Promoter transition metal oxides

The sulfate promoted transition metal oxides focussed considerable attention in recent years due to attractive catalytic properties. Most of the research carried out to date centered on sulfated zirconias,1 5 not surprisingly perhaps, as they exhibit the highest surface acidity (Ho <-16.04) among the members of this family of materials and appear to be able to initiate isomerization reactions in temperatures as low as 298 K. Far less interest attracted sulfated porous titanias, mainly owing to a lower surface acidity,6 although it may be a useful property in many catalytic situations. Thus closer inspection of the preparation procedures for sulfated titanias may be of interest, in particular as the reports on preparation and properties of these materials are scarce and we are not familiar with any work dealing with titania-sulfate aerogels. 

Such an expression is expected to be valid when the promoting action is limited to the perimeter of the promoter patches on the metal surface. Three steps can in principle be influenced by promoters (transition metal oxides) ... 

This process has many similarities to the Phillips process and is based on the use of a supported transition metal oxide in combination with a promoter. Reaction temperatures are of the order of 230-270°C and pressures are 40-80 atm. Molybdenum oxide is a catalyst that figures in the literature and promoters include sodium and calcium as either metals or as hydrides. The reaction is carried out in a hydrocarbon solvent. 

The interaction and sorption of metal ions with metal oxide and clay surfaces has occupied the attention of chemists, soil scientists, and geochemists for decades (1-4). Transition metal oxides receiving particular emphasis have included various oxides of manganese and iron (5). Interest in sorption phenomena is promoted by the desire to better understand incorporation of metals into minerals, especially marine deposits ( ), the removal of trace metal pollutants and radionuclides from rivers and streams, via sorption and/or precipitation phenomena (1,6), and the deposition of metals on solid substrates in the preparation of catalysts (7,8). 

Selective partial oxidation of hydrocarbons poses considerable challenges to contemporary research. While by no means all, most catalytic oxidations are based on transition-metal oxides as active intermediates, and the oxidative dehydrogenation of ethylbenzene to styrene over potassium-promoted iron oxides at a scale of about 20 Mt/year may serve as an example [1]. Despite this... 

On the other hand, the origin of the promoter metal and metal oxide effects is not always clear, despite the many detailed characterization studies. In what follows, we will give first a possible definition of the different promotion phenomena described in literature, as well as their mode of operation. The second part deals with an extensive literature overview of the effect of each promoter element on the F-T activity, selectivity and stability of the active Co phase. The different modes of operation will be evaluated for each element. Special attention will be paid to noble metal and transition metal oxide promotion effects. 

Water-gas shift reaction. The water-gas shift (WGS) reaction (reaction (2)) made by particles composed of a promoter element close to a supported cobalt particle leads to a change in the local CO/H2 ratio, which may affect the surface coverage of cobalt. As a result, both the activity and the selectivity of the catalyst can be altered. Some transition metal oxides are known to act as WGS reagents. 

Transition Metal Oxide Promotion Effects. Many transition metal oxides have been investigated as potential promoters for Co-based F-T catalysts 139,143 145,147 149,151 152,154,158 161,165,166,168 173,251,252,255 259 Although... 

Early in the nineties Ruiz et al. reported enhanced catalyst activities and increased selectivities to alkenes and higher hydrocarbons upon addition of V, Mg, and Ce oxides to Co-based F-T catalysts.These variations were attributed to electronic effects induced by the transition metal oxide. Similar results were obtained by Bessel et al. using a Cr promoter in Co/ZSM-5 catalysts.This group observed that the addition of Cr improved the catalyst activity, and shifted the selectivity from methane to higher, generally more olefinic, hydrocarbons. Based on H2 and CO chemisorption, as well as TPR and TPD results, they suggested that the promotion was caused by an interaction between the transition metal oxide and the cobalt oxide, which inhibits... 

Rhodium is a unique metal since it can catalyze several transformations.222,223 It is an active methanation catalyst and yields saturated hydrocarbons on an inert support. Methanol is the main product in the presence of rhodium on Mg(OH)2. Transition-metal oxides as supports or promoters shift the selectivity toward the formation of C2 and higher oxygenates. 

As reviewed by Ponec,18 the formation of alcohols is observed when a metal is promoted by a transition metal oxide. Kiennemann et al,19 has associated the presence of anion vacancies at the metal-support interface with the capability to dissociate CO and allow CO insertion to produce higher alcohols. This model can be used to explain our results on tungsten carbides. 

As for the complete oxidation of propene, propane and methane, Nieuwenhuys and coworkers studied the influence of metal oxides additives on the catalytic activity of Au/Al203 [109-115], The addition of 3d transition metal oxides (MnOx, CoOx or FeOx), which were active by themselves, or ceria that was poorly active by itself promoted the catalytic activity of Au/Al203 in the total oxidation of propene [112]. The most active catalyst was Au/Ce0x/Al203, with a T95 at 497 K and with a high stability. In these cases, ceria and the transition metal oxides may act as co-catalysts and the role is twofold it stabilizes the Au NPs against sintering (ceria)... 

The next work [63] discusses the use of hydrogen peroxide and alkyl peroxides as effective oxidants in applied studies. Effective oxidation catalysts consisting of promoter transition metals are described. 

Abstract. Tungstated zirconia catalysts are stable and highly selective catalytic materials for the isomerization of alkanes when promoted by platinum and a transition metal oxide and when dihydrogen is present in the feed. Physical properties and the catalytic performance of these solids for the isomerization of n-pentane are discussed. 

K).8"10 The promotion of SZ catalysts by the addition of noble metals and transition metal oxides improved their stability, activity and selectivity even further. However, SZ catalysts suffer from several problems that impede their practical application.11... 

In nonreactive molten salts, on the other hand, flux components are not incorporated into the product phase. Here, the molten salt acts more in the classical sense as a reagent to promote the reaction at a lower temperature than would be required by the ceramic, or direct, route (Section 5.2). This is accomplished by two attributes of molten salts an acid-base equilibrium that enables the general dissolution-recrystallization of metal oxides and a highly electropositive (oxidizing) environment that stabilizes the highest oxidation state of many transition metals (Gopalakrishnan, 1995), which can lead to mixed valency. A plethora of complex transition metal oxides have been synthesized in nonreactive molten alkali metal hydroxides, carbonates, and hypochlorites. Examples of such molten salt routes to mixed transition metal oxides include (Rao and Raveau, 1998) ... 

It is perhaps worthwhile noting that the promoter patches on the metal can be either created during the wet steps of the catalyst preparation, or when a transition metal oxide is used as a support, they can be created by migration of the support material on the metal upon high temperature reduction. The metal surface can be kept almost completely covered in vacuo (SMSI effect) [52], but in the presence of CO or of the reaction mixture, the layer of oxide recrystallizes and the metal surface becomes accessible again from the gas phase [33]. 

Lanthanides as modifiers to other oxides in aluminas In zirconias In iron oxide Lanthanide oxides in mixed oxides With aluminas With iron oxides With other transition metal oxides To maintain surface area To increase oxidation rates To increase methanation rates For conduction in electrocatalysis For ammonia synthesis promotion To provide sulfur oxides (SO.,) control For dehydrogenation in carbon monoxide reactions For oxidation... 

Because of the complex nature of the reactions that take place in the converter, a mixture of catalysts is used. The most effective catalytic materials are transition metal oxides and noble metals such as palladium and platinum. A catalytic converter typically consists of platinum and rhodium particles deposited on a ceramic honeycomb, a configuration that maximizes the contact between the metal particles and the exhaust gases. In studies performed during the last ten years researchers at General Motors have shown that rhodium promotes the dissociation of NO molecules adsorbed on its surface, thereby enhancing the conversion of NO, a serious air pollutant, to N2, a natural component of pure air. 

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