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Hydrate networks under mechanical stress – A case study for Co3(PO4)2·8H2O

  • The nature of the bound water in solids with hydrogen-bonded networks depends not only on temperature and pressure but also on the nature of the constituents. The collapse and reorientation of these network structures determines the stability of hydrated solids and transitions to other crystalline or amorphous phases. Here, we study the mechanochemically induced loss of bound water in Co₃(PO₄)₂·8H₂O and compare this process to the behavior under hydrostatic pressure. The associated phase transition and its kinetics were monitored by X-ray powder diffraction with Synchrotron radiation and quantitative IR spectroscopy. High shearing forces are responsible for the degradation of the hydrogen-bonded network and the concomitant crystalline–amorphous transformation. UV/Vis spectroscopy, extended X-ray absorption spectroscopy (EXAFS), and X-ray absorption near-edge spectroscopy (XANES) provided information about the short-range order in the amorphous solid, and thermal analysis revealed itsThe nature of the bound water in solids with hydrogen-bonded networks depends not only on temperature and pressure but also on the nature of the constituents. The collapse and reorientation of these network structures determines the stability of hydrated solids and transitions to other crystalline or amorphous phases. Here, we study the mechanochemically induced loss of bound water in Co₃(PO₄)₂·8H₂O and compare this process to the behavior under hydrostatic pressure. The associated phase transition and its kinetics were monitored by X-ray powder diffraction with Synchrotron radiation and quantitative IR spectroscopy. High shearing forces are responsible for the degradation of the hydrogen-bonded network and the concomitant crystalline–amorphous transformation. UV/Vis spectroscopy, extended X-ray absorption spectroscopy (EXAFS), and X-ray absorption near-edge spectroscopy (XANES) provided information about the short-range order in the amorphous solid, and thermal analysis revealed its composition and showed that the moderate charge densities of the Co²⁺ and PO₄³⁻ ions, which make the hydration enthalpy comparable to the binding energy of the counteranions, and the Formation of hydrogen-bonded networks favor multistage crystallization processes associated with the release and uptake of coordinated water. The changes of the Co²⁺ coordination induce a color change from pink to blue; therefore, Co₃(PO₄)₂·8H₂O can be used as an overheat temperature indicator.zeige mehrzeige weniger

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Autor*innen:S. Bach, E. Visnow, M. Panthöfer, T. Gorelik, Ana de Oliveira Guilherme BuzanichORCiD, A. Gulo, U. Kolb, Franziska EmmerlingORCiD, C. Lind, W. Tremel
Dokumenttyp:Zeitschriftenartikel
Veröffentlichungsform:Verlagsliteratur
Sprache:Englisch
Titel des übergeordneten Werkes (Englisch):European Journal of Inorganic Chemistry
Jahr der Erstveröffentlichung:2016
Verlag:Wiley-VCH Verlag GmbH & Co. KGaA
Verlagsort:Weinheim, Germany
Jahrgang/Band:2016
Ausgabe/Heft:13-14
Erste Seite:2072
Letzte Seite:2081
DDC-Klassifikation:Naturwissenschaften und Mathematik / Chemie / Analytische Chemie
Technik, Medizin, angewandte Wissenschaften / Ingenieurwissenschaften / Ingenieurwissenschaften und zugeordnete Tätigkeiten
Freie Schlagwörter:Amorphous materials; Cobalt; Hydrates; Mechanochemistry; Phosphates
DOI:10.1002/ejic.201501481
ISSN:1434-1948
ISSN:1099-0682
Verfügbarkeit des Dokuments:Datei im Netzwerk der BAM verfügbar ("Closed Access")
Datum der Freischaltung:10.06.2016
Referierte Publikation:Ja
Datum der Eintragung als referierte Publikation:21.06.2016
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