Metal supported rhodium-iron catalysts

TPR and TPO patterns of silica-supported rhodium, iron, and iron-rhodium catalysts are shown in Fig. 11.5 [14]. These catalysts were prepared by pore volume impregnation from aqueous solutions of iron nitrate and rhodium chloride. Note the difference in reduction temperature between the noble metal rhodium and the non-noble metal iron. The bimetallic combination reduces largely in the same temperature range as the rhodium catalyst does, indicating that rhodium catalyzes the reduction of the iron. This forms evidence that rhodium and iron are well mixed in the fresh catalyst. The TPR patterns of the freshly prepared catalysts consist of two peaks, one coincides with that of the TPR pattern of the fully oxidized catalyst (right panel of Fig. 11.5) and can thus be... 

The metal-catalysed hydrogenation of cyclopropane has been extensively studied. Although the reaction was first reported in 1907 [242], it was not until some 50 years later that the first kinetic studies were reported by Bond et al. [26,243—245] who used pumice-supported nickel, rhodium, palladium, iridium and platinum, by Hayes and Taylor [246] who used K20-promoted iron catalysts, and by Benson and Kwan [247] who used nickel on silica—alumina. From these studies, it was concluded that the behaviour of cyclopropane was intermediate between that of alkenes and alkanes. With iron and nickel catalysts, the initial rate law is... 

A similar dependence of the activity of bimetallic catalysts on their composition is observed in the synthesis of hydrocarbons with increasing content of palladiiun, the activity drops by 1-2 orders of magnitude. Supporting of iron, cobalt, rutheniiim, or rhodium carbonyls on Cu/Si02 also suppressed the activity of these metals for synthesis of hydrocarbons from CO and H2 by 1-2 orders of magnitude. 

The type of intermediate shown in structure (B) has also been supported by Muller and Gault (119) who showed that in the reaction of 1,1-dimethylcyclopropane with deuterium over a series of thick evaporated metal film catalysts, it was only on platinum that 1,1,3-da-neopen-tane (and 1,1,3,3-d4-neopentane) were dominant products. On palladium, iron, rhodium, nickel, and cobalt the major product was 1,3-d2-neopentane. 

The phenomenon of metal transport via the creation of volatile metal carbonyls is familiar to workers using carbon monoxide as a reactant. It is often found that carbon monoxide is contaminated with iron pentacarbonyl, formed by interactions between carbon monoxide and the walls of a steel container. Thus, it is common practice to place a hot trap between the source of the CO and the reaction vessel. Iron carbonyl decomposes in the hot trap and never reaches the catalyst that it would otherwise contaminate or poison. Transport of a number of transition metals via volatile metal carbonyls is common. For example, Collman et al. (73) found that rhodium from rhodium particles supported on either a polymeric support or on alumina could be volatilized to form rhodium carbonyls in flowing CO. 

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... 

The metal catalysts active for steam reforming of methane are the group VIII metals, usually nickel. Although other group VIII metals are active, they have drawbacks for example, iron rapidly oxidizes, cobalt cannot withstand the partial pressures of steam, and the precious metals (rhodium, ruthenium, platinum, and palladium) are too expensive for commercial operation. Rhodium and ruthenium are ten times more active than nickel, platinum, and palladium. However, the selectivity of platinum and palladium are better than rhodium [1]. The supports for most industrial catalysts are based on ceramic oxides or oxides stabilized by hydraulic cement. The commonly-used ceramic supports include a-alumina, magnesia, calcium-aluminate, or magnesium-alu-minate [4,8]. Supports used for low temperature reforming (< 770 K) are... 

Platinum is an effective oxidation catalyst for carbon monoxide and the complete oxidation of hydrocarbons. Palladium also promotes the oxidation of carbon monoxide and hydrocarbons but is more sensitive to poisoning than platinum in the exhaust environment. Both platinum and palladium promote the reduction of nitric oxide but are less effective than rhodium. In addition to the noble metals, three-way catalysts contain the base metal cerium and possibly other additives such as lanthanum, nickel or iron. These base metal additives are believed to improve catalyst performance by extending conversion during the rapid air-fuel ratio perturbations and help to stabilize the alumina support against thermal degradation. 

A key question is whether the diatomic molecule in its interaction with metal surfaces remains molecular or dissociates into carbon and oxygen. Broden et al. (3) predicted, by the perturbation of molecular orbitals for CO adsorbed, that only iron could dissociate CO. However, other metals in Group VIII such as nickel (A) ruthenium (5) and rhodium (6) can dissociate CO. Recently Ichikawa et al.(7) observed that disproportionation of CO to CO2 and carbon occurs on small particles of silica-supported palladium. These results show that carbon deposition phenomena may occur via either dissociation of CO on the metals used or disproportionation of CO to CO and carbon on small platinum particles. Cant and Angove (8) studied the apparent deactivation of Pt/Si02 catalyst for the oxidation of carbon monoxide and they suggested that adsorbed CO forms patches and that oxygen atoms are gradually consumed. 

This new single-step synthesis unites the simplicity of preparation and lower production costs, with the outstanding properties of the final catalysts. By the single-step procedure proposed here, deposition of dispersed nanoparticles of noble metals on ceramic supports with customised textural properties and shape was achieved. Noble metals including platinum, palladium, rhodium, ruthenium, iridium, etc. and metal oxides including copper, iron, nickel, chromimn, cerium oxides, etc on sepiolite or its mixtures with alumina, titania, zirconia or other refractory oxides have been also studied. 

Iron and its compounds (carbide, nitride), as well as ruthenium, cobalt, rhodium, and molybdenum compounds (sulfide, carbide), are used most frequently to produce high-molecular-weight hydrocarbons. Iron can be prepared as a high-surface-area catalyst (==300 m /g) even without using a microporous oxide support. 7-AI2O3, Ti02, and silica are frequently used as supports of the dispersed transition-metal particles. Recently zeolites, as well as thorium oxide and lanthanum oxide, have... 

Other isocyanate syntheses that have recently been reported include several well-known reactions. One area which has attracted considerable attention is that of the direct production of isocyanates by the carbonylation of nitro-arenes. Both mono- and di-isocyanates are claimed to have been produced using various catalysts palladium, rhodium, and iron compounds often being cited. Other preparative reactions for isocyanates which have appeared in the literature include the acid catalysed hydrolysis of isocyanide dihalides and the reaction between alkyl halides and alkali-metal cyanates, although the latter has been given a modern flavour by the use of a polymer-supported reagent. ... 

The following facts support the assumption that the true catalysts are the transition metal hydrocarbonyls rather than the corresponding metal carbonyls. Only metals which can form hydrocarbonyls, like cobalt, rhodium and iron, can act as catalysts [123, 280, 673, 674], whereas nickel, e.g., is inactive [123, 673] in most cases. Furthermore it is known that cobalt, rhodium and iron carbonyls, under the reaction conditions applied, are able to abstract hydrogen from alcohols, amines and even from the unreactive cycloparaffins to form metal hydrocarbonyls [121-124]. 

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