American Chemical Society
cm3c02346_si_004.pdf (4.39 MB)

Nonclassical Crystallization Pathway of Transition Metal Phosphate Compounds

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journal contribution
posted on 2023-12-12, 13:20 authored by Stephanos Karafiludis, Zdravko Kochovski, Ernesto Scoppola, Anika Retzmann, Vasile-Dan Hodoroaba, Johan E. ten Elshof, Franziska Emmerling, Tomasz M. Stawski
Here, we elucidate nonclassical multistep crystallization pathways of transition metal phosphates from aqueous solutions. We followed precipitation processes of M-struvites, NH4MPO4·6H2O, and M-phosphate octahydrates, M3(PO4)2·8H2O, where M = Ni, Co, or NixCo1–x, by using in situ scattering and spectroscopy-based techniques, supported by elemental mass spectrometry analyses and advanced electron microscopy. Ni and Co phosphates crystallize via intermediate colloidal amorphous nanophases, which change their complex structures while agglomerating, condensing, and densifying throughout the extended reaction times. We reconstructed the three-dimensional morphology of these precursors by employing cryo-electron tomography (cryo-ET). We found that the complex interplay between metastable amorphous colloids and protocrystalline units determines the reaction pathways. Ultimately, the same crystalline structure, such as struvite, is formed. However, the multistep process stages vary in complexity and can last from a few minutes to several hours depending on the selected transition metal(s), their concentration, and the Ni/Co ratio.