen, Ming-Liang;Bae, Jang-Soon;Yoon, Hee-Seung;Lim, Chang-Sung;Oh, Won-Chun
    • Bulletin of the Korean Chemical Society
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    • v.32 no.3
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    • pp.815-820
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    • 2011
  • Three kinds of organometallic compounds (chromium acetylacetonate, magnesium acetate and vanadyl acetylacetonate) were used as transition metal precursor, titanium n-butoxide and multi-walled carbon nanotube as titanium and carbon precursor to prepare metal oxide-CNT/$TiO^2$ composites. The surface properties and morphology of metal oxide-CNT/$TiO^2$ composites were by Brauer-Emett-Teller (BET) surface area measurement, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersive X-ray (EDX) analysis. The photocatalytic activity of prepared metal oxide-CNT/$TiO^2$ composites was determined by the degradation effect of methylene blue in an aqueous solution under irradiation of visible light.

Synthesis and Spectroscopic Characterization of Vanadium incorporated V-AlMCM-41 Molecular Sieves

  • Back, Gern-Ho;Yu, Jong-Sung;Lee, Hye-Young;Lee, Yong-Ill
    • Journal of the Korean Magnetic Resonance Society
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    • v.10 no.2
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    • pp.141-154
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    • 2006
  • A solid-state reaction of $V_2O_5$ with AlMCM-41 followed by calcinations generated $V^{5+}$ species in the mesoporous materials. Dehydration results in the formation of a vanadyl species, $VO^{2+}$, that can be characterized by electron spin resonance (ESR). The chemical environment of the vanadium centers in V-AlMCM-41 was investigated by XRD, EDX, diffuse reflectance UV-VIS, ESR, $^{29}Si,\;^{27}Al,\;and\;^{51}V$ NMR. It was found that the vanadium species on the wall surface and inside the wall of the hexagonal tubular wall of the V-AlMCM-41 were completely oxidized to tetrahedral $V^{5+}$ and transformed to square pyramidal by additional coordination to water molecules upon hydration. The oxidized $V^{5+}$ species on the wall surfaces and inside the wall were also reversibly reduced to $VO^{2+}$ species or lower valences by thermal process.

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MAS NMR and XRD Study on the Vanadium Site pf Vanadium Silicate Mesoporous Molecular Sieve MCM-41

  • 박동호;Chi-Feng Cheng;Jacek Klinowski
    • Bulletin of the Korean Chemical Society
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    • v.18 no.1
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    • pp.70-75
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    • 1997
  • A wide range (10 < Si/V) of mesoporous vanadium silicate molecular sieves with the MCM-41 structure have been synthesized using vanadyl sulfate as the source of vanadium and characterized by XRD, 51V MAS NMR and 29Si MAS NMR. The increase of the unit cell parameter and the decrease of Q3/Q4 ratio of 29Si spectra with the vanadium content suggest the incorporation of vanadium in the framework of MCM-41 structure. 51V MAS NMR demonstrates that vanadiums in as-synthesized V-MCM-41 are present in the chemical environment of octahedra and octahedral vanadium is decreased and tetrahedral vanadium is increased inversely with raising the calcination temperature. Though the thermal treatment in rotor of hydrated sample resulted in the change from tetrahedral environment to octahedral one and the steaming and the acid treatment affect to the chemical environment of vanadium, the spectrum similar to originally calcined sample is regenerated after recalcination. This indicates that the vanadium is belong to the framework in a relatively exposed site. The best quality XRD pattern of the product of Si/V=27 may be attributable to heterogeneous nucleation mechanism. V-MCM-41's having the Si/V ratio lower than 20 are completely collapsed after calcination.

V(IV) Species, Location and Adsorbate Interactions in VH-SAPO-42 Studied by ESR and Electron Spin-Echo Modulation Spectroscopies

  • Back, Gern-Ho;Yu, Jong-Sung;Lee, Hye-Young;Kim, Min-Sik;Lee, Yong-Ill
    • Journal of the Korean Magnetic Resonance Society
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    • v.11 no.2
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    • pp.95-109
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    • 2007
  • Vanadium-incorporated aluminophosphate microporous molecular sieve VH-SAPO-42 has been studied by electron spin resonance(ESR) and electron spin-echo modulation (ESEM) spectroscopies to determine the vanadium location and interaction with various adsorbate molecules. The results are interpreted in terms of V(IV) ion location and coordination geometry. Assynthesized VH-SAPO-42 contains only vanadyl species with distorted octahedral or trigonal bipyramidal coordination. Vanadium incorporated into H-SAPO-42 occupied extra-framework site. After calcinations in $O_2$ and exposure to moisture, only species A is observed with reduced intensities. Species A is identified as a $VO(H_2O)_2^{2+}$ complex coordinated to three framework oxygen atoms bonded to aluminum. When hydrated VH-SAPO-42 is dehydrated at elevated temperature by calcination, species A loses its water ligand and transforms to $VO^{2+}$ ions coordinated to three framework oxygens (species B). Species B reduces its intensities significantly after treatment with $O_2$ at high temperature, thus suggesting oxidation of $V^{4+}$ to $V^{5+}$. When dehydrated VH-SAPO-42 makes contact with $D_2O$ at room temperature, the ESR signal of species A is regained. The species is assumed as a $VO(O_f)_3(D_2O)_2$ by considering three framework oxygens. Adsorption of deuterated methanol on dehydrated VH-SAPO-42 results in another new vanadium species D, which is identified as a $VO(CD_3OH)_2$ complex. When deuterated ethylene is adsorbed on dehydrated VH-SAPO-42, another new vanadium species E identified as a $VO(C_2D_4)^{2+}$, is observed. Possible coordination geometries of these various complexes are discussed.

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A Study on the Thermochromic properties of Ti-doped Vanadium Dioxide (티타늄이 도핑된 이산화 바나듐의 열변색 특성에 관한 연구)

  • Park, Jin Wook;Park, Seong-Soo;Ahn, Byung Hyun;Hong, Seong-Soo;Lee, Gun Dae
    • Clean Technology
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    • v.21 no.4
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    • pp.235-240
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    • 2015
  • In this study, vanadium dioxide was doped with titanium (0~0.5 at %) to improve thermochromic properties. The titanium doped vanadium dioxide (Ti-VO2) particles were prepared via thermolysis process using vanadyl sulfate, ammonium bicarbonate and titianium chloride as precursors. The crystal structure, morphology, chemical bonding and thermochromic properties were investigated by using XRD, FE-SEM, XPS, DSC and UV-Vis-NIR spectroscopy. It was found that titanium was successfully doped into the crystal lattice of VO2 and the obtained Ti-VO2 particles have monoclinic structure. With increasing Ti concentration, the particle size and phase transition temperature of Ti-VO2 particles decreased and NIR switching efficiency increased.

Chemical Species of Uranium and Vanadium in Organic Acid Media (유기산용액에서 우라늄과 바나듐의 화학종에 관한 연구)

  • Ki-Won Cha;Cong-Sik Yu;Jong-Hun Kim
    • Journal of the Korean Chemical Society
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    • v.29 no.6
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    • pp.615-622
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    • 1985
  • The chemical species formed by uranium and vanadium and their equilibria have been investigated in the various concentrations of oxalic and acetic acids by the ion exchange chromatography and UV-Vis spectrophotometry. Uranyl and vanadyl ions seem to be form the complex as $UO_2(C_2O_4)_2=$, $UO_2(C_2O_4)_3^{4-}$ and $VO_2(C_2O_4)-2^{3-}$ respectively in the concentration range of 0.005∼0.05M oxalic acid concentration. In the case of acetic acid the equilibria of $UO_2^{2+}+3Ac^-=UO_2(Ac)_3^-$ and $VO_2^++2Ac^-=VO_2(Ac)_2^-$ were existed individually according to the increase of acetic acid concentration.

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Study on the Vanadium Redox Flow Battery using Cation Exchange Membrane and Ammonium Metavanadate (메타바나듐산암모늄과 양이온교환막을 활용한 바나듐 레독스 흐름전지에 관한 연구)

  • Jung, Bo-Young;Ryu, Cheol-Hwi;Hwang, Gab-Jin
    • Membrane Journal
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    • v.31 no.4
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    • pp.262-267
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    • 2021
  • The electrochemical performance of all vanadium redox flow battery (VRFB) using an electrolyte prepared from ammonium metavanadate and a cation exchange membrane (Nafion117) was evaluated. The electrochemical performance of VRFB was measured at a current density of 60 mA/cm2. The average current efficiency of VRFB using the electrolyte prepared from ammonium metavanadate was 94.9%, the average voltage efficiency was 82.2%, and the average energy efficiency was 78.0%. In addition, it was confirmed that the efficiencies of VRFB using the electrolyte prepared from ammonium metavanadate had almost the same value as the efficiencies of VRFB using the electrolyte prepared with vanadyl sulfate (VOSO4).