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Iron near absorption edge X-ray spectroscopy at aqueous-membrane interfaces

Journal Article · · Physical Chemistry Chemical Physics
DOI:https://doi.org/10.1039/C4CP00657G· OSTI ID:1157659
Employing synchrotron X-ray scattering, we systematically determine the absorption near-edge spectra (XANES) of iron in its ferrous (Fe2+) and ferric (Fe3+) states both as ions in aqueous solutions and as they bind to form a single layer to anionic templates that consist of carboxyl or phosphate groups at aqueous/vapor interfaces. While the XANES of bulk iron ions show that the electronic state and coordination of iron complexes in the bulk are isotropic, the interfacial bound ions show a signature of a broken inversion-symmetry environment. The XANES of Fe2+ and Fe3+ in the bulk possess distinct profiles however, upon binding they practically exhibit similar patterns. This indicates that both bound ions settle into a stable electronic and coordination configuration with an effective fractional valence (for example, Fe[2+nu]+, 0 < nu < 1) at charged organic templates. Such two dimensional properties may render interfacial iron, abundant in living organisms, a more efficient and versatile catalytic behavior.
Research Organization:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
DOE Contract Number:
AC02-07CH11358
OSTI ID:
1157659
Report Number(s):
IS-J 8373
Journal Information:
Physical Chemistry Chemical Physics, Journal Name: Physical Chemistry Chemical Physics Journal Issue: 26 Vol. 16; ISSN 1463-9076; ISSN PPCPFQ
Country of Publication:
United States
Language:
English

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