guest ::
| Home > Publications database > The Chemistry of Spinel Ferrite Nanoparticle Nucleation, Crystallization, and Growth |
| Home > Publications database > The Chemistry of Spinel Ferrite Nanoparticle Nucleation, Crystallization, and Growth |
| Journal Article | PUBDB-2024-01932 |
; ; ; ;
2024
Soc.
Washington, DC
This record in other databases: 
Please use a persistent id in citations: doi:10.1021/acsnano.3c08772 doi:10.3204/PUBDB-2024-01932
Abstract: The nucleation, crystallization, and growth mechanisms of MnFe$_2$O$_4$, CoFe$_2$O$_4$, NiFe$_2$O$_4$, and ZnFe$_2$O$_4$ nanocrystallites prepared from coprecipitated transition metal (TM) hydroxide precursors treated at sub-, near-, and supercritical hydrothermal conditions have been studied by in situ X-ray total scattering (TS) with pair distribution function (PDF) analysis, and in situ synchrotron powder X-ray diffraction (PXRD) with Rietveld analysis. The in situ TS experiments were carried out on 0.6 M TM hydroxide precursors prepared from aqueous metal chloride solutions using 24.5% NH$_4$OH as the precipitating base. The PDF analysis reveals equivalent nucleation processes for the four spinel ferrite compounds under the studied hydrothermal conditions, where the TMs form edge-sharing octahedrally coordinated hydroxide units (monomers/dimers and in some cases trimers) in the aqueous precursor, which upon hydrothermal treatment nucleate through linking by tetrahedrally coordinated TMs. The in situ PXRD experiments were carried out on 1.2 M TM hydroxide precursors prepared from aqueous metal nitrate solutions using 16 M NaOH as the precipitating base. The crystallization and growth of the nanocrystallites were found to progress via different processes depending on the specific TMs and synthesis temperatures. The PXRD data show that MnFe$_2$O$_4$ and CoFe$_2$O$_4$ nanocrystallites rapidly grow (typically <1 min) to equilibrium sizes of 20–25 nm and 10–12 nm, respectively, regardless of applied temperature in the 170–420 °C range, indicating limited possibility of targeted size control. However, varying the reaction time (0–30 min) and temperature (150–400 °C) allows different sizes to be obtained for NiFe$_2$O$_4$ (3–30 nm) and ZnFe$_2$O$_4$ (3–12 nm) nanocrystallites. The mechanisms controlling the crystallization and growth (nucleation, growth by diffusion, Ostwald ripening, etc.) were examined by qualitative analysis of the evolution in refined scale factor (proportional to extent of crystallization) and mean crystallite volume (proportional to extent of growth). Interestingly, lower kinetic barriers are observed for the formation of the mixed spinels (MnFe$_2$O$_4$ and CoFe$_2$O$_4$) compared to the inverse (NiFe$_2$O$_4$) and normal (ZnFe$_2$O$_4$) spinel structured compounds, suggesting that the energy barrier for formation may be lowered when the TMs have no site preference.
; 
; 
; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; Essential Science Indicators ; IF >= 15 ; JCR ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection
|
The record appears in these collections: |
PDF
PDF (PDFA)