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Journal Article

Nucleation and Crystallization of Ferrous Phosphate Hydrate via an Amorphous Intermediate

Authors
/persons/resource/apaskin

Paskin,  Alice
3.5 Interface Geochemistry, 3.0 Geochemistry, Departments, GFZ Publication Database, Deutsches GeoForschungsZentrum;

Reinsch,  Stefan

/persons/resource/rblukis

Blukis,  Roberts
3.5 Interface Geochemistry, 3.0 Geochemistry, Departments, GFZ Publication Database, Deutsches GeoForschungsZentrum;

/persons/resource/benning

Benning,  Liane G.
3.5 Interface Geochemistry, 3.0 Geochemistry, Departments, GFZ Publication Database, Deutsches GeoForschungsZentrum;

/persons/resource/couasnon

Couasnon,  Thais
3.5 Interface Geochemistry, 3.0 Geochemistry, Departments, GFZ Publication Database, Deutsches GeoForschungsZentrum;

/persons/resource/jpperez

Perez,  J.P.H.
3.2 Organic Geochemistry, 3.0 Geochemistry, Departments, GFZ Publication Database, Deutsches GeoForschungsZentrum;

/persons/resource/slobanov

Lobanov,  Sergey
3.6 Chemistry and Physics of Earth Materials, 3.0 Geochemistry, Departments, GFZ Publication Database, Deutsches GeoForschungsZentrum;

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5019727.pdf
(Publisher version), 9MB

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Citation

Paskin, A., Reinsch, S., Blukis, R., Benning, L. G., Couasnon, T., Perez, J., Lobanov, S. (2023): Nucleation and Crystallization of Ferrous Phosphate Hydrate via an Amorphous Intermediate. - Journal of the American Chemical Society, 145, 28, 15137-15151.
https://doi.org/10.1021/jacs.3c01494


Cite as: https://gfzpublic.gfz-potsdam.de/pubman/item/item_5019727
Abstract
The fundamental processes of nucleation and crystallization are widely observed in systems relevant to material synthesis and biomineralization; yet most often, their mechanism remains unclear. In this study, we unravel the discrete stages of nucleation and crystallization of Fe3(PO4)2·8H2O (vivianite). We experimentally monitored the formation and transformation from ions to solid products by employing correlated, time-resolved in situ and ex situ approaches. We show that vivianite crystallization occurs in distinct stages via a transient amorphous precursor phase. The metastable amorphous ferrous phosphate (AFEP) intermediate could be isolated and stabilized. We resolved the differences in bonding environments, structure, and symmetric changes of the Fe site during the transformation of AFEP to crystalline vivianite through synchrotron X-ray absorption spectroscopy at the Fe K-edge. This intermediate AFEP phase has a lower water content and less distorted local symmetry, compared to the crystalline end product vivianite. Our combined results indicate that a nonclassical, hydration-induced nucleation and transformation driven by the incorporation and rearrangement of water molecules and ions (Fe2+ and PO43–) within the AFEP is the dominating mechanism of vivianite formation at moderately high to low vivianite supersaturations (saturation index ≤ 10.19). We offer fundamental insights into the aqueous, amorphous-to-crystalline transformations in the Fe2+–PO4 system and highlight the different attributes of the AFEP, compared to its crystalline counterpart.