J. Synchrotron Rad. (2015). 22, doi:10.1107/S1600577514025880
Supporting information
Volume 22 (2015)
Supporting information for article:
Identification of the iron oxidation state and coordination geometry
in iron oxide- and zeolite-based catalysts using pre-edge XAS
analysis
Alexey Boubnov, Henning Lichtenberg, Stefan Mangold and Jan-Dierk
Grunwaldt
J. Synchrotron Rad. (2015). 22, doi:10.1107/S1600577514025880
Supporting information, sup-1
XANES spectra and detailed view of the pre-edge peak
The X-ray absorption near-edge structure (XANES) spectra of the reference compounds,
mechanical mixtures and mixed spectra subject to pre-edge analysis in present work are
shown in Figures S1, S2 and S3.
J. Synchrotron Rad. (2015). 22, doi:10.1107/S1600577514025880
Supporting information, sup-2
High-resolution transmission XANES, binary mixtures
Normalised absorption
a
1.4
1.4
1.4
1.2
1.2
1.2
1.0
1.0
1.0
0.8
0.8
0.8
0.6
0.6
0.6
0.4
0.4
staurolite
mix 48 : 52
FeO
0.2
0.0
7110 7120 7130 7140 7150
0.4
FePO4
0.2
0.0
mix 63 : 37
staurolite
7110 7120 7130 7140 7150
0.0
1.4
1.4
1.4
1.2
1.2
1.2
1.0
1.0
1.0
0.8
0.8
0.8
0.6
0.6
0.6
0.4
0.4
FePO4
0.2
0.0
mix 45 : 55
-Fe2O3
7110 7120 7130 7140 7150
7110 7120 7130 7140 7150
0.4
FeO
mix 35 : 65
-Fe2O3
0.2
0.0
staurolite
mix 33 : 67
-Fe2O3
0.2
7110 7120 7130 7140 7150
FePO4
0.2
0.0
mix 63 : 37
FeO
7110 7120 7130 7140 7150
Energy [eV]
b
High-resolution transmission XANES (detail), binary mixtures
0.2
0.2
staurolite
mix 48 : 52
FeO
Normalised absorption
0.1
7112
7116
7120
0.2
0.0
7108
0.1
7112
7116
7120
0.2
FePO4
0.1
7116
7120
0.0
7108
7112
7116
7120
7116
7120
0.2
FePO4
mix 63 : 37
FeO
0.1
7112
0.0
7108
FeO
mix 35 : 65
-Fe2O3
mix 45 : 55
-Fe2O3
0.0
7108
staurolite
mix 33 : 67
-Fe2O3
mix 63 : 37
staurolite
0.1
0.0
7108
0.2
FePO4
0.1
7112
7116
7120
0.0
7108
7112
Energy [eV]
Figure S1 High-resolution transmission XANES spectra (a) and detail of pre-edge peak (b) of the
reference compounds and their binary mechanical mixtures. The stoichiometric Fe proportions in the
binary mixtures were determined by linear combination analysis.
J. Synchrotron Rad. (2015). 22, doi:10.1107/S1600577514025880
Supporting information, sup-3
Conventional-resolution XANES, binary linear combinations
Normalised absorption
a
1.4
1.4
1.4
1.2
1.2
1.2
1.0
1.0
1.0
0.8
0.8
0.6
0.6
staurolite
75 : 25
48 : 52
25 : 75
FeO
0.4
0.2
0.0
0.8
FePO4
7110 7120 7130 7140 7150
80 : 20
63 : 37
40 : 60
20 : 80
staurolite
0.4
0.2
0.0
7110 7120 7130 7140 7150
staurolite
80 : 20
60 : 40
33 : 67
20 : 80
-Fe2O3
0.6
0.4
0.2
0.0
7110 7120 7130 7140 7150
energy
1.4
1.4
1.4
1.2
1.2
1.2
1.0
1.0
0.8
0.8
0.6
FePO4
0.6
0.4
75 : 25
45 : 55
25 : 75
-Fe2O3
0.4
0.2
0.0
1.0
FeO
90 : 10
80 : 20
60 : 40
35 : 65
20 : 80
10 : 90
-Fe2O3
7110 7120 7130 7140 7150
0.2
0.0
7110 7120 7130 7140 7150
0.8
FePO4
0.6
80 : 20
63 : 37
40 : 60
20 : 80
FeO
0.4
0.2
0.0
7110 7120 7130 7140 7150
Energy [eV]
b
Conventional-resolution XANES (detail), binary linear combinations
0.2
0.2
staurolite
75 : 25
48 : 52
25 : 75
FeO
80 : 20
63 : 37
40 : 60
20 : 80
staurolite
Normalised absorption
0.1
0.0
7108
0.2
FePO4
0.1
7112
7116
7120
0.0
7108
staurolite
80 : 20
60 : 40
33 : 67
20 : 80
-Fe2O3
0.1
7112
7116
7120
0.0
7108
7112
7116
7120
7116
7120
energy
0.2
0.2
FePO4
75 : 25
45 : 55
25 : 75
-Fe2O3
0.1
0.1
0.0
7108
7112
7116
7120
0.0
7108
0.2
FeO
90 : 10
80 : 20
60 : 40
35 : 65
20 : 80
10 : 90
-Fe2O3
7112
FePO4
80 : 20
63 : 37
40 : 60
20 : 80
FeO
0.1
7116
7120
0.0
7108
7112
Energy [eV]
Figure S2 Standard-resolution XANES (a) and detail of pre-edge peak (b) of the reference
compounds and binary mixtures. The spectra of the binary mixtures are linear combinations of the
normalised XANES spectra of the reference compounds with indicated stoichiometric proportions.
J. Synchrotron Rad. (2015). 22, doi:10.1107/S1600577514025880
Supporting information, sup-4
Standard-resolution transmission XANES, reference compounds
Normalised absorption
a
4.0
Fe
3+
2+
4.0
Fe and others
3.5
3.5
3.0
3.0 others:
2.5
Fe3O4
Td: ceylonite
-Fe2O3
2.5
Fe phth.cyan.
staurolite
2.0
2.0 T : sanidine
d
Oh: bronzite
1.5
1.5
olivine
1.0
FePO4·xH2O
FeO
7100
7110
Fe(III)acac
0.5
Fe(II)oxalate
0.0
Oh: aegirine
1.0
siderite
0.5
FePO4
Fe(NO3)3·9H2O
-Fe2O3
0.0
7120
7130
7140
7150
7100
7110
7120
7130
7140
7150
Energy [eV]
Standard-resolution transmission XANES (detail), reference compounds
b
1.0
Fe
2+
3+
Fe and others
1.2 others:
Fe3O4
Normalised absorption
0.8 Td: ceylonite
1.0
staurolite
-Fe2O3
Fe phth.cyan.
0.8 T : sanidine
d
0.6 Oh: bronzite
olivine
FePO4
0.6
0.4
siderite
Oh: aegirine
Fe(II)oxalate
0.4
FePO4·xH2O
0.2
0.2
FeO
0.0
Fe(III)acac
7108
Fe(NO3)3·9H2O
-Fe2O3
7112
7116
7120
0.0
7108
7112
7116
7120
Energy [eV]
Figure S3
XANES spectra (a) and the detail of pre-edge peak (b) of all reference compounds
measured with standard resolution. The Fe site specification in the compounds labelled “others” is
presented in Error! Reference source not found..