Zirconia metal oxide catalysts

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-... 

A controlled modification of the rate and selectivity of surface reactions on heterogeneous metal or metal oxide catalysts is a well-studied topic. Dopants and metal-support interactions have frequently been applied to improve catalytic performance. Studies on the electric control of catalytic activity, in which reactants were fed over a catalyst interfaced with O2--, Na+-, or H+-conducting solid electrolytes like yttrium-stabilized zirconia (or electronic-ionic conducting supports like Ti02 and Ce02), have led to the discovery of non-Faradaic electrochemical modification of catalytic activity (NEMCA, Stoukides and Vayenas, 1981), in which catalytic activity and selectivity were both found to depend strongly on the electric potential of the catalyst potential, with an increase in catalytic rate exceeding the rate expected on the basis of Faradaic ion flux by up to five orders of... 

Sulfated metal oxide catalysts represent a class of extremely attractive strong solid acids showing widespread application in different areas of chemical fransformafions. It was reported that sulfated zirconia (SZ) prepared by treatment of zirconia with sulfuric acid or ammonium sulfafe exhibifs exfremely sfrong acidity, and it is able to catalyze the isomerization of bufane to isobutane at room temperature. This behavior... 

In order to address both fundamental and application aspects of electrochemical promotion in this Chapter, the combustion of ethylene over Ir02 or RUO2 catalysts and the reduction of NO with propylene over Rh catalysts —all deposited on yttria-stabilized zirconia (YSZ) solid electrolyte— have been chosen as model catalytic systems. While the literature of electrochemical promotion deals mainly with metal catalysts, our laboratory has a long experience with promotion of metal oxide catalysts, such as Ir02 and RUO2. In fact, ethylene combustion with Ir02/YSZ film catalyst was the first catalytic system found to exhibit the phenomenon of permanent electrochemical promotion, which manifests itself as a shift in the steady-state open-circuit activity due to polarization, and is attributed to a change in... 

In this chapter, the common methods of supported metal oxide catalyst preparation are presented. The molecular and nanoscale structure (i.e., textural properties) of supported metal oxides, specifically tungstated zirconia, are also discussed. Finally, several new synthesis techniques are presented, through which simultaneous control of the molecular and nanoscale structures may be possible. 

As we will see, the differences in OSC are not solely influenced by thermodynamic factors. Depending on the temperature at which the OSC is measured and also on the nature of the reducing agent (H2,C0), other surface-related processes may have a significant influence on the measured OSC values. Kinetic factors and, in connection with them, the surface structure of the oxides have a relevant role. In general, the interplay between surface and bulk structure determines the observed total OSC values. As with the OSC differences between ceria and ceria-zirconia metal-loaded catalysts, a more in-depth analysis is required in order to fully understand the redox response of thermally aged oxides. 

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... 

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. 

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. 

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). ... 

This review summarizes the recent works on syntheses of solid superacids and their catalytic action, including Lewis acids and liquid superacids in the solid state, as discussed in Sections Il-IV. Sections VI and VII describe new types of solid superacids we have studied in this decade sulfate-supported metal oxides and tungsten or molybdenum oxide supported on zirconia. Perfluorinated sulfonic acid, based on the acid form of DuPont s Nafion brand ion membrane resin, is also gaining interest as a solid superacid catalyst Nafion-H-catalyzed reactions are reviewed in Section V. 

Solid catalysts can be used at elevated temperatures, though their acidities are much weaker than those of liquid ones. From this point of view, solid superacids based on Lewis acids and liquid superacids discussed in Sections II—1V are not sufficiently stable Nafion-H is also unsatisfactory, its maximum operating temperature being below 200°C. A new type of the sulfate-supported metal oxides is more stable because of preparatory heat treatment at high temperatures, but elimination of the sulfate is sometimes observed during reaction, thus it is hoped to synthesize superacids with the system of metal oxides. Another type of superacid, tungsten or molybdenum oxide supported on zirconia, has been prepared by a new preparation method, and its stability is satisfactory so far. It is hoped that the preparation method will be extensively applied to other metal oxides for new solid superacids. 

Another important and well studied paramagnetic ion in the lattice of oxide semiconductors is Zr3+ in Zr02. Zirconia dioxide is widely used both as a catalyst of different chemical processes, and as a carrier for constructing supported metal-complex catalysts. In the last years, sulfated zirconia attracted significant interest as an active and selective catalyst in skeletal isomerization of normal alkanes at low temperatures, cracking of paraffins, alkylation and acylation of aromatics [42, 53 and Refs therein]. The appropriate experimental data are collected in the following Table 8.2. 

Although the decomposition of ozone to dioxygen is a thermodynamically favoured process,126 it is thermally stable up to 523 K and catalysts are needed to decompose it at ambient temperature in ventilation systems, in the presence of water vapour and at high space velocity. A limited number of catalysts have been evaluated and active components are mainly metals such as platinum, palladium and rhodium, and metal oxides including those of manganese, cobalt, copper, iron, nickel and silver. Supports that have been used include 7-alumina, silica, zirconia, titania and activated carbon.125,170... 

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