Zirconia Metal Oxides

Introduction of all these materials on the market is driven primarily by then-superior stability at high mobile-phase pH and temperature range. 

There is a very limited selection of commercially available materials due to higher inertness of the metal oxide surface, and there are almost no reproducible methods of chemical surface modification [37]. Most of the surface chemistry alteration is achieved by coating and not bonding. Control of the surface area and porosity is also limited. 

The commercial availability of zirconia-based HPLC packings are mainly related to the enormous extensive research of P. Carr and other workers [37, 38]. They applied zirconia as the starting material for a number of different polymer-coated RP phases. 

Carr and others have described the preparation and properties of polybutadiene (PBD) and polyethyleneimine (PEI), as well as aromatic polymer-coated and carbon-clad zirconia-based RP phases. The preparation of PBD-coated zirconia and the chromatographic evaluation of these phases have been described extensively by Carr, McNeff, and others [39 1]. From these studies, the authors conclude that at least for neutral analytes PBD zirconia-coated phases behave quite similar with respect to retention and efficiency compared to silica-based RP phases [42]. For polar and ionic analytes, however, substantial differences with respect to retention, selectivity, and efficiency have been reported [43]. 

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The small precious metal crystals can exist as metal crystallites or as metal oxides, both of which are catalytic (31). Rodium oxide has a tendency to react with alumina to form a soHd solution (35). To minimize this reaction, zirconia is used with the alumina (36). PubHcations regarding the TWC function of precious metals abound (37—42). 

Raman spectroscopy has provided information on catalytically active transition metal oxide species (e. g. V, Nb, Cr, Mo, W, and Re) present on the surface of different oxide supports (e.g. alumina, titania, zirconia, niobia, and silica). The structures of the surface metal oxide species were reflected in the terminal M=0 and bridging M-O-M vibrations. The location of the surface metal oxide species on the oxide supports was determined by monitoring the specific surface hydroxyls of the support that were being titrated. The surface coverage of the metal oxide species on the oxide supports could be quantitatively obtained, because at monolayer coverage all the reactive surface hydroxyls were titrated and additional metal oxide resulted in the formation of crystalline metal oxide particles. The nature of surface Lewis and Bronsted acid sites in supported metal oxide catalysts has been determined by adsorbing probe mole-... 

Out of the metal oxides, sulfated titania and tin oxide performed slightly better than the sulfated zirconia (SZ) catalyst and niobic acid (Nb205). However, SZ is cheaper and readily available on an industrial scale. Moreover, it is already applied in several industrial processes (7,8). Zirconia can be modified with sulfate ions to form a superacidic catalyst, depending on the treatment conditions (11-16). In our experiments, SZ showed high activity and selectivity for the esterification of fatty acids with a variety of alcohols, from 2-ethylhexanol to methanol. Increasing... 

H-ZSM-5, Y and Beta) Sulfated metal oxides (zirconia, titania, tin oxide) Niobic acid (Nb205)... 

Preparation of mixed metal oxides - The sulfated metal oxides (zircoiua, titaiua and tin oxide) were synthesized using a two-step method. The first step is the hydroxylation of metal complexes. The second step is the sulfonation with H2SO4 followed by calcination in air at various temperatures, for 4 h, in a West 2050 oven, at the temperature rate of 240°C hSulfated zirconia Zr0Cl2.8H20 (50 g) was... 

Together with the fast oxidation (at low temperatures) of NO to N02, the plasma causes the partial HC oxidation (using propylene, the formation of CO, C02, acetaldehyde and formaldehyde was observed). Both the effects cause a large promotion in activity of the downstream catalyst [86]. For example, a "/-alumina catalyst which is essentially inactive in the SCR of NO with propene at temperatures 200°C allows the conversion of NO of about 80% (in the presence of NTP). Formation of aldehydes follows the trend of NO concentration suggesting their role in the reaction mechanism. Metal oxides such as alumina, zirconia or metal-containing zeolites (Ba/Y, for example) have been used [84-87], but a systematic screening of the catalysts to be used together with NTP was not carried out. Therefore, considerable improvements may still be expected. 

FIGURE 19.12 Considerations for the interpretation of SSITKA data. Case 1 Three formates can exist, including (a) rapid reaction zone (RRZ)—those reacting rapidly at the metal-oxide interface (b) intermediate surface diffusion zone (SDZ)—those at path lengths sufficient to eventually diffuse to the metal and contribute to overall activity, and (c) stranded intermediate zone (SIZ)—intermediates are essentially locked onto surface due to excessive diffusional path lengths to the metal-oxide interface. Case 2 Metal particle population sufficient to overcome excessive surface diffusional restrictions. Case 3 All rapid reaction zone. Case 4 For Pt/zirconia, unlike Pt/ceria, the activated oxide is confined to the vicinity of the metal particle, and the surface diffusional zones are sensitive to metal loading. 

An interesting variation on sulfated metal oxide type catalysts was presented by Sun et al. (198), who impregnated a dealuminated zeolite BEA with titanium and iron salts and subsequently sulfated the material. The samples exhibited a better time-on-stream behavior in the isobutane/1-butene alkylation (the reaction temperature was not given) than H-BEA and a mixture of sulfated zirconia and H-BEA. The product distribution was also better for the sulfated metal oxide-impregnated BEA samples. These results were explained by the higher concentration of strong Brpnsted acid sites of the composite materials than in H-BEA. 

With XPS it is possible to obtain good analytical information on the amount of metal adsorbed and, in favourable cases, to identify the chemical form of that metal. Oxidation states are readily determined and it can be shown, for example, that adsorption of Co(II) on manganese oxides results in oxidation to Co(III) (38,39), whereas adsorption of Co(II) on zirconia and alumina leads to the formation of cobalt(II) hydroxide (40). With Y-type zeolites hexaaquacobalt(II) is adsorbed as Co(II), and cobalt(III) hexaammlne is adsorbed as Co(III). The XPS spectrum of Co(II) adsorbed on chlorite was consistent with the presence of the hexaaquacobalt(II) ion for pH 3-7 and indicated that no cobalt(II) hydroxide was present (41). With kaollnlte and llllte, Co is adsorbed as Co(II) over the pH range 3-10 (39,42), it being bound as the aqua ion below pH 6 and as the hydroxide above pH 8. Measurements involving Pb have... 

Moreover, the efficiency of these catalysts could be modihed by tailoring the nature of the metal oxide support and/or reaction conditions (especially the reaction temperature). In this way, interesting conclusions can be obtained when comparing the isobutane/2-butene alkylation catalyzed on two of the most studied catalysts, that is, beta zeolite and sulfated zirconia, when operating at different reaction temperatures. (Table 13.2). ... 

The net result is the formation of a dense and uniform metal oxide layer in which the deposition rate is controlled by the diffusion rate of ionic species and the concentration of electronic charge carriers. This procedure is used to fabricate the solid electrolyte yttria stabilized zirconia (YSZ). 

Zirconia membranes on carbon supports were originally developed by Union Carbide. Ultrafiltration membranes are commercially available now under trade names like Ucarsep and Carbosep. Their outstanding quality is their high chemical resistance which allows steam sterilization and cleaning procedures in the pH range 0-14 at temperatures up to 80°C. These systems consist of a sintered carbon tube with an ultrafiltration layer of a metallic oxide, usually zirconia. Typical tube dimensions are 10 mm (outer diameter) with a wall thickness of 2 mm (Gerster and Veyre 1985). 

Neodymium is a moderately strong reducing agent. It reduces several metal oxides, such as magnesia, alumina, silica, and zirconia at elevated temperatures, converting these oxides to their metals. 

Typical n-alkyl ligand densities that can be achieved with -alkylchlorosi lanes are within the range of 2.5-3.2pmolm-2, whilst with disilazanes, ligand densities approaching the limited values can be reached under optimized conditions, i.e. between 3.50 and 4.20 pmolm-2. Surface-modified zirconia or other metal oxide based RPC sorbents can be similarly prepared by either of the above two strategies. Compared to n-alkylsilicas, these ceramic RPC sorbents show different selectivities with synthetic peptides, as well as different chemical stability profiles. Consequently, RPC sorbents based on these types on surface-modified, porous metal oxide materials fulfill useful and complementary roles, but at this point in time, have achieved a more limited range of applications for the resolution of synthetic peptides due to their limited availability. 

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