Supplementary Information Influence of Facets and ...S1 Supplementary Information Influence of...
Transcript of Supplementary Information Influence of Facets and ...S1 Supplementary Information Influence of...
S1
Supplementary Information
Influence of Facets and Heterojunctions in
Photoactive Bismuth Oxyiodide
Aijuan Han,a,b Jiulong Sun,a,b Xuanhao Lin,a Cheng-Hui Yuan,a Gaik Khuan Chuah*a
and Stephan Jaenicke*a
a Department of Chemistry, National University of Singapore, 3 Science Drive 3,
Singapore 117543, Singapore
b NUS Environmental Research Institute, National University of Singapore, 5A
Engineering Drive 1, #02-01, Singapore 117411, Singapore
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2015
S2
Fig. S1 UV-vis diffuse reflectance spectra of BiOI samples synthesized at
different pH.
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
200 300 400 500 600 700 800
Ku
be
lka
-M
un
k F
un
ctio
n
Wavelength (nm)
pH 2.3
pH 3
pH 4
pH 5
pH 6
pH 7
pH 8
S3
Fig. S2 BiOI samples prepared at different pH.
BiOI-pH2.3 BiOI-pH3 BiOI-pH4
BiOI-pH6 BiOI-pH7 BiOI-pH8BiOI-pH5
S4
Fig. S3 Kinetic plots for p-cresol photodegradation over BiOI prepared at
different pH.
0
1
2
3
4
0 2 4 6 8
ln(C
0/C
)
Time (h)
pH 2.3
pH 3
pH 4
pH 5
pH 6
pH 7
pH 8
S5
Fig. S4 TGA and derivative weight loss for BiOI-pH6.
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
-1E-15
60
65
70
75
80
85
90
95
100
0 200 400 600 800
De
riva
tive
we
igh
t (%
/oC
)
We
igh
t (%
)
T (oC)
17 %
Bi 4
O5I 2
19 %
Bi 7
O9I 3
27 %
Bi 5
O7I
32 %
Bi 2
O3
S6
Fig. S5 X-ray diffractograms (25o to 40o) of as-synthesized and calcined
BiOI-pH6 samples.
25 30 35 40
Inte
nsity (cp
s)
2 theta (o)
BiOI-pH6
* BiOI▲ Bi4O5I2Bi7O9I3○ Bi5O7I
**
* *
○
○ ○○
○ ○
○
○
○
○○
▲*
▲ *
○
BiOI-pH6-300-1
BiOI-pH6-350-1
BiOI-pH6-350-3
BiOI-pH6-350-5
BiOI-pH6-400-1
S7
Fig. S6 SEM images of (a) BiOI-pH6-300-1, (b) BiOI-pH6-350-1,
(c) BiOI-pH6-350-5, and (d) BiOI-pH6-400-1.
(a) (b)
(c) (d)
S8
Fig. S7 UV-vis diffuse reflectance spectra of BiOI-pH6 calcined at 300 - 400 ℃
for 1 to 5 h
0
2
4
6
8
10
12
200 400 600 800
Ku
be
lka
-Mu
nk F
un
ctio
n
Wavelength (nm)
pH6
pH6-300-1
pH6-350-1
pH6-350-3
pH6-350-5
pH6-400-1
S9
Fig. S8 BiOI-pH6 calcined at different temperatures and times.
BiOI-pH6 BiOI-pH6-300-1
BiOI-pH6-350-1 BiOI-pH6-350-3
BiOI-pH6-350-5 BiOI-pH6-400-1
S10
Fig. S9 Total and partial density of state of BiOI.
0
3
6
9
12
-20 -10 0 10 20
Energy (eV)
total
O
I
Bi
TDOS for BiOI
0
3
6
9
12/
eV
cell)
s
pPDOS for O
0
3
6
9
12
DO
S (S
tate
tes
s
p
PDOS for I
0
3
6
9
12
15s
pPDOS for Bi
S11
Fig. S10 Total organic carbon and degradation efficiency for p-cresol versus time
over BiOI-pH6-350-3.
0
20
40
60
80
100
0
4
8
12
16
20
0 0.5 1 1.5 2
DE
(%
)
TO
C (
pp
m)
Time (h)
S12
Compound X (eV) Eg (eV) EVB (eV) ECB (eV)
BiOI 5.94 1.90 2.39 0.49
Bi4O5I2 5.39 2.04 1.91 -0.13
Bi7O9I3 5.46 2.56 2.24 -0.32
Bi5O7I 5.92 3.16 3.00 -0.16
Fig. S11 Conduction and valence band positions of various bismuth oxyiodides.
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
E /
eV
Bi4O5I2
BiOI
2.5
6 e
V
3.1
6 e
V
2.0
4eV
1.9
eV
Bi7O9I3 Bi5O7I
S13
Fig. S12 (a) Photodegradation efficiency for p-cresol over recycled BiOI-pH6-350-3
and (b) x-ray diffractograms of fresh and used BiOI-pH6-350-3.
0
20
40
60
80
100
1 2 3 4
DE
(%
)
Run
(a)
5 15 25 35 45 55 65 75
Inte
nsity (cp
s)
2 theta (o)
fresh
recycled
(b)
S14
Fig. S13 Photocatalytic degradation of p-cresol over BiOI-pH6-350-3 in the presence
of 1 mmol/L NaCl and NH4NO3.
0
20
40
60
80
100
0 0.5 1 1.5 2
DE
(%
)
Time (h)
NaCl
NH4NO3
no
S15
Fig. S14 Fluorescence spectrum of terephthalic acid solution after different
illumination times in the presence of BiOI-pH6-350-3.
0
40000
80000
120000
350 400 450 500 550 600
Flu
ore
sce
nce
Wavelength (nm)
0 min
30 min
60 min
120 min
S16
106.8
139.7
214.7
-MS, 13.7min #1970
0
1
2
3
4
5
6x10
Intens.
100 150 200 250 300 350 400 450 m/z
(a)
92.9
105.8
122.7
145.6
155.6
170.7 198.7 212.8
246.7
282.9 325.1 339.1353.1 381.2 395.1 412.2 440.2 454.3 468.2 496.2
-MS, 3.7min #534
0
1
2
3
4
5
6
5x10
Intens.
100 150 200 250 300 350 400 450 m/z
(b)
120.7
126.6
145.6
156.7
170.7
-MS, 6.1min #867
0.00
0.25
0.50
0.75
1.00
1.25
1.50
5x10
Intens.
80 100 120 140 160 180 200 220 m/z
(c)
S17
Fig. S15 Mass spectra of species detected in p-cresol photodegradation (a) p-cresol
and (b-e) degradation intermediates.
170.7 184.7
212.7
226.7
254.9
268.9
283.0
297.0 313.0 323.0 339.0 351.2
365.1386.1
393.2407.1
423.2437.2
451.3
-MS, 26.2min #3755
0.0
0.5
1.0
1.5
2.0
2.55x10
Intens.
200 250 300 350 400 450 m/z
(d)
126.6
136.6
145.6
184.7
212.7
254.9
282.9
296.9 323.0353.1
367.1384.1
398.1409.2 423.2 437.3 454.2 468.2 482.2
-MS, 26.5min #3801
0.0
0.5
1.0
1.5
2.0
5x10
Intens.
100 150 200 250 300 350 400 450 m/z
(e)
S18
S1. Theoretical calculation of the angles between different planes
The theoretical value for the angles (φ) between different (hkl) planes of tetragonal
BiOI is determined by the following formula:
cosφ =
1a2
(h1h2 + k1k2) +1c2
l1l2
√[1a2
(h12 + k1
2) +1c2
l12][
1a2
(h22 + k2
2) +1c2
l22]
The angle between (110) and (200) is 45.0 o, while the angle between )( 131 and
)( 101 is 42.8 o using a = 0.3994 nm and c = 0.9149 nm.