Supported niobium oxide catalysts

Datka, J. Turek, A.M. Jehng, J.M. Wachs, I.E. Acidic properties of supported niobium oxide catalysts An infrared spectroscopy investigation. J. Catal. 1992, 35, 186-199. 

The aqueous preparation oT supported niobium oxide catalysts was developed by using niobium oxalate as a precursor. The molecular states oT aqueous niobium oxalate solutions were investigated by Raman spectroscopy as a -function o-f pH. The results show that two kinds o-f niobium ionic species exist in solution and their relative concentrations depend on the solution pH and the oxalic acid concentration. The supported niobium oxide catalysts were prepared by the incipient wetness impregnation technique and characterized by Raman, XRD, XPS, and FTIR as a -function o-f niobium oxide coverage and calcination temperature. The Raman studies reveal that two types o-f sur-face niobium oxide species exist on the alumina support and their relative concentrations depend on niobium oxide coverage. Raman, XRD, XPS, and FTIR results indicate that a monolayer oT sur-face niobium oxide corresponds to 19%... 

Supported niobium oxide catalysts have recently been shown to be e-f-fective catalysts Tor many catalytic reactions pollution abatement, selective oxidation,... 

Niobium ethoxide [Nb(0C2H5)g] has traditionally been used as a precursor Tor the preparation oT supported niobium oxide catalysts. This non-aqueous preparation... 

The crystalline Nb205 phase in the supported niobium oxide catalysts was detected by an APD 3600 automated X-... 

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. 

Antonelli and co-workers have recently demonstrated that room temperature stoichiometric ammonia synthesis is possible with their mesoporous titanium and niobium oxide catalysts. In this study, they proposed that the ammonia species are formed via the reaction activated nitrogen with the underlying moisture of the support. Reversible, inter-conversion of and NH2 species via exposure to moist air for aluminophosphate oxynitride catalysts has been observed by FTIR and XPS by Marquez and co-workers. There has been a lot of interest in the literature in the development of novel routes for the low temperature stoichiometric conversion of nitrogen to ammonia, e.g.. However, in principle this could be realised by the nitridation of Li, followed by hydrolysis, although the kinetics would be very slow. 

A series of supported niobium oxide on alumina catalysts, 0-45% Nb205/Al203, were further characterized by XRD, XPS, CO2 chemisorption, as well as Raman spectroscopy in order to determine the monolayer content of the Nb205/Al203 system. The transition from a two-dimensional metal oxide overlayer to three-dimensional metal oxide particles can be detected by monitoring the... 

Catalysts containing niobia supported on various oxides have been the subject of considerable recent interest [1-4]. The molecular structures and reactivity of niobium oxides supported on alumina, titania, zirconia and silica have been intensively investigated over the last few years. Niobia supported on silica has been shown to be active for the dehydrogenation and dehydration of alcohols, photo-oxidation of propene and oxidative decomposition of methyl tertiary butyl ether. Titania supported niobia is active for the selective catalytic reduction (SCR) of NO by NH3. 

Niobium oxide (niobia) is an active catalyst, and can be used as a support for metal nanoparticles or oxides, and it can serve as a promoter in some reactions ([43 5] and references therein). Catalytic applications of niobia include the Fischer-Tropsch synthesis, oxidative dehydrogenation of alkanes, and oxidative coupling of methane. Studies on high-surface-area niobium oxides are complicated by a high degree of complexity because several stable structures (NbO, NbO and Nb O ) exist and the resulting surfaces of high-surface-area niobium oxides are not simple truncations of bulk niobia structures. This is even more so for supported metal oxides when two-dimensional thin films of niobium oxide partially cover a support oxide (Al Oj, SiOj, ZrOj, TiOj, [43]). Nb Oj was also used as a support for V, Cr, Re, Mo, and W oxide overlayers [45, 46]. 

Oxidative dehydrogenation of ethane over vanadium and niobium oxides supported catalysts... 

In this work, the activity and selectivity of catalysts based on niobium and vanadium oxides supported on high surface area anatase Ti02 in ethane ODH have been investigated. Specifically, the influence of the cooperation of vanadium and niobium oxides supported phases as components inducing respectively redox and acid properties, together with the effect of the preparation conditions on the catal3dic performances have been studied. 

The Ti02 support and the 6Nb/Ti catalyst undergo a very poor reduction compared to that occurring when vanadium is present in the catalyst. The Ti02 support shows a tailed peak with maximum at 554 C while the addition of niobium oxide results in the appearance of a new peak at 609°C. 

A timeline for the development of olefin metathesis, adapted from a review by Grubbs, is shown in Figure 21.3. Olefin metathesis is more than 50 years old. " It was first conducted with ill-defined rhenium, molybdenum, and tungsten systems generated from perrhenate, aluminum oxide, - and tetraethyl lead as additive, from molybdenum oxide on p-TiO and tetramethyltin as additive, ° or from tungsten phenoxides supported on niobium oxide and silicon oxide activated with alkylaluminum reagents. The temperatures for these processes are hi, but the catalysts are relatively inexpensive and can be long lived. These are the types of catalysts that have been used for the synthesis of commodity chemicals by olefin metathesis. 

A 2000 study from Buffon [69] examined the reaction of Schrock-type, alkoxy-Mo-alkylidenes with the surface OH groups of silica, silica-alumina, and niobium oxide. The specific mode of attachment of the Mo-complex was found to be highly dependent upon the acid-base properties of the support. For silica, it appears to be a Lewis acid-base interaction between the Mo center and surface silanols, whereas in the case of silica-alumina, the attachment appears to occur via the addition of a surface OH group across the Mo-imido bond. In the case of niobium oxide, it is possible that the OH adds across the Mo-alkylidene, deactivating the complex, as the resulting material was completely inactive for metathesis. The activities of both immobilized catalysts were less than the parent homogeneous... 

The work was strongly inspired by Union Carbide s Ethoxene process, a route for manufacturing ethylene from ethane and oxygen by oxidative dehydrogenation. The first catalysts consisted of molybdenum, vanadium, and niobium oxides. The selectivity for ethylene was very high but, unfortunately, the conversion of ethane was low ( 10%). Therefore, scientists at the time focused on the co-production of ethylene and acetic acid. A catalyst consisting of molybdenum, vanadium, niobium, calcium, and antimony supported on a molecular sieve was developed (63% selectivity to acetic acid, 14% selectivity to ethylene, and 3% conversion of ethane). In addition, Rhone-Poulenc (catalyst vanadium oxide or vanadyl pyrophosphate) and BP (catalyst combination of rhenium and tungsten) patented processes for the production of acetic acid from ethane. Very efficient catalysts were also disclosed by Hoechst (molybdenum vanadate, promoted with Nb, Sb, Ca, and Pd, 250-280 °C, 15 bar, 86% selectivity to acetic add at 11% conversion of ethane per pass) and Sabic (phosphorus-modified molybdenum-niobium vanadate, 260 °C, 14 bar, 50% selectivity to acetic acid at 53% conversion of ethane). 

Acetyl ligands, in niobium complexes, C-H BDEs, 1, 298 Achiral phosphines, on polymer-supported peptides, 12, 698 Acid halides, indium compound reactions, 9, 683 Acidity, one-electron oxidized metal hydrides, 1, 294 Acid leaching, in organometallic stability studies, 12, 612 Acid-platinum rf-monoalkynes, interactions, 8, 641 Acrylate, polymerization with aluminum catalysts, 3, 280 Acrylic monomers, lanthanide-catalyzed polymerization,... 

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