Nucleation and Crystallization of Ferrous Phosphate Hydrate via an Amorphous Intermediate

• DOI: 10.1021/jacs.3c01494
• Publication Date: 2023-07-06T08:52:02Z
• Authors: Alice Paskin; Thaïs Couasnon; Jeffrey Paulo H. ...; Sergey S. Lobanov; Roberts Blukis; Stefan Reinsch; Liane G. Benning
• Keywords: info:eu-repo/classification/ddc/540; Nucleation; 540; Crystallization; 500 Naturwissenschaften und Mathematik::540 Chemie::540 Chemie und zugeordnete Wissenschaften; Diffraction

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