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Supporting Information
Highly conductive nanostructured PEDOT polymer confined
into the mesoporous MIL-100(Fe)
Pablo Salcedo-Abraira,a† Andrea Santiago-Portillo,b† Pedro Atienzar,b Pierre Bordet,c
Fabrice Salles,d Nathalie Guillou,e Erik Elkaim,f Hermenegildo García,b Sergio
Navalon,b,* Patricia Horcajadaa,*
aAdvanced Porous Materials Unit, IMDEA Energy, Avda. Ramón y Cajal 3, 28935
Móstoles-Madrid, Spain
bDepartment of Chemistry and Instituto de Tecnología Química, Consejo Superior de
Investigaciones Científicas-Universitat Politècnica de València, Universitat Politècnica
de València, C/Camino de Vera, s/n, 46022, Valencia, Spain
cInstitute NEEL CNRS/UGA, 25 rue des Martyrs, Grenoble cedex 9, France.
dInstitut Charles Gerhardt Montpellier, UMR 5253 CNRS UM ENSCM, Université
Montpellier, Place E. Bataillon, 34095 Montpellier Cedex 05, France
eInstitut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles St-Quentin
en Yvelines, Université Paris Saclav, 45 Av. des Etats-Unis, 78035 Versailles, France
fCRISTAL Beamline, Synchrotron Soleil, L'orme des Merisiers, Saint-Aubin, BP 48,
91192 Gif-sur-Yvette Cedex, France
† These authors contributed to this manuscript equally
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2019
100 200 300 400 500 6000
20
40
60
80
100
MIL-100 (Fe)
Acetonitrile
58.0
18.43
Weig
ht
loss (
%)
T (ºC)
27.81
74.94
82.5
45.2
68.3
22.6
Hexane
Figure S1.TGA curves of PEDOT@MIL-100(Fe) encapsulated in acetonitrile (blue) or hexane
(red), together with the empty MIL-100(Fe) solid (black)
100 200 300 400 500 6000
20
40
60
80
100
90% (w/w) EDOT
180% (w/w) EDOT
18.4322.65
Weig
ht
loss (
%)
T (ºC)
81.6980.00
45.2
56.76
12.87
91.5
31.58
45% (w/w) EDOT
Figure S2. TGA curves of PEDOT@MIL-100 (Fe)-1 (blue), 2 (red) and 3 (orange) composites
4000 3000 2000 1000
PEDOT
PEDOT (180 wt%)/MIL100Fe-hex
PEDOT (45 wt%)/MIL100Fe-hex
PEDOT (90 wt%)/MIL100Fe-hex
PEDOT (90 wt%)/MIL100Fe-acet
Tra
nsm
itta
nce (
%)
Wavenumber (cm-1)
MIL100Fe
Figure S3. FTIR spectra of MIL-100(Fe) (a), PEDOT-MIL100(Fe)-1 (b), PEDOT-MIL100(Fe)-
2 (c), PEDOT-MIL100(Fe)-3 (d) and as-prepared PEDOT (c).
Figure S4. PXRD patterns of MIL-100(Fe) (Black) and PEDOT@MIL-100(Fe)-1 (pink), 2
(red) and-3 (green) composites.
Table S1. Elemental composition of free PEDOT and amount of PEDOT inside the MIL-
100(Fe)-2
Theo. vs exp.
Free PEDOT Fe/S at. ratio 0 vs 0,08 ± 0,05
Free PEDOT Cl/S at. ratio 0,3 vs 0,33 ± 0,12
PEDOT@MIL-
100(Fe)-2.
PEDOT (%wt; dry empty solid) 60 ± 9
Number of EDOT monomer/u.c. 1062 ± 174
Number EDOT monomer/large cage 58 ± 9
Number EDOT monomer/small cage 37 ± 6
Number total Cl/u.c. 1365 ± 363
Cl/S at. Ratio 1.28 ± 0.33
Considering 1 Cl- / 3 EDOT 354 ± 58
Number excess Cl/u.c. 1011 ± 319
Number Fe total/u.c. 2003 ± 581
Number Fe MIL100/u.c. 1152
Number Fe excess/u.c. 851 ± 581
Excess Fe/Fe MIL100 (u.c.) 0,74 ± 0,50
Figure S5. XPS of MIL-100(Fe). Legend: (a) C 1s; (b) O 1s; (c) Fe 2p; (d) Cl 2p; (e) F 1s.
282 284 286 288 290 292 2940
20000
40000
60000
80000
100000C
PS
Binding energy (eV)
Csp2
O=C-O
525 530 535 540
20000
40000
60000
80000
100000
120000
140000
CP
S
Binding energy (eV)
185 190 195 200 205 210 215 220
4800
5200
5600
6000
6400
CP
S
Binding energy (eV)
680 685 690 695 70067500
70000
72500
75000
77500
CP
S
Binding energy (eV)
a) b)
c) d)
e)
710 720 730
70000
80000
90000
100000
110000
120000
130000
CP
S
Binding energy (eV)
Fe(III)
Fe(III) satellites
Figure S6. XPS of PEDOT@MIL-100(Fe)-2. Legend: (a) C 1s; (b) O 1s; (c) Fe 2p; (d) Cl 2p;
(e) F 1s; (f) S 2p
Figure S7. PXRD patterns collected by using synchrotron radiation
Figure S8. Left: Simulated and experimental PDF analysis of EDOT molecule. Right: DFT
Simulated chemical structure of isolated EDOT together with the main atomic distances.
Figure S9. Top: experimental PDFs of EDOT and PEDOT up to 10 (left) and 25 Å (right).
Bottom: DFT simulated chemical structure of free PEDOT together with the main atomic
distances. Sulphur, carbon, oxygen, hydrogen and chlorine are in yellow, grey, red, white and
blue respectively.
Figure S10. Comparison of the PDFs of MIL-100(Fe) and PEDOT@MIL-100(Fe).
Figure S11. Top: Subtracted PDF contribution of the EDOT in the EDOT@MIL-100(Fe)
compared with the free EDOT. Bottom: Subtracted PDF contribution of the PEDOT in the
PEDOT@MIL-100(Fe)-2 compared with the free PEDOT. Sulphur, carbon, oxygen, hydrogen
and iron are in yellow, grey, red, white and purple respectively
Figure S12. a) FTIR spectra of MIL-100(Fe) (red), PEDOT@MIL-100(Fe)-2 (black) and
isolated PEDOT (blue) (Asterisk indicate the presence of PEDOT bands in PEDOT@MIL-
100(Fe)) and b) zoom of the selected areas.
Figure S13. XRD patterns of: a) PEDOT@MIL-100(Fe)-2 thin film on FTO before (bottom)
and after (up) of 50 cycles of cyclic voltammetry and b) PEDOT@MIL-100(Fe)-2 thin film on
FTO before (bottom) and after (up) of 20 cycles of electrochromic switching. Asterisk indicate
diffraction peaks corresponding to the MIL-100(Fe) material.
Figure S14 SEM-EDX analysis of the PEDOT-MIL-100(Fe)-2 flat surface supported on FTO
employed for cyclic voltammetry measurements (left) and for electrochromism measurements
(right).
Figure S15. SEM-EDX analysis of the PEDOT-MIL-100(Fe)-2 film thickness supported on
FTO employed for cyclic voltammetry measurements (left) and for electrochromism
measurements (right)
Figure S16. FIB-SEM images of: (a) the fresh PEDOT@MIL-100(Fe)-2 film; (b) the used
PEDOT@MIL-101(Fe)-2 sample after 50 cycles of voltammetry; PEDOT@MIL-100(Fe)-2
before (c) and after (d) used in the 50 cycles of the cyclic voltammetry. Note: fast SEM images
were recorded (c,d) with low quality on purpose to properly measure the thickness minimizing
possible error due to the movement of the sample.
Figure S17. AFM images of PEDOT@MIL-100(Fe)-2 film before (a) and after (b) 50 cyclic
voltammetry cycles and roughness estimation.
Roughness (Ra) 301 nm
Roughness (Ra) 356 nm
a)
b)
Figure S18: Result of the fit of the PDF from the Ni standard sample.
Figure S19: Conformations of the PEDOT investigated by DFT calculations
Figure S20: Model of MIL-100 from literature (Horcajada et al., Chem. Commun., 2007, 2820-
2822)