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Electronic State of Iron Complexes in the Interlayer of Hydrotalcite-Like Materials

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Clays and Clay Minerals

Abstract

Infrared and Mössbauer spectroscopic studies were made on hydrotalcite-like materials, Mg6Al2(OH)16(NO3)2·4H2O, anion exchanged in aqueous solution of K3Fe(CN)6, K4Fe(CN)6·3H2O, or Na2Fe(CN)5NO·2H2O. The material anion-exchanged in aqueous solution of K3Fe(CN)6 gave infrared (IR) absorption bands at 2120 and 2040 cm-1 in the C≡N stretching region, suggesting that part of the ferrate(III) complex was reduced to ferrate(II) complex on the intercalation chiefly because pure K3Fe(III)(CN)6 and K4Fe(II)(CN)6·3H2O gives bands at 2120 and 2040 cm-1, respectively. On the intercalation of Fe(CN)64-, no change in the oxidation state of iron was observed. These features were confirmed by Mössbauer spectroscopy. In the IR spectra of material anion-exchanged in aqueous solution of Na2Fe(CN)5NO·2H2O, the intensity of bands due to N≡O (1940 cm-1) and C≡N stretching was much less than that observed for Na2Fe(CN)5NO·2H2O, indicating that most of N≡O ligand was eliminated during the intercalation. Four bands were observed in the C≡N stretching region: a band at 2143 cm-1 was assigned to C≡N groups in Fe(CN)5NO2-; a band at 2120 cm-1 was tentatively assigned to Fe(CN)5H2O2-; bands at 2040–2050 cm-1 were assigned to Fe(CN)5H2O3-.

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References

  • Allmann, R. (1970) Doppelschichtstrukturen mit bruci-tähnlichen Schichtionen [Me(II)1_xMe(HI)I(OH)2+: Chi-mia 24, 99–108.

    Google Scholar 

  • Bor, G. (1961) High-resolution infra-red spectrum of the [Fe(CN)5NO]2- ion: J. Inorg. Nuel. Chem. 17, 174–175.

    Article  Google Scholar 

  • Brown, D. B. (1971) On the effective charge of iron in ni-troprusside: Inorg. Chim. Acta. 5, 314–316.

    Article  Google Scholar 

  • Brown, D. B. and Shriver, D. F. (1969) Structures and solid-state reactions of prussian blue analogs containing chromium, manganese, iron, and cobalt: Inorg. Chem. 8, 37–42.

    Article  Google Scholar 

  • Carrado, K. A., Kostapapas, A., and Suib, S. L. (1988) Layered double hydroxides (LDHs): Solid State Ionics 26, 77–86.

    Article  Google Scholar 

  • Cavalcanti, F. A. P., Schutz, A., and Biloen, P. (1987) In-terlayer accessibility in layered double-metal hydroxides: in Preparation of Catalysts IV, B. Delmon, P. Grange, P. A. Jacobs, and G. Poncelet, eds., Elsevier, Amsterdam, 165–174.

    Google Scholar 

  • Costa, N. L., Danon, J., and Xavier, R. M. (1962) Measurement of nuclear quadrupole interaction in iron complexes using the Mössbauer effect: J. Phys. Chem. Solids 23, 1783–1785.

    Article  Google Scholar 

  • Champion, A. R. and Drickamer, H. G. (1967) Effect of pressure on the Mössbauer resonance in potassium ferro-cyanide, potassium ferricyanide, and insoluble prussian blue: J. Chem. Phys. 47, 2591–2594.

    Article  Google Scholar 

  • Drickamer, H. G., Lewis, G. K., Jr., and Fung, S. C. (1969) The oxidation state of iron at high pressure: Science 163, 885–890.

    Article  Google Scholar 

  • Fluck, E., Kerler, W., and Neuwirth, W. (1963) The Mössbauer effect and its significance in chemistry: Angew. Chem., Int. Ed. Engl. 2, 277–287.

    Article  Google Scholar 

  • Frondel, C. (1941) Constitution and polymorphism of the pyroaurite and sjogrenite groups: Amer. Miner. 26, 295–315.

    Google Scholar 

  • Fukushima, Y. and Kamigaito, O. (1984) Layered oxide compounds—Reactions in the intercalated compounds and its applications: Seramikkusu 19, 109–113.

    Google Scholar 

  • Gordon, B. M., Williams, L. L., and Sutin, N. (1961) The kinetics of the oxidation of iron(II) ions and of coordination complexes: J. Amer. Chem. Soc. 83, 2061–2064.

    Article  Google Scholar 

  • Itaya, K., Chang, H.-C., and Uchida, I. (1987) Anion-ex-changed hydrotalcite-like-clay-modified electrodes: Inorg. Chem. 26, 624–626.

    Article  Google Scholar 

  • Kikkawa, S. and Koizumi, M. (1982) Ferrocyanide anion bearing Mg,Al hydroxide: Mat. Res. Bull. 17, 191–198.

    Article  Google Scholar 

  • Larsen, H. A. and Drickamer, H. G. (1957) Chemical effects of plastic deformation at high pressure: J. Phys. Chem. 61, 1249–1252.

    Article  Google Scholar 

  • Miyata, S. (1975) The synthesis of hydrotalcite-like compounds and their structures and physico-chemical proper-ties-I. The systems Mg2+-Al3+-NO3~, Mg2+-Al3+-CL, Mg2+-Al3+-C104-, Ni2+-Al3+-CL, andZn2+-Al3+-Cl-: Clays & Clay Minerals 23, 369–375.

    Article  Google Scholar 

  • Miyata, S. (1980) Physico-chemical properties of synthetic hydrotalcites in relation to composition: Clays & Clay Minerals 28, 50–55.

    Article  Google Scholar 

  • Miyata, S. (1983) Anion-exchange properties of hydrotalcite-like compounds: Clays & Clay Minerals 31, 305–311.

    Article  Google Scholar 

  • Miyata, S. and Hirose, T. (1978) Adsorption of N2,O2, CO2, and H2 on hydrotalcite-like system. Mg2+-Al3+-(Fe(CN)6)4-: Clays & Clay Minerals 26, 441–447.

    Article  Google Scholar 

  • Miyata, S. and Kumura, T. (1973) Synthesis of new hydrotalcite-like compounds and their physico-chemical properties: Chem. Lett., 843–848.

    Google Scholar 

  • Miyata, S. and Okada, A. (1977) Synthesis of hydrotalcite-like compounds and their physico-chemical properties— The systems Mg2+-Al3+-SO42- and Mg2+-Al3+-CrO,2-: Clays & Clay Minerals 25, 14–18.

    Article  Google Scholar 

  • Pelizzetti, E., Mentasti, E., and Baiocchi, C. (1976) Kinetics and mechanism of oxidation of quinols by hexachloroiri-date(IV) in aqueous acidic Perchlorate media: J. Phys. Chem. 80, 2979–2982.

    Article  Google Scholar 

  • Suzuki, E., Idemura, S., and Ono, Y. (1989) Properties of hexacyanocobaltate(III)-exchanged hydrotalcite-like minerals: Clays & Clay Minerals 37, 173–178.

    Article  Google Scholar 

  • Tosi, L. and Danon, J. (1964) Infrared spectral evidence of ir-bonding in the Fe(CN),NO2~ ion: Inorg. Chem. 3, 150–151.

    Article  Google Scholar 

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Idemura, S., Suzuki, E. & Ono, Y. Electronic State of Iron Complexes in the Interlayer of Hydrotalcite-Like Materials. Clays Clay Miner. 37, 553–557 (1989). https://doi.org/10.1346/CCMN.1989.0370608

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