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Surface Hydration and Cationic Sites of Nanohydroxyapatites with Amorphous or Crystalline Surfaces: A Comparative Study

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    Surface Hydration and Cationic Sites of Nanohydroxyapatites with Amorphous or Crystalline Surfaces: A Comparative Study
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    Dipartimento di Chimica IFM & Centro di Eccellenza Interdipartimentale “NIS”, Università di Torino, Via P. Giuria 7, 10125 Torino, Italy, Dipartimento di Chimica “G. Ciamician”, Università di Bologna, Via Selmi 2, 40126 Bologna, Italy, Dipartimento di Scienze Mediche, Università del Piemonte Orientale, Via Solaroli 4, 28100 Novara, Italy, and ISTEC−CNR, Via Granarolo 64, 48018 Faenza, Italy
    * To whom correspondence should be addressed. Fax: +39-011 670 7855. Tel: +39-011 670 7538. E-mail: [email protected]
    †Università di Torino.
    ‡Università di Bologna.
    §Università del Piemonte Orientale.
    ∥ISTEC−CNR.
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2010, 114, 39, 16640–16648
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    https://doi.org/10.1021/jp105971s
    Published September 2, 2010
    Copyright © 2010 American Chemical Society
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    Abstract

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    This paper is an extension of previous work devoted to the characterization of platelet-like hydroxyapatite (HA) nanoparticles constituted by a crystalline core coated by an amorphous surface layer 1−2 nm thick (Bertinetti et al. J. Phys. Chem. C. 2007, 111, 4027−4035). By increasing the preparation temperature, the platelet morphology was retained but HA nanoparticles exhibited a higher degree of crystallinity (evaluated by X-ray diffractometry). High-resolution transmission electron microscopy revealed that, in this case, the crystalline order was extended up to the particles’ surfaces, which were of the (010), (100), and (001) types. IR spectroscopy was used to investigate the surface hydration of both materials, in terms of adsorbed H2O molecules and surface hydroxy groups, as well as the Lewis acidity of surface cations, by removing water and adsorbing CO. For both features, strong similarities between amorphous and crystalline surfaces were found.

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    Supporting Information

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    (1) XRD patterns, (2) IR spectra of HA-am and HA-cry exchanged with D2O and then outgassed at b.t., (3) example of data elaboration for the extraction of the signals due to adsorbed H2O, (4) plot of the integrated intensity of νOH versus δH2O for HA-am and HA-cry, (5) IR spectra of HA-am in the νOH, δH2O, and carbonate νCO regions, (6) IR spectra, in the δH2O and carbonate νCO regions of HA-am outgassed at increasing temperature and then contacted with 20 mbar of H2O, (7) IR spectra of HA-am and HA-cry stepwise outgassed at increasing temperature and then contacted with 20 mbar of H2O, outgassed at b.t., exchanged with D2O, and outgassed at b.t. This material is available free of charge via the Internet at http://pubs.acs.org.

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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2010, 114, 39, 16640–16648
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    https://doi.org/10.1021/jp105971s
    Published September 2, 2010
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