A spectroscopic study of calcium surface sites and adsorbed iron species at aqueous fluorapatite by means of 1H and 31P MAS NMR

Dan E Sandström; Mathias Jarlbring; Oleg N Antzutkin; Willis Forsling

doi:10.1021/la0602158

A spectroscopic study of calcium surface sites and adsorbed iron species at aqueous fluorapatite by means of 1H and 31P MAS NMR

Langmuir. 2006 Dec 19;22(26):11060-4. doi: 10.1021/la0602158.

Authors

Dan E Sandström¹, Mathias Jarlbring, Oleg N Antzutkin, Willis Forsling

Affiliation

¹ Department of Chemical Engineering and Geoscience, Division of Chemistry, Luleå University of Technology, SE-97187 Luleå, Sweden.

PMID: 17154584
DOI: 10.1021/la0602158

Abstract

Assignments of the protolytic speciation at the calcium hydroxyl surface sites of synthetic fluorapatite and the chemical interactions between fluorapatite-maghemite and fluorapatite-Fe2+ ions have been studied by means of 1H and 31P single-pulse and 31P CP MAS NMR. Three possible forms of calcium hydroxyl surface sites have been suggested and assigned to [triple bond] CaOH, [triple bond]Ca(OH)2-, and [triple bond]CaOH2+, and their mutual ratios were found to vary as a function of pH. Due to their paramagnetic properties, iron species and Fe2+ ions adsorbed at the fluorapatite surface display a broad spinning sideband manifold in the single-pulse 31P MAS NMR spectra. The resonance lines in the 31P CP MAS NMR spectra originating from the bulk phosphate groups PO4(3-) and phosphorus surface sites [triple bond]POx and [triple bond]POxH decrease with increasing Fe2+ ion adsorption. When iron species originating from maghemite are adsorbed at the fluorapatite surface, no 31P NMR signal is detected, which supports the hypothesis that surface reactions occur between the phosphorus surface sites of fluorapatite and iron species.