Connecting Observations of Hematite (a Fe2O3) Growth Catalyzed by Fe(II)
Electron exchange between aqueous Fe(II) and structural Fe(III) in iron oxides and oxyhydroxides is important for understanding degradation of environmental pollutants through its apparent constitutive role underlying highly reactive “sorbed Fe(II)” and by catalyzing phase interconversion among these minerals. Although a mechanistic understanding of relationships between interfacial Fe(II)ads-Fe(III)oxide electron transfer, bulk electron conduction, and phase transformation behavior is emerging, much remains unclear in part due to poorly interconnected investigations. The focus of this study is on reconciling two mutually similar observations of Fe(II)-catalyzed hematite growth documented spectroscopically and microscopically under substantially different chemical conditions. Here we employ iron isotopic labeling to demonstrate that hematite grown on the (001) surface in Fe(II)-oxalate solution at low pH and elevated temperature has temperature-dependent magnetic properties that closely correspond to those of hematite grown in Fe(II) solution at circumneutral pH at room temperature. The temperature evolution and extent of the Morin transition displayed in these two materials strongly suggest a mechanistic link between the two studies, and that this mechanism involves in part trace structural Fe(II) incorporation into the growing hematite. Our findings indicate that Fe(II) catalyzed growth of hematite on hematite can occur under environmentally relevant conditions and may be due to bulk electron conduction previously demonstrated for hematite single crystals.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 974935
- Report Number(s):
- PNNL-SA-67480; 25629; KC0303020; TRN: US201007%%894
- Journal Information:
- Environmental Science & Technology, 44(1):61-67, Vol. 44, Issue 1
- Country of Publication:
- United States
- Language:
- English
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