The reduction of iron oxide supported on alumina, anatase and rutile and the interactions between iron oxides and these supports have been studied using temperature-programmed reduction, Mossbauer spectroscopy and X-ray diffraction. The intermediates formed during reduction depend strongly on the nature of the support, the iron loading and the reduction conditions used. Several iron species such as bulk a-Fe,O,, superparamagnetic a-Fe203 and surface iron-aluminium oxides are found in the alumina-supported iron oxide samples. The ironaluminium species can be formed either by incorporation of A13+ into the structure of iron oxide in acidic solution during the preparation of the samples or by incorporation of Fe2+ into the structure of the alumina support under high-temperature reduction. For the as-prepared Fe/TiO, samples, the anatase and rutile have only weak interactions with the iron oxide as only bulk a-Fe,O, species have been detected. However, some intermediates such as (1x)FeTiO,-xFe203 solid solution, surface iron-titanium oxide and bulk FeTiO, phase can be formed during reduction because of the reducibility and mobility of titanium ions on the surface. Surface titanium ions can act as an electron-transfer medium for the reduction of Fe3+ to Fe2+ and can even be substituted for Fe3+ ions in the octahedral sites of magnetite formed during the reduction. In all cases, when the loading of iron oxide is low, Fe3+ and Fe2+ ions are stable during reduction due to the formation of iron oxide-support intermediates by strong interactions between iron oxides and the supports.
Microcalorimetric and infrared spectroscopy studies of ammonia and carbon dioxide adsorption were carried out to investigate the number, strength, and type of acidhase sites of europium oxide supported on y-Alz03 and SiO2. X-ray diffraction, luminescence spectroscopy, and Mossbauer spectroscopy were used to characterize the structure, bonding, and valence of the europium atoms. Europium oxide neutralizes acid sites on y-AlzOs, lowering the initial heat of ammonia adsorption from 155 to 120 kJ/mol. Both Lewis and Bransted acid sites exist on Eu203/A1203 samples, with Lewis acid sites in dominance. Europium oxide increases the number and strength of base sites on y-AlzO3, with the initial heat of carbon dioxide adsorption increasing from 145 to 160 kJ/mol. Surface hydroxyl groups and oxygen anions are responsible for base sites on the Eu203/ A1203 samples. The addition of europium oxide to Si02 increases the number and strength of acid sites, with the initial heat for ammonia adsorption increasing from 85 to 125 kl/mol. Europium oxide on silica shows few basic sites. Luminescence spectra show that Eu3+ ions occupy a range of dissimilar bonding sites on both supports, particularly at low concentrations. At the higher concentrations, Eu3+ ions occupy more welldefined sites, having a weaker interaction with the support. The acidhase properties of these supported europium oxides can be related to the electronegativities of these samples, with higher electronegativity enhancing acidic properties and suppressing basic properties.
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