Exotic Fe II /Fe III Local Environments in the Hexagonal Channels of Hydroxyapatite.

Autor: Bazin T; CNRS, Université de Bordeaux, Bordeaux INP, ICMCB, UMR 5026, F-33600 Pessac, France.; Université de Limoges, IRCER─Centre Européen de la Céramique, UMR CNRS 7315, F-87068 Limoges, France., Duttine M; CNRS, Université de Bordeaux, Bordeaux INP, ICMCB, UMR 5026, F-33600 Pessac, France., Julien I; Université de Limoges, IRCER─Centre Européen de la Céramique, UMR CNRS 7315, F-87068 Limoges, France., Champion E; Université de Limoges, IRCER─Centre Européen de la Céramique, UMR CNRS 7315, F-87068 Limoges, France., Demourgues A; CNRS, Université de Bordeaux, Bordeaux INP, ICMCB, UMR 5026, F-33600 Pessac, France., Gaudon M; CNRS, Université de Bordeaux, Bordeaux INP, ICMCB, UMR 5026, F-33600 Pessac, France.
Jazyk: angličtina
Zdroj: Inorganic chemistry [Inorg Chem] 2022 Sep 12; Vol. 61 (36), pp. 14377-14388. Date of Electronic Publication: 2022 Aug 31.
DOI: 10.1021/acs.inorgchem.2c02212
Abstrakt: In this fundamental solid-state chemistry study, two sample series were investigated in depth: iron(III)-doped hydroxyapatite (HA) compounds obtained from a co-sintering process of hematite and pure HA under air and iron(III)-doped HA compounds obtained from a co-sintering process from iron(II) acetate and pure HA under an argon atmosphere. X-ray diffraction, UV-visible, Fourier transform infrared, 1 H and 31 P NMR, electron paramagnetic resonance (EPR,) and Mössbauer spectroscopy methods were coupled to unravel the Fe valence states, the interactions with other anionic species (OH - and PO 4 3- ), and finally the complex local environments in hexagonal channels in both the series. In particular, we highlighted the associated mechanism to ensure electroneutrality with a focus on deprotonation versus calcium substitution. By diverging mechanisms, Fe 3+ and Fe 2+ ions were found to be located in different coordinated sites: 4(+1) coordinated site for Fe 3+ and 2(+3) coordinated site for Fe 2+ and clearly associated with very different Mössbauer and EPR signatures as various absorption bands (leading to different sample colors).
Databáze: MEDLINE