(A) Fe K-edge
XANES spectra of MIL-100(Fe) and MIL-100(Al,Fe) samples
and reference iron oxide compounds with iron valence states between
Fe2+ and Fe3+ [Fe2+: FeSO4·7H2O; Fe2.67+: Fe3O4; Fe3+: Fe2O3 (hematite), α-FeOOH
(goethite)]. The spectra are shifted vertically for clarity. The vertical
dashed line is plotted at the Fe K-edge position of 7125 eV to facilitate
the comparison of the Fe K-edge energy positions in different Fe compounds.
(B) Fourier transform magnitude of k3-weighted
Fe EXAFS spectra of MIL-100(Fe) and MIL-100(Al,Fe) samples, calculated
in the k range of 3–14 Å–1. Experiment, circles; best-fit EXAFS models in the R range from 1.0–3.3 Å, solid lines. (C) Fe Mössbauer
spectra of MIL-100(Fe) and MIL-100(Al,Fe) can be modeled well by at
least three contributions. Three equally intense individual components,
comprising the fit of the spectrum of MIL-100(Fe), are shown. The
three components can be assigned to three crystallographically slightly
different Fe sites within the 3Fe trimers. (D) X-band EPR spectra
of MIL-100(Fe) (red bullets) and MIL-100(Al,Fe) (blue circles) recorded
at 295 and 30 K. The thin black lines are the fits of the spectra
(see the Supporting Information). The positions
of the resonances with g = 2.09 and g = 4.3 are marked with vertical lines. The narrow signal indicated
by a star is due to the dielectric resonator. The spectra are vertically
shifted for clarity.