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  Detection of the electronic structure of iron-(III)-oxo oligomers forming in aqueous solutions

Seidel, R., Kraffert, K., Kabelitz, A., Pohl, M. N., Kraehnert, R., Emmerling, F., et al. (2017). Detection of the electronic structure of iron-(III)-oxo oligomers forming in aqueous solutions. Physical Chemistry Chemical Physics, 19(48), 32226-32234. doi:10.1039/c7cp06945f.

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 Creators:
Seidel, Robert1, 2, Author
Kraffert, Katrin3, Author
Kabelitz, Anke2, 4, Author
Pohl, Marvin Nicolas5, Author           
Kraehnert, Ralph3, Author
Emmerling, Franziska4, Author
Winter, Bernd5, Author           
Affiliations:
1Helmholtz-Zentrum Berlin für Materialien und Energie, Institute for Material Development, Albert-Einstein-Strasse 15, D-12489 Berlin, Germany, ou_persistent22              
2Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Str. 2, D-12489 Berlin, Germany, ou_persistent22              
3Technische Universität Berlin, Department of Chemistry, Strasse des 17. Juni 124, D-10623 Berlin, Germany, ou_persistent22              
4BAM Federal Institute for Materials Research and Testing, Richard-Willstätter Strasse 11, D-12489 Berlin, Germany, ou_persistent22              
5Molecular Physics, Fritz Haber Institute, Max Planck Society, ou_634545              

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 Abstract: The nature of the small iron-oxo oligomers in iron-(III) aqueous solutions has a determining effect on the chemical processes that govern the formation of nanoparticles in aqueous phase. Here we report on a liquid-jet photoelectron-spectroscopy experiment for the investigation of the electronic structure of the occurring iron-oxo oligomers in FeCl3 aqueous solutions. The only iron species in the as-prepared 0.75 M solution are Fe3+ monomers. Addition of NaOH initiates Fe3+ hydrolysis which is followed by the formation of iron-oxo oligomers. At small enough NaOH concentrations, corresponding to approximately [OH]/[Fe] = 0.2–0.25 ratio, the iron oligomers can be stabilized for several hours without engaging in further aggregation. Here, we apply a combination of non-resonant as well as iron 2p and oxygen 1s resonant photoelectron spectroscopy from a liquid microjet to detect the electronic structure of the occurring species. Specifically, the oxygen 1s partial electron yield X-ray absorption (PEY-XA) spectra are found to exhibit a peak well below the onset of liquid water and OH- (aq) absorption. The iron 2p absorption gives rise to signal centered between the main absorption bands typical for aqueous Fe3+. Absorption bands in both PEY-XA spectra are found to correlate with an enhanced photoelectron peak near 20 eV binding energy, which demonstrates the sensitivity of resonant photoelectron (RPE) spectroscopy to mixing between iron and ligand orbitals. These various signals from the iron-oxo oligomers exhibit maximum intensity at [OH]/[Fe] = 0.25 ratio. For the same ratio, we observe changes in the pH as well as in complementary Raman spectra, which can be assigned to the transition from monomeric to oligomeric species. At approximately [OH]/[Fe] = 0.3 we begin to observe particles larger than 1 nm in radius, detected by small-angle X-ray scattering.

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Language(s): eng - English
 Dates: 2017-10-112017-11-022017-11-132017-12-28
 Publication Status: Issued
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/c7cp06945f
 Degree: -

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Title: Physical Chemistry Chemical Physics
  Abbreviation : Phys. Chem. Chem. Phys.
Source Genre: Journal
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Publ. Info: Cambridge, England : Royal Society of Chemistry
Pages: 9 Volume / Issue: 19 (48) Sequence Number: - Start / End Page: 32226 - 32234 Identifier: ISSN: 1463-9076
CoNE: https://pure.mpg.de/cone/journals/resource/954925272413_1