Niobium alkoxides preparation

The sol-gel method of preparing lithium niobate used lithium and niobium alkoxides. Alkoxides are often used in CVD methods, but unfortunately for the preparation of lithium niobate, lithium alkoxides are much less volatile than niobium alkoxides and to get the two metals deposited together it is better to use compounds of similar volatility. One way around this problem is to use a more volatile compound of lithium. One reported synthesis uses a p diketonate of lithium in which lithium is coordinated to 2,2,6,6-tetramethylheptan-3,5-dione (Me3CCOCH2COCMe3) (Figure 3.11). 

The bismuth aUcoxide was insoluble in methoxyethanol because of its own strong association however, it easily dissolved in methoxyethanol containing strontium alkoxide in Sr(OR)2 Bi(OR)3 molar ratios of >0.5 (Katayama and Sekine, 1991). As previously reported, the strong association of the bismuth alkoxide can be destroyed by the formation of a strontium-bismuth double alkoxide. The formation of the strontium-bismuth double alkoxide is discussed next. Also, the bismuth alkoxide was insoluble in strontium-tantalum or strontium-niobium double alkoxide solutions. The strontium-bismuth double alkoxide formed and then reacted with the tantalum or niobium alkoxide to prepare uniform alkoxide complex solutions (Kato et al., 1998). 

Niobium Products Co., 50 m /g). Many different synthesis methods have been used to prepare supported metal oxide catalysts. In the case of supported vanadium oxide catalysts, the catalysts were prepared by vapor phase grafting with VOCI3, nonaqueous impregnation (vanadium alkoxides), aqueous impregnation (vanadium oxalate), as well as spontaneous dispersion with crystalline V2O5 [4]. No drastic reduction of surface area of the catalysts was observed. 

Lithium niobate is a ferroelectric material used as an optical switch. Preparation by the simple ceramic method leads to problems in obtaining the correct stoichiometry, and a mixture of phases often results. Several sol-gel preparations have been described, their advantage being the lower temperature required for the preparation and the greater homogeneity of the product. One such preparation starts with lithium ethoxide (LiOC2H5 (or LiOEt)) and niobium ethoxide Nb2(OEt)io. Each ethoxide was dissolved in absolute ethanol and the two solutions mixed. The addition of water leads to partial hydrolysis giving hydroxy-alkoxides, for example ... 

Peercy, P.S., Dosch, R.G., and Morosin, B., "Preparation and Structural Studies of the Hydrolysis Products of Titanium, Niobium and Zirconium Alkoxides," SAND76-O556, Sandia Laboratories, Albuquerque, NM (1976). 

Vinyl ethers have also been prepared by addition of alkoxides to acetylene,6 7 6 elimination from halo ethers and related precursors,6 8 and vinyl exchange reactions.6 Reaction of an electrophilic tungsten carbenoid with methylene phosphorane or diazomethane also produces vinyl ethers.9 Enol ethers have resulted from the reaction of some tantalum and niobium carbenoids with esters,10 and the reaction of phosphoranes with electrophilic esters.4... 

In addition to the bimetallic complexes of rhenium and alkaline metals formed as byproducts in the exchange reactions of rhenium halids with alkali alkoxides (such as, for example, LiReO(OPr )5 xLiCl(THF)2 [519]) there has been recently prepared a number ofbimetallic complexes ofrhenium and molybdenum, rhenium and tungsten, and rhenium and niobium [904, 1451]. The latter are formed either due to the formation of a metal-metal bond, arising due to combination of a free electron pair on rhenium (V) and a vacant orbital of molybdenum (VI) atom or via insertion of molybdenum or tungsten atoms into the molecular structure characteristic of rhenium (V and VI) oxoalkox-ides. The formation of the compounds with variable composition becomes possible in the latter case. 

Preparation of metal oxide thin film by means of stepwise absorption of metal alkoxide has been carried out in the past for the activation of heterogeneous catalysts [13]. For example, Asakura et al. prepared one-atomic layer of niobium oxide by repeating chemisorption of Nb(OEt)5 on silica beads. The catalyst obtained by immobilizing platinum particles on a niobum oxide layer showed improved reactivity for hydrogenation of ethylene in comparison with... 

Preparation of heterometallic alkoxides between pairs of metals as similar to each other as aluminum and gallium (137) or even niobium and tantalum (138) were described. However, the formation constants of the latter derivative were found to be rather low, precluding its isolation in view of the dynamism of the equilibrium. 

Hydrolytic and non-hydrolytic sol-gel routes are implemented to prepare various pure and silica-dispersed vanadium- or niobium-based oxide catalysts corresponding to the compositions Nb-V, Sb-V and Nb-V-M (M = Sb, Mo, Si). Starting reagents in the hydrolytic procedure are isopropanol solutions of the metal alkoxides. The non-hydrolytic route is based on reactions between metal and Si alkoxides and hexane suspensions of niobium(V) chloride. The catalysts are tested in propane oxidative dehydrogenation. NbVOs, SbV04 and Nb2Mo30n are the major crystalline phases detected in the fresh catalysts, but structural modifications are in some cases observed after the use in the catalytic tests. At 500 C, propane conversions of 30 % and selectivities to propene between 20 and 40 % are attained. When the space velocity is decreased, acrolein is in some cases found as by-product. 

SBN is a solid solution system containing strontium, barium, and niobium oxides. The sol-gel solution preparation requires special precautions. This is because the alkaline-earth metal alkoxides dissolve in alcohols slowly and they are extremely moisture sensitive. Although alkoxides of both barium and stron-... 

Mesoporous oxides from elements other than sihca have been reported as early as 1994. Cieslaetal. [169] found that metals such as Sb, Fe, Zn, Pb,W, and Mo also form mesoporous oxides. However, many of the mesophases obtained were lamellar and were not porous after template removal (calcination). Antonelli and Ying reported the transformation of titanium, niobium, and tantalum alkoxides into stable mesophases [170]. Subsequently, mesoporous oxides based on zirconium, hafnium, and manganese have been synthesized (for a recent review on these materials see [171]). Bagshaw and Pinnavaia [172] prepared mesoporous alumina with worm-like pores and a specific surface area of more than 400 m g . Mesoporous alumina with surface areas above 700 m g have been reported by Vaudry et al. [173]. 

The alkali alkoxide method has been extended to the preparation of alkoxides of the hexanuclear niobium and tantalum cluster units, e.g., [M6Xi2](OMe)2.4MeOH (where M = Nb or Ta and X = Cl or Br), and M2[Ta2Cli2](OMe)6.6MeOH. 

The method was extended by Mehrotra and co-workers for the preparation of tertiary alkoxides of a number of metals lanthanides, " titanium, hafnium, vanadium,niobium, tautalum, " iron, and gallium. ... 

Thomas prepared tantalum and niobium penta-alkoxides by the method of Eq. (2.101). For example, the alcoholysis of tris-(dialkylamido) monoalkylimidotan-talum yielded pentaalkoxides very conveniently ... 

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