Supporting Information
Mesoporous Hybrid Polypyrrole-Silica Nanocomposite Films with a
Strata-Like Structure
Ahmed A. Farghaly and Maryanne M. Collinson*
Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284-2006,
United States
■ Authors information
Ahmed A. Farghaly ORCID ID Orcid.org/0000-0001-7948-3700
Maryanne M. Collinson, ORCID ID Orcid.org/0000-0001-6839-5334
Corresponding Author
*E-mail: [email protected]. Phone: 804-828-7509
Contents
Figure S1. Photographs at different intervals during the coelectrodeposition of the
nanocomposite film. The electrogenerated nitrosonium NO+ ions started to diffuse beyond the
electrode surface at t = 60 sec and complete diffusion was achieved at t = 600 sec. The pyrrole
monomers in the bulk oxidized at t = 800 sec. The progress of reaction indicates that Ppy
deposited within and around the silica mesopores. At t = 0 sec, the working electrode appears
dark because of the shadows from the reference/counter electrodes.
Figure S2. SEM images of Ppy-SiO2-Ag@Au nanocomposite films prepared at: -0.6 volts (a &
b) and -0.8 volts (c & d) for 30 min.
Figure S3. SEM images reflect the effect of different concentration parameters on the
morphology of Ppy-SiO2-Ag@Au nanocomposite films electrodeposited at -1.0 volts for 30 min.
Figure S4. SEM images of Ppy@Ag thin film obtained by treating sample B with HF (a-c). Ppy
free-standing free obtained by treating sample B with HF and HNO3, successively (d-f). PpySiO2 free-standing film obtained by treating sample B with HNO3 (g-i). Ppy free-standing film
obtained by treating sample B with HNO3 and HF, successively (j-l). The non-destruction of the
film reflects its homogeneity.
1
Figure S5. Surface profiles of the as-prepared Ppy-SiO2-Ag@Au nanocomposite film (sample
A), Ppy-Ag free-standing nanocomposite film (sample A + HF) and Ppy free-standing film
(sample A + HF + HNO3). The homogeneity of the deposited nanocomposite film is evident by
the similarity in film thickness.
Figure S6. EDX spectra of the as-prepared Ppy-SiO2-Ag@Au (sample A), Ppy-SiO2 (sample B,
after Ag substrate removal) free-standing film and Ppy free-standing film obtained by treating
sample A with HNO3 and HF, successively. The success of the coelectrodeposition process and
the etching strategy is evident.
Figure S7. EDX elemental mapping images of the as-prepared Ppy-SiO2@Ag (sample B). The
inset SEM image in the bottom right displays the area over which the maps collected.
Figure S8. EDX elemental mapping images of the free-standing Ppy-Ag hybrid film obtained by
treating sample A with HF. The inset SEM image in the bottom right displays the area over
which the maps collected.
Figure S9. EDX elemental mapping images of the free-standing Ppy film obtained by treating
sample A with HNO3 and HF, successively. The SEM image in the bottom displays the area over
which the maps collected.
Figure S10. EDX elemental mapping images of the free-standing Ppy-SiO2 film obtained by
treating sample B with HNO3. The SEM image in the bottom right displays the area over which
the maps collected. The bottom left image is an overlay of all the elemental maps. Note: the
color of the Si map in this figure is different from that in the other figures due to the fact that the
elemental maps for this sample were collected on a different SEM-EDS instrument.
Figure S11. Single point-scan EDX spectrum of Ppy-SiO2 free-standing film obtained by
treating sample B (Ppy-SiO2@Ag) with HNO3.
Figure S12. Cyclic voltammograms of a Ppy-SiO2 free-standing film loaded on a gold substrate
(red) and at a bare gold electrode (black) in 1.0 M Na2SO4 at a scan rate of 1000 mV/s (a). CVs
of Ppy-SiO2 free-standing film loaded on a gold substrate in 1.0 M Na2SO4 at different scan rates
(b).
Figure S13. Cyclic voltammograms of the Ppy-SiO2 free-standing film loaded on ITO substrate
(red solid line, a), anodically deposited Ppy on ITO substrate (red solid line, b) and bare ITO
electrode (black solid line in a, b) in 10 mM K3Fe(CN)6] in 0.2 M KCl (pH ~ 7) at a scan rate of
20 mV/s-1.
Figure S14. Kinetics of Ppy and silica electrodeposition during the formation of Ppy-SiO2Ag@Au nanocomposite film (sample A) as presented by (a and b) the cross-sectional selected
area EDX data and (c) EDX spectral data (Wt%) collected at different deposition times.
2
Figure S15. Kinetics of Ppy and silver electrodeposition during the formation of Ppy-SiO2Ag@Au nanocomposite film (sample A) as presented by EDX spectral data (Wt%) collected at
different deposition times.
3
Figure S1. Photographs acquired at different intervals during the
coelectrodeposition of the nanocomposite film. The electrogenerated nitrosonium
NO+ ions started to diffuse beyond the electrode surface at t = 60 sec and
complete diffusion was achieved at t = 600 sec. The pyrrole monomers in the
bulk oxidized at t = 800 sec. The progress of reaction indicates that Ppy deposited
within and around the silica mesopores. At t = 0 sec, the working electrode
appears dark because of the shadows from the reference/counter electrodes.
4
Figure S2. SEM images of Ppy-SiO2-Ag@Au nanocomposite films prepared at: -0.6
volts (a & b) and -0.8 volts (c & d) for 30 min.
5
Figure S3. SEM images reflect the effect of different
concentration parameters on the morphology of PpySiO2-Ag@Au nanocomposite films electrodeposited
at -1.0 volts for 30 min.
6
Figure S4. SEM images of Ppy@Ag thin film obtained by treating sample B with HF
(a-c). Ppy free-standing free obtained by treating sample B with HF and HNO3,
successively (d-f). Ppy-SiO2 free-standing film obtained by treating sample B with
HNO3 (g-i). Ppy free-standing film obtained by treating sample B with HNO3 and HF,
successively (j-l). The non-destruction of the film reflects its homogeneity.
7
Figure S5. Surface profiles of the as-prepared Ppy-SiO2-Ag@Au nanocomposite film
(sample A), Ppy-Ag free-standing nanocomposite film (sample A + HF) and Ppy freestanding film (sample A + HF + HNO3). The homogeneity of the deposited
nanocomposite film is evident by the similarity in film thickness.
8
Figure S6. EDX spectra of the as-prepared Ppy-SiO2-Ag@Au (sample A), Ppy-SiO2
(sample B, after Ag substrate removal) free-standing film and Ppy free-standing film
obtained by treating sample A with HNO3 and HF, successively. The success of the
coelectrodeposition process and the etching strategy is evident.
9
Figure S7. EDX elemental mapping images of the as-prepared Ppy-SiO2@Ag (sample B).
The inset SEM image in the bottom right displays the area over which the maps collected.
10
Figure S8. EDX elemental mapping images of the free-standing Ppy-Ag hybrid film obtained
by treating sample A with HF. The inset SEM image in the bottom right displays the area over
which the maps collected.
11
Figure S9. EDX elemental mapping images of the free-standing Ppy film obtained by
treating sample A with HNO3 and HF, successively. The SEM image in the bottom displays
the area over which the maps collected.
12
Figure S10. EDX elemental mapping images of the free-standing Ppy-SiO2 film
obtained by treating sample B with HNO3. The SEM image in the bottom right displays
the area over which the maps collected. The bottom left image is an overlay of all the
elemental maps. Note: the color of the Si map in this figure is different from that in the
other figures due to the fact that the elemental maps for this sample were collected on a
different SEM-EDS instrument.
13
Figure S11. Single point-scan EDX spectrum of Ppy-SiO2 free-standing film obtained by
treating sample B (Ppy-SiO2@Ag) with HNO3.
14
Figure S12. Cyclic voltammograms of a Ppy-SiO2 free-standing film loaded on
a gold substrate (red) and at a bare gold electrode (black) in 1.0 M Na2SO4 at a
scan rate of 1000 mV/s (a). CVs of Ppy-SiO2 free-standing film loaded on a
gold substrate in 1.0 M Na2SO4 at different scan rates (b).
15
Figure S13. Cyclic voltammograms of the Ppy-SiO2 free-standing
film loaded on an ITO substrate (red solid line, a), anodically
deposited Ppy on ITO substrate (red solid line, b) and a bare ITO
electrode (black solid line in a, b) in 10 mM K3Fe(CN)6] in 0.2 M
KCl (pH ~ 7) at a scan rate of 20 mV/s.
16
Figure S14. Kinetics of Ppy and silica electrodeposition during the formation of Ppy-SiO2Ag@Au nanocomposite film (sample A) as presented by (a and b) the cross-sectional selected
area EDX data and (c) EDX spectral data (Wt%) collected at different deposition times.
17
Figure S15. Kinetics of Ppy and silver electrodeposition during the formation of PpySiO2-Ag@Au nanocomposite film (sample A) as presented by EDX spectral data
(Wt%) collected at different deposition times.
18