Supplementary Information (SREP-12-03460)
Controlled Assembly of Sb2S3 Nanoparticles on Silica/Polymer Nanotubes:
Insights into the Nature of Hybrid Interfaces
Huaming Yang, Mei Li, Liangjie Fu, Aidong Tang & Stephen Mann
Table S1 Comparison of lattice parameters for various samples
c (Å)
Lattice volume (Å3)
calcined Sb2S3
11.226
11.321
3.838
487.81
calcined Sb2S3/HNTs
11.226
11.307
3.835
486.82
Sb2S3 (JCPDS 06-0474)
11.229
11.310
3.839
487.55
242
232
370
560
271
531
132
501
141
421
041
231
311
b
151
301
240
220
020
Intensity / a.u.
120
221
b (Å)
211
a (Å)
130
Sample
a
10
20
30
40
50
60
70
2 Theta / degree
Figure S1 XRD patterns of (a) as-synthesized Sb2S3 and (b) calcined Sb2S3 at 400 ºC under N2.
1
249
371
451
291
186
150
Intensity
b
a
100
200
300
400
500
Raman shift / cm
600
700
800
-1
Figure S2 Raman spectra of (a) as-synthesized Sb2S3/HNTs and (b) heated Sb2S3/HNTs at 400 ºC under N2.
2
Figure S3 (a) FTIR spectra of HNTs and as-synthesized Sb2S3/HNTs. The large increase in the intensity of the
O–H and –NHs stretching vibrations at 3437 cm-1, and C=O stretching vibration at 1637 cm-1, as well as the
appearance of a C-N stretching vibration at 1040 cm-1, is associated with the acetamide byproduct of the reaction
of TAA with antimony chloride. (b) FTIR spectra of as-synthesized Sb2S3/HNTs and calcined Sb2S3/HNTs at
400 ºC under N2.
3
Full survey XPS spectra
a
Intensity (a.u.)
Sb3d
Sb2S3
Sb3p
SbAuger
C1s
S2s S2p
Sb4d
Sb2S3/HNTs
Si2p
1000 900
800
700
600
500
400
300
200
100
0
Binding Energy / eV
Figure S4 (a) XPS survey spectra of the as-synthesized Sb2S3 and Sb2S3/HNTs. Trace amounts of carbon in the
control sample originate from residual impurities during the synthesis procedure. High-resolution XPS profiles
and fitted lines for (b) Sb 3d and O 1s, (c) S 2p and (d) C 1s regions for as-synthesized Sb2S3/HNTs.
4
Figure S5 (a) Solid-state UV-vis spectra and (b) plots of (αhν)2 versus hν of as-synthesized Sb2S3/HNTs and
the calcined Sb2S3/HNTs at 400 ºC under N2.
5
17
16
15
14
Intensity
13
c
b
12
11
10
9
a
0.2
0.0
665
670
675
680
685
690
695
700
705
Wavelength (nm)
Figure S6 Fluorescence spectra of (a) original HNTs, (b) as-synthesized Sb2S3 and (c) Sb2S3/HNTs.
6
c
O
Si
H
Total DOS
DOS (states/eV)
80
40
0
-8
-6
-4
-2
0
2
4
6
8
Energy (eV)
Figure S7 Structural model of amorphous silica surface. (a) Side view, (b) top view, and (c) corresponding
total density of states (DOS) and atom-projected density of states (PDOS).
7
Probability density (1/Angstrom)
a
Bond distribution
16
8
1.0
c
1.2
1.4
1.6
1.8
Bond length (Angstrom)
2.0
Probability density (1/Angstrom)
0
Si-C
80
40
0
120
1.83
1.84
1.85
Bond length (Angstrom)
e
Probability density (1/Angstrom)
Probability density (1/Angstrom)
Probability density (1/Angstrom)
Probability density (1/Angstrom)
24
C-S
80
40
0
1.79
1.80
1.81
Bond length (Angstrom)
b
Si-O
40
20
0
1.56
80
1.58
1.60
1.62
1.64
Bond length (Angstrom)
C-C
d
60
40
20
0
60
1.50
1.51
1.52
1.53
Bond length (Angstrom)
S-H
f
40
20
0
1.34
1.36
1.38
Bond length (Angstrom)
Figure S8 Bond length distributions of the HNTs surface.
8
1.40
Bond distribution
Probability density (1/Angstrom)
6
4
2
0
1.0
1.2
1.4
1.6
1.8
Bond length (Angstrom)
Figure S9 Bond length distribution on a mercaptopropyl-functionalized amorphous silica surface after 5 ps
dynamic equilibrium.
DOS (states/eV)
c
b
a
-20
-16
-12
-8
-4
Energy (eV)
0
4
Figure S10 Total density of states (DOS). The calculated band gaps were: (a) pure Sb2S3 (1.75 eV), (b)
mercaptopropyl-functionalized silica surface (HNTs, 3.75 eV), and (c) Sb2S3/HNT nanocomposites (2.0 eV). The
latter two values agreed well with the experimental results (solid-state UV-vis spectroscopy, Figure S5). The
underestimate of the band gap is mainly due to the well-known LDA problem, but it does not influence the
theoretical analysis.
9
Figure S11
TEM images of the individual HNT coated with Sb2S3 nanoparticles for the as-synthesized
Sb2S3/HNTs prepared by simultaneously adding TAA and HNTs to a Sb(III) solution at Sb:Si molar ratio of (a)
1:1 and (b) 1:10. (c) Sample prepared by adding TAA followed by a HNTs suspension.
Figure S12
Low magnification TEM image of as-synthesized Sb2S3/HNTs at Sb:Si=1:10.
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