Supported Iron

Dehydrogenation of ethylbenzene with carbon nanofiber supported iron oxide... 

Fig. 1(b) represents the selectivity to styrene as a ftmcfion of time fijr the above catal ts. It is observed that the selectivity to styrene is more than 95% over carbon nauofiber supported iron oxide catalyst compared with about 90% for the oxidized carbon nanofiber. It can be observed that there is an increase in selectivity to styrene and a decrease in selectivity to benzene with time on stream until 40 min. In particrdar, when the carbon nanofiber which has been treated in 4M HCl solution for three days is directly us as support to deposit the iron-precursor, the resulting catalyst shows a significantly lows selectivity to styrene, about 70%, in contrast to more than 95% on the similar catalyst using oxidized carbon nanofiber. The doping of the alkali or alkali metal on Fe/CNF did not improve the steady-state selectivity to styrene, but shortened the time to reach the steady-state selectivity. 

Scheme 9 Tetraaza macrocyclic ligands for supported iron catalysts...

Previous studies by Sorokin with iron phthalocyanine catalysts made use of oxone in the oxidation of 2,3,6-trimethylphenol [134]. Here, 4 equiv. KHSO5 were necessary to achieve full conversion. Otherwise, a hexamethyl-biphenol is observed as minor side-product. Covalently supported iron phthalocyanine complexes also showed activity in the oxidation of phenols bearing functional groups (alcohols, double bonds, benzylic, and allylic positions) [135]. Besides, silica-supported iron phthalocyanine catalysts were reported in the synthesis of menadione [136]. 

Figure 4.17 illustrates how Mossbauer spectroscopy reveals the identity of the major iron phases in a supported iron catalyst after different treatments. The top spectrum belongs to a fresh Fe/Ti02 catalyst, i.e. after impregnation and drying. 

Figure4.17. Mossbauer spectra give detailed information on the state of iron in a Ti02-supported iron catalyst after different treatments. Here reduction was in H2 at 675 K for 18 h, and FTS stands for Fischer-Tropsch synthesis. [Adapted from A.M. van der Kraan, R.C.H. Nonnekens, F. Stoop and J.W. Niemantsverdriet, Appl. Catal. 27 (1986) 285.]...

Characterization of Supported Iron Oxide Particles Using Mdssbauer Spectroscopy and Magnetic Susceptibility... 

PHILLIPS ETAL. Supported Iron Oxide Particles... 

Supported iron catalysts are notoriously difficult to reduce [6-8] and thus a substantial fraction of the iron can be expected to remain inactive for the catalysis of hydrogenation. Particular attention has therefore been paid to the preparation of Fe/MgO catalysts by several different methods and examination of their effectiveness in producing metallic iron of adequate specific surface area after reduction in hydrogen. The activity and selectivity for primary amine formation have been determined for the hydrogenation of ethanenitrile (acetonitrile) and propanenitrile. 

As already indicated, the difficulty of reducing supported iron in hydrogen is well-known [6,8,11]. It probably arises from a combination of causes, the two most important of which are a strong interaction with the support [6,8] and reoxidation or inhibition by water vapour in the pores of the oxide [14]. With MgO as support, there is undoubtedly a strong tendency for iron, especially at the Fe2+ stage of reduction, to be present at least in part as FeO-MgO (Fe Mgi.jjO) solid solution [6,8]. This need not be deleterious to the ultimate formation of finely-divided iron, provided the method of preparation has led to a solid solution in which the Fe2+ ions are well-distributed. The iron particles are limited in size... 

The basis of the demonstration can be based on already published data on the surface reaction between NOz and adsorbed organic compounds. Yokoyama and Misono have shown that the rates of N02 reduction over zeolite or silica are proportional to the concentration of adsorbed propene [29], whereas Il ichev et al. have demonstrated that N02 reacts with pre-adsorbed ethylene and propylene on H-ZSM-5 and Cu-ZSL-5 to form nitro-compounds [30], Chen et al [2-4] have observed the same nitrogen-containing deposits on MFI-supported iron catalysts. The question on the pairing of nitrogen atoms is not considered here. 

A facile method for the oxidation of alcohols to carbonyl compounds has been reported by Varma et al. using montmorillonite K 10 clay-supported iron(III) nitrate (clayfen) under solvent-free conditions [100], This MW-expedited reaction presumably proceeds via the intermediacy of nitrosonium ions. Interestingly, no carboxylic acids are formed in the oxidation of primary alcohols. The simple solvent-free experimental procedure involves mixing of neat substrates with clayfen and a brief exposure of the reaction mixture to irradiation in a MW oven for 15-60 s. This rapid, ma-nipulatively simple, inexpensive and selective procedure avoids the use of excess solvents and toxic oxidants (Scheme 6.30) [100]. Solid state use of clayfen has afforded higher yields and the amounts used are half of that used by Laszlo et al. [17,19]. 

Van Steen, E., andPrinsloo, F. F. 2002. Comparison of preparation methods for carbon nanotubes supported iron Fischer-Tropsch catalysts. Catalysis Today 71 327-34. 

McDonald, M.A., Storm, D.A., and Boudart, M. 1986. Hydrocarbon synthesis from carbon monoxide-hydrogen on supported iron Effect of particle size and interstitials. J. Catal. 102 386 -00. 

Brown, R., Cooper, M., and Whan, D. 1982. Temperature programmed reduction of alumina-supported iron, cobalt and nickel bimetallic catalysts. Appl. Catal. 3 177-86. 

Miller, D.G., and Moskovits, M. 1988. A study of the effects of potassium addition to supported iron catalysts in the Fischer-Tropsch reaction. J. Phys. Chem. 92 6081-85. 

Teule-Gay, F. Transient studies of the CO/H2 reaction on various supported iron catalysts. M. S. Thesis, University of Connecticut, 1981. 

Iron-catalyzed cross-coupling reactions of various acyl chlorides or thioesters with Grignard reagents have been pioneered by Marchese et al. and other research groups.322 These transformations provide general and convenient access to a wide range of ketones and have been further extended to the use of a supported iron(lll) complex.323... 

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