Electronic Supplementary Material (ESI) for Energy & Environmental Science
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A Red Anatase TiO2 Photocatalyst for Solar Energy Conversion
Gang Liu,1† Li-Chang Yin,1† Jianqiang Wang,2 Ping Niu,1 Chao Zhen,1 Yingpeng
Xie,1 Hui-Ming Cheng1*
1
Shenyang National Laboratory for Materials Science, Institute of Metal Research,
Chinese Academy of Sciences, 72 Wenhua Road, Shenyang 110016, China
2
Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics,
Chinese Academy of Sciences, 239 Zhangheng Road, Shanghai, 201800, China
TiN
o
Intensity / a.u.
800 C
o
750 C
o
700 C
o
650 C
o
600 C
Pristine
20
30
40
50
2 theta / degree
60
Fig S1 XRD patterns of the white TiO2 microspheres treated in gaseous ammonia
atmosphere at different temperatures from 600 oC to 800 oC for 1 h.
R
(ii)
R
R
204A
105A
211A
200A
103A
004A
112A
Intensity (a.u.)
101A
Electronic Supplementary Material (ESI) for Energy & Environmental Science
This journal is © The Royal Society of Chemistry 2012
R
(i)
20 25 30 35 40 45 50 55 60 65
2 theta (degree)
Fig S2 XRD patterns of the (i) white and (ii) red TiO2 microspheres. A: anatase; R:
rutile.
Absorbance (a.u.)
(i)
(ii)
300
400 500 600 700
Wavelength (nm)
800
Fig S3 UV-visible absorption spectra of the reference anatase TiO2 without interstitial
boron (i) before and (ii) after nitrogen doping.
Electronic Supplementary Material (ESI) for Energy & Environmental Science
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Intensity (a.u.)
Eg
B1g
Eg
A1g
Eg
(ii)
(i)
150
300 450 600 750
-1
Raman shift (cm )
900
Fig S4 Raman spectra of the (i) white and (ii) red TiO2 microspheres.
Table 1 Comparing XPS binding energies of Ti 2p, O 1s, B 1s and N 1s in the white
and red TiO2 microspheres. The data was collected from the pristine surface.
Sample
White TiO2
Red TiO2
Ti 2p (eV)
Percent (%)
458.9
458.3
O 1s
Percent (%)
530.1
529.5
N 1s
Percent (%)
--397.6
Ti
( )O
①: 1.95Å
①
②: 2.00Å
Fig. S5 A 2×2×1supercell for anatase TiO2.
②
B 1s
Percent (%)
192.2
191.6/190.1
Energy / eV
Electronic Supplementary Material (ESI) for Energy & Environmental Science
This journal is © The Royal Society of Chemistry 2012
2.0
2.0
1.5 CBM
1.5
Total
O2p
1.0
N2p
0.5
Ti3d
VBM
0.0
1.0
0.5
0.0
-0.5
-0.5

X R
Z 
M A
Z DOS / a.u.
Fig S6 The calculated band structures of anatase TiO2 doped with [BO4-xNx] (x = 4).
2.0
white TiO2
K-M
1.5
red TiO2
1.0
0.5
1.94
0.0
1.5
2.0
2.5
3.22
3.0 3.5 4.0
Energy (eV)
4.5
5.0
Fig S7 Plots of the transformed Kubelka–Munk function vs. the energy of light for the
white and red TiO2 microspheres.
Electronic Supplementary Material (ESI) for Energy & Environmental Science
This journal is © The Royal Society of Chemistry 2012
TCD2 B, 后部信号 (FID\CH4001097.D)
25 µV
0h
-18.35
-18.375
-18.4
-18.425
-18.45
-18.475
-18.5
-18.525
-18.55
0.2
0.4
0.6
0.8
1
TCD2 B, 后部信号 (FID\CH4001099.D)
25 µV
-17.85
1h
-18.16
-18.18
1.2
1.4
1.6
min
1.8
TCD2 B, 后部信号 (FID\CH4001100.D)
25 µV
-18.14
-17.9
2h
-17.95
-18.2
-18
-18.22
-18.05
-18.24
-18.26
-18.1
-18.28
-18.15
-18.3
-18.2
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
min
0.2
TCD2 B, 后部信号 (FID\CH4001102.D)
-17.7
-17.75
0.4
0.6
0.8
1
1.2
1.4
1.6
min
1.8
TCD2 B, 后部信号 (FID\CH4001103.D)
25 µV
25 µV
-17.55
3h
-17.6
4h
-17.65
-17.8
-17.7
-17.85
-17.75
-17.9
-17.8
-17.85
-17.95
-17.9
-18
-17.95
-18.05
-18
0.25
0.5
0.75
1
1.25
1.5
1.75
2 min
0.2
TCD2 B, 后部信号 (FID\CH4001105.D)
-17.5
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
min
TCD2 B, 后部信号 (FID\CH4001108.D)
25 µV
25 µV
5h
-17
6h
-17.1
-17.6
-17.2
-17.7
-17.3
-17.4
-17.8
-17.5
-17.9
-17.6
0.25
0.5
0.75
1
1.25
1.5
1.75
min
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
min
Fig S8 GC signal spectra of H2 detected in the gaseous product from the
photoelectrochemical cell after different irradiation times.