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Synthesis, electronic state, and particle size stabilization of nanoparticulate [Co(OH)2(H3O) +δ ]δ+

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Abstract

We have synthesized nanoparticulate cobalt(II) hydroxide containing Co2+ in tetrahedral oxygen coordination (Co 2+ Td ), atypical of such systems: nano- [Co(OH)2(H3O) +δ ]δ+. The (Co 2+ Td ) coordination in the hydroxide is inferred from its electronic diffuse reflectance spectrum, which shows a multiplet of strong absorption bands at 14500, 15000, and 16000 cm−1 (4 A 2(F)-4 T 1(P) transition). Nanoparticulate cobalt(II) hydroxide forms in a weakly acidic medium under essentially nonequilibrium conditions due to supersaturation (by three to four orders of magnitude) with the starting reagents (CoCl2 and LiOH) at the instant of the formation of the poorly soluble phase Co(OH)2. Presumably, colloidal particles of nanoparticulate cobalt(II) hydroxide in a weakly acidic aqueous medium have a positive surface charge, compensated by a counter-ion (Cl−) layer: nano-[Co(OH)2(H3O) +δ ]δ+ · δCl−. The XRD patterns of pastes (gels) containing this hydroxide show three broad-ened lines with d = 5.31 (2θ = 16.7°), 2.77 (2θ = 32.3°), and 2.32 Å (2θ = 38.8°). According to small-angle X-ray scattering data, nano-[Co(OH)2(H3O) +δ ]δ+ has a narrow particle size distribution (1.0–2.0 nm). Synthesis and storage conditions are identified which ensure stabilization of the electronic state and particle size of nano-[Co(OH)2(H3O) +δ ]δ+ for a long time.

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References

  1. Oswald, H.R. and Asper, R., Bivalent Metal Hydroxides, in Preparation and Crystal Growth of Materials with Layered Structures, Dordrecht: Kluwer, 1977, pp. 71–140.

    Google Scholar 

  2. Pertlik, Fr., The Distortion of the Hexagonal Close Packing of Oxygen Atoms in Co(OH)2 Compared to Isotypic Brucite-Type Structures, Monatsh. Chem., 1999, vol. 130, no. 9, pp. 1083–1088.

    CAS  Google Scholar 

  3. Xu, Z.P. and Zeng, H.C., Interconversion of Brucite-Like and Hydrotalcite-Like Phases in Cobalt Hydroxide Compounds, Chem. Mater., 1999, vol. 11, no. 1, pp. 67–74.

    Article  CAS  Google Scholar 

  4. Xu, Z.P. and Zeng, H.C., A New Approach for Design and Synthesis of CoII and CoII,III Hydroxide Materials, Int. J. Inorg. Mater., 2000, vol. 2, nos. 2–3, pp. 187–196.

    Article  CAS  Google Scholar 

  5. Zhu, Y., Li, H., Koltypin, Yu., and Gedanken, A., Preparation of Nanosized Cobalt Hydroxides and Oxyhydroxide Assisted by Sonication, J. Mater. Chem., 2002, vol. 12, no. 3, pp. 729–733.

    Article  CAS  Google Scholar 

  6. Kamath, P.V. and Gopalakrishnan, J., On the Existence of Hydrotalcite-Like Phases in the Absence of Trivalent Cations, J. Solid State Chem., 1997, vol. 128, no. 1, pp. 38–41.

    Article  CAS  Google Scholar 

  7. Rajamathi, M., Kamath, P.V., and Seshadri, R., Chemical Synthesis of α-Cobalt Hydroxide, Mater. Res. Bull., 2000, vol. 35, no. 2, pp. 271–278.

    Article  CAS  Google Scholar 

  8. Ma, R., Liu, Z., Takada, K., et al., Tetrahedral Co(II) Coordination in α-Type Cobalt Hydroxide: Rietveld Refinement and X-Ray Absorption Spectroscopy, Inorg. Chem., 2006, vol. 45, no. 10, pp. 3964–3969.

    Article  CAS  Google Scholar 

  9. Zhao, Z., Geng, F., Bai, J., and Cheng, H.-M., Facile and Controlled Synthesis of 3D Nanorods-Based Urchinlike and Nanosheets-Based Flowerlike Cobalt Basic Salt Nanostructures, J. Phys. Chem. C, 2007, vol. 111, no. 10, pp. 3848–3852.

    Article  CAS  Google Scholar 

  10. Grimer, A. and Fournet, G., Small-Angle Scattering of X-Rays, New York: Wiley, 1955.

    Google Scholar 

  11. PCPDF Win (2003), Swarthmore: JCPDS-ICDD, 2003, file 25-0242.

  12. ICSD RETRTEVE (2005), Collection Code 24685.

  13. Lever, A.B.P., Inorganic Electronic Spectroscopy, Amsterdam: Elsevier, 1987.

    Google Scholar 

  14. Khimicheskaya entsiklopediya (Chemical Encyclopedia), Knunyants, I.L., Ed., Moscow: Sovetskaya Entsiklopediya, 1990, vol. 2, p. 826.

    Google Scholar 

  15. Fizicheskaya i kolloidnaya khimiya (Physical and Colloidal Chemistry), Belyaev, A.P., Ed., Moscow: GEOTAR-Media, 2008, p. 541.

    Google Scholar 

  16. Guinier, A., Theorie et technique de la radiocristallographie, Paris: Dunod, 1956.

    Google Scholar 

  17. Caruso, F., Colloids and Colloid Assemblies, New York: Wiley-VCH, 2004, p. 56.

    Google Scholar 

  18. Ferguson, J., Wood. T.E. Electronic Absorption Spectra of Tetragonal and Pseudotetragonal Cobalt (II): II. CoCl2 · 6H2O and CoCl2 · 6D2O, Inorg. Chem., 1975, vol. 14, no. 1, pp. 184–189.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, pr. Akademika Lavrent’eva 5, Novosibirsk, 630090, Russia

    O. P. Krivoruchko, T. V. Larina, V. F. Anufrienko, I. Yu. Molina & E. A. Paukshtis

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  1. O. P. Krivoruchko
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  2. T. V. Larina
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  3. V. F. Anufrienko
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  4. I. Yu. Molina
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  5. E. A. Paukshtis
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Correspondence to T. V. Larina.

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Original Russian Text © O.P. Krivoruchko, T.V. Larina, V.F. Anufrienko, I.Yu. Molina, E.A. Paukshtis, 2009, published in Neorganicheskie Materialy, 2009, Vol. 45, No. 12, pp. 1451–1457.

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Krivoruchko, O.P., Larina, T.V., Anufrienko, V.F. et al. Synthesis, electronic state, and particle size stabilization of nanoparticulate [Co(OH)2(H3O) +δ ]δ+ . Inorg Mater 45, 1355–1361 (2009). https://doi.org/10.1134/S0020168509120097

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  • DOI: https://doi.org/10.1134/S0020168509120097

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