Iron oxide-catalysed

This oxide catalyses the violent or even explosive decomposition of hydrogen peroxide. This reaction explains the numerous accidents mentioned involving the contact of hydrogen peroxide with rusted iron. Two accidents of this nature dealt with mixtures of hydrogen peroxide with ammonia and an alkaline hydroxide The detonations took place after a period of induction of respectively several hours and four minutes. Iron (III) oxide also catalyses the explosive decomposition of calcium hypochlorite. 

It is dangerous to prepare phthalic anhydride because of the oxidation exothermicity and risks of accidental catalysis by rust. This reaction forms naphthoquinone as a by-product. This compound may have caused a large number of accidents (that caused the compounds to ignite spontaneously) causing the compounds to combust. These accidents may have been caus by the naphthoquinone oxidation catalysed by iron phthalates, which are present in this reaction. However, it will be seen later that phthalic anhydride can also decompose in certain conditions that may be combined here. 

In a review of the course and mechanism of the catalytic decomposition of ammonium perchlorate, the considerable effects of metal oxides in reducing the explosion temperature of the salt are described [1], Solymosi s previous work had shown reductions from 440° to about 270° by dichromium trioxide, to 260° by 10 mol% of cadmium oxide and to 200°C by 0.2% of zinc oxide. The effect of various concentrations of copper chromite , copper oxide, iron oxide and potassium permanganate on the catalysed combustion of the propellant salt was studied [2], Similar studies on the effects of compounds of 11 metals and potassium dichromate in particular, have been reported [3], Presence of calcium carbonate or calcium oxide has a stabilising effect on the salt, either alone or in admixture with polystyrene [4],... 

It is unfortunately the case that when we incubate apoferritin with a certain number of iron atoms (for example as ferrous ammonium sulfate), the product, after elimination of non-protein-bound iron, does not have a homogeneous distribution of iron molecules which were able to (i) take up iron rapidly through the three fold channels, (ii) quickly transfer it and form a diiron centre on a ferroxidase site, and (iii) to transfer the iron inward to a nucleation site, where (iv) it will begin to catalyse iron oxidation on the surface of the growing crystallite, will accumulate iron much more rapidly, and in much greater amounts than molecules in which steps (i), (ii) and (iii) are slower, for whatever reasons (perhaps most importantly subunit composition, and the disposition of subunits of the two types H and L, one with regard to the other). This polydispersity makes the analysis of the process of iron uptake extremely difficult. 

About a quarter of the total body iron is stored in macrophages and hepatocytes as a reserve, which can be readily mobilized for red blood cell formation (erythropoiesis). This storage iron is mostly in the form of ferritin, like bacterioferritin a 24-subunit protein in the form of a spherical protein shell enclosing a cavity within which up to 4500 atoms of iron can be stored, essentially as the mineral ferrihydrite. Despite the water insolubility of ferrihydrite, it is kept in a solution within the protein shell, such that one can easily prepare mammalian ferritin solutions that contain 1 M ferric iron (i.e. 56 mg/ml). Mammalian ferritins, unlike most bacterial and plant ferritins, have the particularity that they are heteropolymers, made up of two subunit types, H and L. Whereas H-subunits have a ferroxidase activity, catalysing the oxidation of two Fe2+ atoms to Fe3+, L-subunits appear to be involved in the nucleation of the mineral iron core once this has formed an initial critical mass, further iron oxidation and deposition in the biomineral takes place on the surface of the ferrihydrite crystallite itself (see a further discussion in Chapter 19). 

Hence, the overall reaction for iron oxidation and hydrolysis at the ferroxidase centre, followed by further hydrolysis and migration to the core nucleation sites consists of two reactions, the protein-catalysed ferroxidase reaction itself and the Fe(II) plus H202 detoxification reaction (Equations (19.7) and (19.8), respectively) ... 

The importance of bacteria in mediating Mn(II) oxidation in certain environments is evident. But, the mechanisms whereby bacteria oxidize Mn(II) are poorly understood. Some bacteria synthesize proteins or other materials that enhance the rate of Mn(II) oxidation (.52). Other strains of bacteria require oxidized manganese to oxidize Mn(II) (53), suggesting that they may catalyse the oxidation of Mn(II) on the manganese oxide surface. Other bacteria may catalyse the oxidation of Mn(II) on iron oxide surfaces, as iron is associated with manganese deposits on bacteria collected in the eastern subtropical North Pacific (54). 

Iron oxides in the finely divided form have the power to promote (catalyse) a range of redox and photochemical reactions (Tab. 11.7). The preliminary step is the adsorption of the reacting species on the iron oxide. This may be followed either by direct reaction with the Fe surface atoms or surface functional groups or the surface may promote reaction between the adsorbed species and a solution species such as dissolved oxygen. 

The principal iron oxides used in catalysis of industrial reactions are magnetite and hematite. Both are semiconductors and can catalyse oxidation/reduction reactions. Owing to their amphoteric properties, they can also be used as acid/base catalysts. The catalysts are used as finely divided powders or as porous solids with a high ratio of surface area to volume. Such catalysts must be durable with a life expectancy of some years. To achieve these requirements, the iron oxide is most frequently dis-... 

In some major reactions, the iron oxide is the starting material for the actual catalyst which is active iron metal. Quite often both the metal and its oxide can catalyse the reaction, but the activity and selectivity of the metal is greater. Furthermore, the oxide catalyst may be reduced to some intermediate product during the reaction, particularly a reaction involving H2 and high temperature. This may lead to loss of catalytic activity as the intermediate may be a less suitable catalyst than the starting oxide or the actual metal. To avoid this occurrence, the oxide is frequently prereduced , i.e. converted to the metal by a thermal/reduction pretreatment in a preliminary step. 

Laboratory studies have indicated an increasing number of further processes for which iron oxides may be used as catalysts. A sodium promoted iron oxide on a support of Si02 catalyses the gas phase oxidation (377-427 °C) by nitrous oxide, of pro-pene to propene oxide (Duma and Honicke, 2000). Ferrihydrite or akaganeite can be used to catalyse the reduction (at 55-75 °C) by hydrazine, of aromatic nitro compounds to aromatic amines (which are the starting materials for a huge range of chemicals) these Fe oxides have the potential to provide a safe and economical pathway to the production of these important organics (Lauwiner et al., 1998). 

Shaikhudtinov, Sh.K. Weiss, W. (2000) Adsor-balt dynamics on iron oxide surfaces studies by scanning tunnelling microscopy. J. Molecular Catalyses A. Chem. 158 129-133... 

Iron oxides have served man for centuries. Since the red and yellow ochres were first used to help produce prehistoric paintings in caves such as those at Lascaux, the role of iron oxides has expanded enormously. Their application as pigments and their ability to catalyse various chemical reactions, their role as the precursors of iron and steel and their activity as adsorbants in the ecosphere are just a few examples of the contribution of these compounds to the well-being of man. 

A third example is the water-gas-shift reaction catalysed by iron catalysts. The active phase is an intermediate iron oxide (Fe304), distinctly different from the manufactured catalyst (Fe203). So, mild reduction should be carried out. In optimising the pretreatment procedure it should be realized that over-reduction is to be avoided because of the danger of carbon deposition and methane formation (highly exothermic). It has been found that a well-controlled reduction in a H2/H2O mixture is possible, whereas the use of H2 and steam separately should be avoided. 

Oxidation happens very slowly at the low pH values found in acid mine waters. However, below pH 3.5 iron oxidation is catalysed (see Box 4.4) by the iron bacterium Thiobacillus thiooxidans. At pH 3.5-4.5 oxidation is catalysed by Metallogenium. Ferric iron may react further with pyrite ... 

The generally accepted mechanism for phenolic oxidations catalysed by horseradish peroxidase (HRP), the most thoroughly studied peroxidase, involves an initial two-electron oxidation of the iron(III) resting state of the enzyme by the hydroperoxide (or hydrogen peroxide) to give compound I (HRP I) which is subsequently reduced back to the iron(III) haem, in two one-electron steps, via compound II (HRP II) (Scheme 1). The phenoxyl radical intermediates react to give products, which depending on their structure, may themselves be further oxidised. 

For the reduction of nitroarenes to aminoarenes by the catalytic hydrazine H-transfer reduction method, the classical hydrogenation catalysts Ni, Pd and Pt are most commonly used [1] [2]. In a more extended study [3] we were able to confirm previously reported observations [4] that these reductions can also be catalysed by modified iron oxides hydroxides. This method for the production of many aromatic amines offers several advantages compared to the conventional processes still employed in industry, such as the environmentally imfavourable Bechamp [5] and Zinin reductions [6]. It is an outstanding feature of the novel reduction method presented here that further reducible substituents in nitroazo compounds, such as... 

---