This semestral thesis deals with problematics of redox flow batteries, especially vanadium batteries. The first part is focused on describing basic terms, describes redox batteries and explains chemical processes. It also deals with vanadium batteries properties and construction. The second part of the thesis describes diagnostic method of spectroscopy, which seems to be very perspective for examining attributes of vanadium redax batteries.

The quadrupolar interaction in sodium orthovanadate dodecahydrate, calcium orthovanadate, vanadinite, descloizite, zirconium divanadate, cadmium divanadate, potassium metavanadate and vanadium pentoxide, was studied by nuclear magnetic resonance. The v51 quadrupole coupling constants in these compounds show a strong correlation with the distortion of the tetrahedral symmetry around the vanadium ion. Vanadium pentoxide is an exception and shows a surprisingly small coupling constant. The point multipole model was found to be inadequate for the calculations of the electric field gradients in these compounds. A covalent model provides an explanation of the small magnitude of the coupling constant of vanadium pentoxide. However, because of the numbers of approximations in this model, only a qualitative correlation with the experimental results was achieved. In addition, the chemical shift tensor of the v51 resonance line in a single crystal of vanadium pentoxide was measured to be very large. This result was correlated with a large Van Vleck term in the magnetic susceptibility of vanadium pentoxide. / Thesis / Doctor of Philosophy (PhD)

Vanadium Redox Flow Batteries VRFBs are promising energy storage systems with highly recyclable electrolytes. The recycling of these systems usually involves ammonium-based salt precipitation steps, which produce toxicgases and contaminated water as waste. In this study, a novel method has been developed to recycle vanadiumdirectly from VRFB electrolyte solutions. The purity and characteristics of the final product have been analyzedusing X-ray Diffraction and Cyclic Voltammetry analysis. The method developed in this study has a precipitationrecovery of 98%. However, further investigation is needed to improve product purity and method optimization. / Sammanfattning på svenska: Vanadium Redox Flödes Batterier VRFB är lovande energilagringssystem medmycket återvinningsbara elektrolyter. Återvinningen av dessa system innefattar vanligtvis ammoniumbaseradesaltutfällningssteg som producerar giftiga gaser och förorenat vatten som avfall. I denna studie har en ny metodutvecklats för återvinning av vanadium direkt från VRFB elektrolytlösningar. Renheten och egenskaperna hosslutprodukten har analyserats med X-ray diffraktion och cyclic voltammetry analys. Metoden som utvecklats idenna studie har återvinnings kapacitet på 98 %. Ytterligare utredning behövs inom förbättring av produktensrenhet samt metods optimering.

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Darbo tikslas yra susintetinti natrio-vanadžio oksidinę bronzą Na0.33V2O5 zolių-gelių sintezės būdu bei nustatyti jos cheminį sąstatą Rentgeno fotoelektronų spektroskopijos metodu. Darbe aprašyti zolių-gelių technologijos pagrindai, vanadžio pentoksido ir jo hidratuotų junginių struktūra, vanadžio oksidinių bronzų savybės ir sintezės būdai bei Rentgeno fotoelektronų spektroskopijos metodo pagrindai. Pateiktas išsamus vanadžio – natrio oksidinės bronzos sintezės zolių-gelių metodu technologijos aprašymas. Aprašyti eksperimentiniai bronzos ir vanadžio – natrio kserogelio Rentgeno fotoelektronų spektrai. Gautas rezultatas: nustatyta, kad zolių – gelių technologija leidžia paprastais metodais, nenaudojant sudėtingos aparatūros, susintetinti norimos cheminės sudėties vanadžio – natrio oksidines bronzas; Rentgeno fotoelektronų spektroskopijos metodas įgalina atlikti bronzų kokybinę bei kiekybinę cheminę analizę ir nustatyti metalų jonų valentines būsenas bronzoje; sintetinant bronzą iš V2O5 ir Na2SO4 galutiniame produkte nėra sieros pėdsakų; susintetintoje bronzoje vanadžio jonai yra dviejose valentinėse būsenose – V4+ ir V5+. / The main aim of the present work was the synthesis of vanadium – sodium oxide bronze by using sol-gel technology and the study of the bronze chemical composition by X-Ray photoelectron spectroscopy. The bases of sol-gel technology, the structure of vanadium pentoxide and its hydrated compounds, the properties and the structure of vanadium oxide bronzes and the bases of X-Ray photoelectron spectroscopy are described in the work. The detailed description of technological process of vanadium – sodium oxide bronze synthesis by sol-gel technology is resulted. The experimental results of the study of X-Ray photoelectron spectra of vanadium - sodium bronze ant its hydrate are described and discussed. As a result of work, it is established that sol-gel technology allows a synthesis of bronzes of necessary structure by simple methods, without using difficult equipment; X-Ray photoelectron spectroscopy method allows making a quantitative and qualitative analysis of the composition of the bronzes and an establishment of the valence of metals ions; when the bronze was synthesized V2O5 and Na2SO4, the sulphur presence was not observed in the bronze; vanadium ions in the bronze are in V4+ and V5+ states.

Industrial catalysts used in commercial processes for the production of maleic anhydride are mainly Vanadium Phosphorous Oxide (VPO) catalysts. The VPO catalyst used is Vanadyl Pyrophosphate (VO)2P207 made from its precursor Vanadium Phosphorous Hemi-Hydrate VOHP04.O.5H20 in an non-aqueous medium. In order for the VPO catalyst to perform optimally, a metal promoter, Ru, was selected as the doping agent in this study. Four catalysts of different metal doping concentrations (undoped, 0.2%, 0.6% and 1%) were subjected to the oxidation of n-butane. Promoters are added to facilitate the oxidation of n-butane to maleic anhydride. n-Butane gas is now being used in many industrial processes, in fixed bed reactors to convert the gas to maleic anhydride. Catalysts were calcined under high temperatures under a nitrogen atmosphere. It was found that with an increase in reaction temperature, there was an increase in conversion of n-butane to maleic anhydride. Selectivity of the product also showed an increase with an increase in temperature at a Gas Hourly Space Velocity (GHSV) of 1960-2170hr-1. Catalysts were characterized using different techniques such as Electron Dispersive X-Ray Spectroscopy, Inductively Coupled Plasma-Atomic Emission Spectroscopy, Fourier Transform - Infra Red, Average Oxidation State, Brunauer Emmett and Teller (surface area), X-Ray Diffraction and Scanning Electron Microscopy. The 0.6% Ru promoted VPO catalyst showed to be most effective in terms of conversion, selectivity and yield, at a temperature of 450°C as compared to the other catalysts studied. The catalysts degenerated after being subjected to higher temperatures. The selectivity obtained by this catalyst was at 70.2% and the yield obtained was 37%. This study showed that with an increase in Ru up to a certain concentration (0.6%), an increase in selectivity and yield was observed, thereafter, with additional Ru doping, a decrease in selectivity and yield was obtained. / Thesis (M.Sc.)-University of Natal, 2003.

Co promoted and unpromoted vanadium-phosphorous-oxide (VPO) catalysts were synthesized via an organic route. The catalyst precursor was calcined and then conditioned in a reactor, forming the active vanadyl pyrophosphate, (VO)2P2O7, phase. Different promoter loaded catalysts were synthesized and their effect on the yield of maleic anhydride (MA) from n-butane oxidation was examined at different temperatures and gas hourly space velocities (GHSV). The catalysts were tested as a powder. The catalysts were examined in the oxidation of n-butane gas, over air as an oxidant, in a specially designed and constructed continuous flow, fixed-bed catalytic micro-reactor equipped with an on-line gas chromatography (GC) monitoring system. A thermal conductivity detector (TCD) was employed for carbon oxide monitoring and a flame ionization detector (FID) for all other products. The catalysts were characterised by X-ray diffraction (XRD) to determine the phases present in the precursor, calcined and used catalysts. The Brunauer-Emmet-Teller (BET) surface area was calculated for the different promoter loaded catalysts. Fourier transform infrared (FT-IR) spectra, via the KBr pellet method, and attenuated total reflectance (ATR) spectra were recorded to determine the anions present in the bulk and surface of the catalyst respectively. Energy dispersive X-ray (EDX) and inductively couple plasma-atomic emission spectroscopic (ICP-AES) techniques were employed to determine the elemental composition on the surface and in the bulk of the catalyst respectively. Scanning electron microscopic (SEM) images of the catalysts during different stages of their investigation were recorded. The average vanadium oxidation state (AV) in the bulk of the catalyst was determined via a titrimetric method. The catalysts were optimized to a high yield and selectivity of MA. The operating temperature, GHSV and promoter loading on the catalyst were the parameters that were changed during the testing of the catalyst. Different stages of the catalyst's life were characterised via the techniques mentioned above. The catalysts were monitored over a 200-hour period on average, usually taking approximately 24 hours to equilibrate. One such Co promoted catalyst yielded 45 % MA at 275°C and GHSV of 2878 hr-1 on equilibration, with an n-butane conversion of 73 %, whilst all previously reported VPO catalysts produce far lower MA yields at this temperature. / Thesis (M.Sc.)-University of Natal, Durban, 2002.

A series of five, tetradentate Schiff-base ligands were synthesised and chelated to vanadyl to form oxovanadium(IV) complexes. The ligands, 4,4’-{benzene-1,2-diylbis[nitrilo(1E)phen-1-yl-1ylidene]}- dibenzene-1,3-diol (H2L1), 4,4’-{ethane-1,2-diylbis[nitrilo(1E)phenyl-1-yl-1-ylidene]}dibenzene-1,3-diol (H2L2), 4,4’-{propane-1,2-diylbis[nitrilo(1E)phen-1-yl-1-ylidene]}dibenzene-1,3-diol (H2L3), 4,4’-{(2- hydroxypropane-1,3-diyl)bis[nitrilo(1E)phen-1-yl-1-ylidene]}dibenzene-1,3-diol (H2L4) and 4,4’-{2,2- dimethylpropane-1,3-diyl)bis-[nitrilo(1E)phen-1-yl-1-ylidene]}-dibenzene-1,3-diol (H2L5), characterised by TOF-MS, IR, electronic absorption, 1H and 13C NMR spectroscopy. The ligand H2L5 was also characterised by XRD. The ligands were shown to have a bis-zwitterionic structure in the solid state, and possibly also in solution. Complexes were characterised by Elemental Analysis, TOF-MS, IR, electronic absorption spectra, EPR and 51V NMR spectroscopy. They form mononuclear complexes, with one ligand binding a single vanadyl ion. EPR spectroscopy was performed on both the powdered form and solutions of the complexes. All the complexes displayed axial symmetry, with increasing distortion from an ideal square pyramidal geometry as the size and bulk of the central chelate ring was increased. Isotropic g0 values suggest solvent interaction with the vanadium ion for the coordinating solvent DMSO. Additional distortion on the coordination geometry, presumably from the benzyl groups of the compounds, causes the isotropic hyperfine coupling constants to be greater than expected. Furthermore, the ability of the complexes to bind peroxide species was investigated by following the addition of H2O2 to the complexes using 51V NMR spectroscopy to observe shielding changes at the vanadium nucleus, and 1H NMR spectroscopy to monitor the bulk magnetic susceptibility, via a modified Evan’s NMR method. Similar experiments were done with sodium hydroxide for comparison. As expected, the oxoperoxovanadium(V) complexes were more stable than their progenitor oxovanadium(IV) complexes. Additionally, increasing the distortion from the ideal pseudo square-pyramidal coordination geometry for the vanadyl ion resulted in a greater increase in the apparent stability of the peroxocomplexes. This latter effect is further enhanced by the addition of a hydrogen-bonding group in close proximity to the vanadium nucleus. DFT calculations of the optimized geometries, natural bond orbitals, electronic absorption and infra-red frequencies were performed for both the ligands and the complexes; nuclear magnetic resonance calculations were performed for the ligands as well. The B3LYP/6-311G (d,p) and B3LYP/LANL2DZ level of theories were used for the ligands and complexes respectively, except for electronic transitions, which were calculated using TD-SCF methods for both ligands and complexes. Calculated and experimental results were compared where possible, and showed reasonable agreement for all calculations performed. The exception to this was for the NMR calculations for the ligands, which were poorly simulated. Finally, the in vitro biological activity of the complexes was evaluated for cytotoxicity against the human tumour cell lines: A549, U251, TK-10 and HT29, via an MTT assay. All complexes showed promising anticancer activity, as evidenced by their low IC50 values for the cell lines A549, U251 and TK-10, which are in general, lower than that observed for cisplatin. They did, however, express negligible activity against the HT29 colon adenocarcinoma cell line; showing an apparent selectivity for certain cell lines. These oxovanadium(IV) complexes, thus warrant further evaluation as chemotherapeutic agents. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2012.

Vanadium pentoxide with loadings varying from 2.5-15 wt% was supported on hydroxyapatite (HAp) by the wet impregnation technique. The materials were characterized by techniques such as X-ray powder diffraction (XRD), Inductively coupled plasma-optical emission spectroscopy (ICP-OES), Brunauer Emmett Teller (BET) surface area measurement, Fourier Transformation- Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Temperature Programmed Desorption (TPD) and Temperature Programmed Reduction (TPR). From XRD and IR analyses, vanadium is found in the vanadium pentoxide phase for the lower loadings, whereas for weight loadings in excess of 10%, an additional pyrovanadate phase exists. Electron microscopy provides evidence of a homogenous distribution of the vanadium species on the hydroxyapatite. Oxidative dehydrogenation reactions carried out in a continuous flow fixed bed reactor showed that selectivity towards desired products was dependent on the vanadium concentration and the phase composition of the catalyst. Good selectivity towards octenes was achieved using the 2.5 wt% V₂O₅ on HAp loaded catalyst. There was a marked decrease in octene selectivity and a significant increase in the formation of C8 aromatics when higher loadings of vanadium were used. At a conversion of 24% at 450 ˚C, the 15 wt% V₂O₅ on HAp showed a selectivity of 72% towards octenes. A maximum selectivity of 10 % for C8 aromatics was obtained using the 15 wt% V₂O₅ on HAp catalyst at a conversion of 36 % at 550 ˚C. Vanadium pentoxide with 2.5 wt% and 10 wt% loading supported on Ca-HAp, Sr-HAp, Mg- HAp, Ba-HAp was tested at different temperatures with varying n-octane to oxygen ratios. The selectivity towards products depended on the hydroxyapatite support. Ca-HAp showed preference towards octenes, Sr-HAp towards aromatics, Mg-HAp towards oxygenates and Ba- HAp towards aromatics and oxygenates. In the development of a more detailed mechanistic study for the oxidative dehydrogenation noctane, the role of the intermediates such as 1-octene, 2-octene, 3-octene, 4-octene and 1, 7- octadiene was investigated. The influence of hydrocarbon to oxygen ratios was also considered. Ethyl benzene and styrene were produced with high selectivities using 1-octene and 1, 7- octadiene as feeds, whereas o-xylene was the main product when 2-octene, 3-octene and 4- octene were used as feedstocks. / Thesis (Ph.D.)-University of KwaZulu-Natal, Durban, 2012.