From iron(III) precursor to magnetite and vice versa
- Division of Materials Chemistry, Ruder Boskovic Institute, P.O. Box 180, HR-10002 Zagreb (Croatia)
The syntheses of nanosize magnetite particles by wet-chemical oxidation of Fe{sup 2+} have been extensively investigated. In the present investigation the nanosize magnetite particles were synthesised without using the Fe(II) precursor. This was achieved by {gamma}-irradiation of water-in-oil microemulsion containing only the Fe(III) precursor. The corresponding phase transformations were monitored. Microemulsions (pH {approx} 12.5) were {gamma}-irradiated at a relatively high dose rate of {approx}22 kGy/h. Upon 1 h of {gamma}-irradiation the XRD pattern of the precipitate showed goethite and unidentified low-intensity peaks. Upon 6 h of {gamma}-irradiation, reductive conditions were achieved and substoichiometric magnetite ({approx}Fe{sub 2.71}O{sub 4}) particles with insignificant amount of goethite particles found in the precipitate. Hydrated electrons (e{sub aq}{sup -}), organic radicals and hydrogen gas as radiolytic products were responsible for the reductive dissolution of iron oxide in the microemulsion and the reduction Fe{sup 3+} {yields} Fe{sup 2+}. Upon 18 h of {gamma}-irradiation the precipitate exhibited dual behaviour, it was a more oxidised product than the precipitate obtained after 6 h of {gamma}-irradiation, but it contained magnetite particles in a more reduced form ({approx}Fe{sub 2.93}O{sub 4}). It was presumed that the reduction and oxidation processes existed as concurrent competitive processes in the microemulsion. After 18 h of {gamma}-irradiation the pH of the medium shifted from the alkaline to the acidic range. The high dose rate of {approx}22 kGy/h was directly responsible for this shift to the acidic range. At a slightly acidic pH a further reduction of Fe{sup 3+} {yields} Fe{sup 2+} resulted in the formation of more stoichiometric magnetite particles, whereas the oxidation conditions in the acidic medium permitted the oxidation Fe{sup 2+} {yields} Fe{sup 3+}. The Fe{sup 3+} was much less soluble in the acidic medium and it hydrolysed and recrystallised as goethite. The {gamma}-irradiation of the microemulsion for 25 h at a lower dose rate of 16 kGy/h produced pure substoichiometric nanosize magnetite particles of about 25 nm in size and with the stoichiometry of Fe{sub 2.83}O{sub 4}.
- OSTI ID:
- 22029752
- Journal Information:
- Materials Research Bulletin, Vol. 44, Issue 10; Other Information: Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0025-5408
- Country of Publication:
- United States
- Language:
- English
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