Reduction and re-oxidation behavior of calcium iron phosphate, Ca9Fe(PO4)7 / Lazoryak B.I., Belik A.A., Kotov R.N., Leonidov I.A., Mitberg E.B., Karelina V.V., Kellerman D.G., Stefanovich S.Yu., Avetisov A.K. // Chemistry of Materials. - 2003. - V. 15, l. 3. - P. 625-631.

ISSN:
08974756
Type:
Article
Abstract:
Reduction (in H2) and re-oxidation (in air) behavior of Ca9Fe(PO4)7 was studied by X-ray powder diffraction, Mössbauer spectroscopy, thermogravimetry, hydrogen absorption, electrical conductivity, and magnetic-susceptibility measurements. The β-Ca3(PO4)2-like framework of Ca9Fe(PO4)7 was stable in 100% H2 up to 820 K. In the temperature range from 680 to 820 K, reversible redox reactions occurred without changing the stoichiometry of oxygen and phosphorus atoms and destroying the structure. The reduction process in Ca9Fe(PO4)7 included the change of the oxidation state of Fe atoms and incorporation of hydrogen atoms into the structure to form Ca9FeHx(PO4)7 (0 < x ≤ 1). Above 820 K, treatment in 100% H2 was accompanied by loss in mass, partial destruction of the structure, and appearance of FeP and Fe2P phases. Re-oxidation studies in air showed that samples partially lost phosphorus atoms during reduction above 820 K. Behavior of Ca9Fe(PO4)7 under a reduction atmosphere depended on H2 concentration and temperature. At low H2 concentration, the sample destruction started from ca. 870 K and proceeded with maintaining the oxidation state of Fe, releasing H2O and forming a β-Ca3(PO4)2-like phase and β-Ca2P2O7. In this case, iron phosphides appeared above ca. 1200 K.
Author keywords:
Index keywords:
calcium derivative; calcium iron phosphate; hydrogen; iron; potassium; unclassified drug; water; article; atmosphere; chemical analysis; chemical structure; electric conductivity; magnetism; measureme
DOI:
10.1021/cm010851l
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Affiliations Department of Chemistry, Moscow State University, 119899 Moscow, Russian Federation; State Sci. Ctr. of Russ. Federation, Karpov Inst. of Physical Chemistry, 103063 Moscow, Russian Federation; Institute of Solid State Chemistry, Ural Branch of RAS, GSP-145, Pervomayskaia 91, 620219 Yekaterinburg, Russian Federation
Chemicals/CAS hydrogen, 12385-13-6, 1333-74-0; iron, 14093-02-8, 53858-86-9, 7439-89-6; potassium, 7440-09-7; water, 7732-18-5
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Correspondence Address Lazoryak, B.I.; Department of Chemistry, Moscow State University, 119899 Moscow, Russian Federation; email: lazoryak@tech.chem.msu.ru
CODEN CMATE
Language of Original Document English
Abbreviated Source Title Chem. Mater.
Source Scopus