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Nonclassical Crystallization Pathway of Transition Metal Phosphate Compounds

  • 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 inHere, 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.zeige mehrzeige weniger

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  • cm3c02346_article.pdf
    eng

    Article

  • cm3c02346_si_001.avi
    eng

    Supporting information 1: 3D tomographic reconstruction of the Ni-PO4 precursor phases at t = 300 s derived from cryo-TEM micrographs is shown in different orientations (−60° < θ < 60°), 360° rotation of the reconstructed object around the z-axis in the x–y-plane (Video S1)

  • cm3c02346_si_002.avi
    eng

    Supporting information 2: 3D tomographic reconstruction of the Co-PO4 precursor phases at t = 600 s, derived from cryo-TEM micrographs is shown in different orientations (−60° < θ < 60°), 360° rotation of the reconstructed object around the z-axis in the x–y-plane (Video S2)

  • cm3c02346_si_003.zip
    eng

    Supporting information 3: Time-resolved pH data of the one-pot synthesis and the in situ scattering experiments are attached in the csv files, for the in situ scattering experiments, the phase fraction curves of the crystalline phases can be found in absolute and normalized values (pH_measurements_Onepotsynthesis.csv, in situ_data_Co.csv, in situ_data_Ni.csv, in situ_data_NiCo.csv)

  • cm3c02346_si_004.pdf
    eng

    Supporting information 4: Supplementary figures, tables, and notes

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Autor*innen:Stephanos KarafiludisORCiD, Z. KochovskiORCiD, E. ScoppolaORCiD, Anika RetzmannORCiD, Vasile-Dan HodoroabaORCiD, J. E. ten ElshofORCiD, Franziska EmmerlingORCiD, Tomasz Maciej StawskiORCiD
Dokumenttyp:Zeitschriftenartikel
Veröffentlichungsform:Verlagsliteratur
Sprache:Englisch
Titel des übergeordneten Werkes (Englisch):Chemistry of Materials
Jahr der Erstveröffentlichung:2023
Organisationseinheit der BAM:1 Analytische Chemie; Referenzmaterialien
1 Analytische Chemie; Referenzmaterialien / 1.3 Instrumentelle Analytik
6 Materialchemie
6 Materialchemie / 6.1 Oberflächen- und Dünnschichtanalyse
6 Materialchemie / 6.3 Strukturanalytik
Verlag:American Chemical Society (ACS)
Verlagsort:Washington D.C.
Jahrgang/Band:35
Ausgabe/Heft:24
Erste Seite:10645
Letzte Seite:10657
DDC-Klassifikation:Naturwissenschaften und Mathematik / Chemie / Analytische Chemie
Technik, Medizin, angewandte Wissenschaften / Ingenieurwissenschaften / Ingenieurwissenschaften und zugeordnete Tätigkeiten
Freie Schlagwörter:Amorphous phases; Intermediate phases; Non-classical crystallization theory; Phosphates; Transition metals
Themenfelder/Aktivitätsfelder der BAM:Chemie und Prozesstechnik
Material
Material / Materialdesign
DOI:10.1021/acs.chemmater.3c02346
ISSN:1520-5002
Verfügbarkeit des Dokuments:Datei im Netzwerk der BAM verfügbar ("Closed Access")
Datum der Freischaltung:14.12.2023
Referierte Publikation:Ja
Datum der Eintragung als referierte Publikation:30.01.2024
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