Niobium oxide fluorides

On the other hand, the 25Nb AlF3 sample recovered after the separation of leached aluminum species became highly selective to hydroxy acids, with a preponderant formation of lactic acid, while the conversion of cellulose decreased only by a few percent when compared with the fresh catalyst (Table 6.9, entry 7). This catalytic performance improvement is clearly due to the leaching of aluminum that enriches the catalyst in niobium oxide fluoride phases (boiled catalyst contains 42.5 mol% Nb and 57.5 mol% A1 as against fresh catalyst (25 mol% Nb and 75 mol% Al)) alongside the introduction of an oxygen/aluminum vacancy adjacent to the niobium sites (NbOF - Lewis acid sites), by the formation of different sixfold coordinated Al units AlF Og. , fivefold coordinated units AIF 05, and fourfold coordinated species AlF 04 t- This way an optimum combination of acidity for the one-pot transformation of cellulose to lactic acid seems to be created. 

Tantalum and niobium oxides dissolve very slowly in HF solutions. Thus, it is recommended to use a high concentration of HF or a mixture of HF and H2SO4 at a temperature of about 70-90°C. The best precursors for the preparation of fluoride solutions are hydroxides. Both tantalum hydroxide, Ta205 nH20, and niobium hydroxide, M Os-nHjO, dissolve well, even in diluted HF solutions. 

Interaction between niobium oxide and fluorides, chlorides or carbonates of alkali metals in an ammonium hydrofluoride melt, yielded monooxyfluoroniobates with different compositions, MxNbOF3+x, where they were subsequently investigated [123-127]. According to DTA patterns of the Nb205 - 6NFL HF2 - 2MF system, (Fig. 18) a rich variety of endothermic effects result from the formation of ammonium monooxyfluoroniobate, its thermal decomposition and its interaction with alkali metal fluorides. The number of effects decreases and separation of ammonium ceases at lower temperatures and when going from lithium to cesium in the sequence of alkali metal fluorides. 

Simultaneous fluorination of niobium oxide and oxides of trivalent metals using an ammonium hydrofluoride melt leads only to oxide-type compounds, MinNbC>4 due to low thermal stability of fluoride or oxyfluoride compounds that contain both niobium and trivalent metals. 

The fluorination process aims to decompose the material and convert tantalum and niobium oxides into complex fluoride compounds to be dissolved in aqueous solutions. The correct and successful performance of the decomposition process requires a clear understanding of the oxygen-fluorine substitution mechanism of the interaction itself. 

It was proposed [445 - 447] that the dissolution of tantalum and niobium oxides in mixtures of hydrofluoric and sulfuric acids takes place through the formation of fluoride-sulfate complexes, at least during the initial steps of the interaction and at relatively low acid concentrations. Nevertheless, it was also assumed that both tantalum and niobium fluoride-sulfate complexes are prone to hydrolysis yielding pure fluoride complexes and sulfuric acid. No data was provided, however, to confirm the formation of fluoride sulfate complexes of tantalum and niobium in the solutions. 

Brown et al. [494] developed a method for the production of hydrated niobium or tantalum pentoxide from fluoride-containing solutions. The essence of the method is that the fluorotantalic or oxyfluoroniobic acid solution is mixed in stages with aqueous ammonia at controlled pH, temperature, and precipitation time. The above conditions enable to produce tantalum or niobium hydroxides with a narrow particle size distribution. The precipitated hydroxides are calcinated at temperatures above 790°C, yielding tantalum oxide powder that is characterized by a pack density of approximately 3 g/cm3. Niobium oxide is obtained by thermal treatment of niobium hydroxide at temperatures above 650°C. The product obtained has a pack density of approximately 1.8 g/cm3. The specific surface area of tantalum oxide and niobium oxide is nominally about 3 or 2 m2/g, respectively. 

Ammonium hydrofluoride is relatively stable, even in the molten state. In addition to being in contact with tantalum or niobium oxide, the compound will initiate the fluorination process yielding complex tantalum or niobium fluoride compounds. There is no doubt that thermal treatment of the hydroxides at high temperatures and/or at a high temperature rate leads to the enhancement of the defluorination processes, which in turn results in an increase in fluorine content of the final oxides. 

Kobayashi et al. [508] developed an effective method to control particle size and fluoride content in granular tantalum oxide and niobium oxide. The resultant powders are suitable for application in the manufacturing of ceramics, single crystals, optical glass, etc. 

The first experiments on the plasma chemical decomposition of fluoride solutions containing tantalum or niobium to obtain tantalum and niobium oxides were reported about fifteen years ago [524]. Subsequent publications were devoted to further development and expansion of the method for other refractory rare metals such as titanium and zirconium [525 - 532]. 

Investigations of the plasma chemical decomposition of tantalum-containing fluoride solutions indicated no significant differences in the process and product parameters compared to the corresponding decomposition of niobium-containing fluoride solution [529, 532]. The particle diameter, shape and specific surface area of both niobium oxide and tantalum oxide powders attest to a gas-phase mechanism of the interaction, with sequential condensation and agglomeration of the oxides. 

S Fluorination of tantalum and niobium oxides by hydrofluorides of ammonium or alkali metals yields fluorotantalate or monooxy-fluoroniobate compounds. Fluorination of tantalum or niobium oxides in the presence of oxides of other metals yields complex fluoride compounds containing both tantalum or niobium and added metals. 

Simple Binary and Related Compounds.—Reviews have been published which describe crystal structures of, and chemical bonding in, the Ta-O system. Structural aspects of niobium and tantalum oxides and oxide fluorides have... 

The alkali niobates are most conveniently prepared by the action of caustic alkalis on niobic acid or on solutions of niobium oxytri-fluoride. Other compounds of niobic acid and bases are generally prepared by fusing niobic add with the oxide, hydroxide, carbonate, or other salt of the metal. Occasionally double decomposition of a soluble alkali niobate and a soluble salt of the metal has been employed. Larsson s method1 consists in predpitating a solution of potassium niobate with a salt of a metal the dried predpitate is fused for thirty-six hours at a high temperature with boric acid, and the melt is boiled with water to which hydrochloric acid has been added. The residue consists of crystals of the insoluble niobate of the metal, usually the metaniobate. 

A number of complex niobium(V) oxide fluoride derivatives, such as... 

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