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Mechanism and Kinetics of Hematite Crystallization in Air: Linking Bulk and Surface Models via Mesoporous Films with Defined Nanostructure

MPG-Autoren
http://pubman.mpdl.mpg.de/cone/persons/resource/persons32777

Klemm,  Hagen
Chemical Physics, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons22076

Schmidt,  Thomas
Chemical Physics, Fritz Haber Institute, Max Planck Society;

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Zitation

Schulz, K., Schmack, R., Klemm, H., Kabelitz, A., Schmidt, T., Emmerling, F., et al. (2017). Mechanism and Kinetics of Hematite Crystallization in Air: Linking Bulk and Surface Models via Mesoporous Films with Defined Nanostructure. Chemistry of Materials, 29(4), 1724-1734. doi:10.1021/acs.chemmater.6b05185.


Zitierlink: http://hdl.handle.net/11858/00-001M-0000-002C-B0DE-A
Zusammenfassung
Iron can form numerous oxides, hydroxides, and oxide−hydroxides. Despite their relevance, many of the transformation processes between these phases are still poorly understood. In particular the crystallization of quasi-amorphous hydroxides and oxide−hydroxides is difficult to assess, since typical diffraction and scattering methods provide only sample-averaged information about the crystallized phases. We report a new approach for the investigation of the crystallization of oxide−hydroxides. The approach relies on model-type films that comprise a defined homogeneous nanostructure. The nanostructure allows quantitative linking of information obtained by bulk-averaging diffraction techniques (XRD, SAXS) with locally resolved information, i.e., domain sizes (SEM, TEM, LEEM) and phase composition (SAED). Using time-resolved imaging and diffraction we deduce mechanism and kinetics for the crystallization of ferrihydrite into hematite. Hematite forms via nucleation of hematite domains and subsequent domain growth that terminates only upon complete transformation. A Johnson–Mehl–Avrami–Kolmogorov model describes the kinetics over a wide temperature range. The derived understanding enables the first synthesis of ferrihydrite films with ordered mesoporosity and quantitative control over the films’ hematite and ferrihydrite content.