1 recent progress of photocatalytic water splitting and preliminary work zhibin lei supervisor:...
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1
Recent Progress of Photocatalytic Water Splitting and Preliminary Work
Zhibin LeiSupervisor: Prof. Can Li
Jan. 13, 2003
State Key laboratory of Catalysis, Dalian Institute of Chemical Physics
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☻ Significance of hydrogen energy
☻ Mechanism of photocatalytic water
splitting
☻ Recent development of water splitting
☻ My preliminary work and next plan
Content
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The concentration change of CO2 in air during the past one thousand years
Significance of hydrogen energy
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1996 1997 1998 1999 2000 20010
500
1000
1500
2000
2500
3000
3500
4000
Year
The funds used for the hydrogen project of USA in the past six years
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我国未来所需氢的预测结果(万吨)
项 目 2010 2020 2050
合成氨 768 936.2 936.2
炼油厂加氢精制 773.1 1141.7 1141.7
燃料电池电动车 326.6 967 8758.4
燃料电池发电 73.2 216.7 1962.8
合 计 1939.1 3261.6 12799.1
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6Predict hydrogen source in the next fifty years
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每年投射到地面上的太阳能约 1.05×1018kWh ,相当于 1.3×106 亿吨标准煤
• Energy source• Environment• Economy
PhotocatalystH2O H2 + ½ O2
hv
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A.Fijishima and K.Honda. Nature. 1972, 238, 37.
TiO2 + 2 hv 2 e–+2 h+ (1) (at the TiO2 electrode)
2 H+ + 2 e– H2 (2) (at the Pt electrode)
H2O + 2 h+ 1/2 O2 + 2 H+ (3) (at the TiO2 electrode)
H2O + 2 hv 1/2 O2 + H2 (4) (overall reaction)
Mechanism of photocatalytic water splitting
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PtH+
H2
hv
H2O
O2
h+
e-
VB
CB
RuO2
Schematic Water oxidation and reduction process over photocatalyst
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h+
e-
VB
CB H+/H2
O2/H2O
2
1
0
-1
E vs NHE(pH=0)
0 V
1.23 Vbadgap
The relationship between the redox potential of H2O and the VB-CB of the semiconductor
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e-
e-
e-+h+
h+
h+H+
H2
H2O
O2
CB
VBh+
e-
hvhv
Schematic photoexicitation process in semiconductor
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300 400 500 600 700 800 900 1000
0.0
0.5
1.0
1.5re
lati
ve in
tens
ity
(a.u
.)
Wavelengthen / nm
Solar energy distribution detected at PM 12 in Japan
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13Vis 400-700nm
UV <400nm
IR >700nm
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O2p
N2p
M nd
CB
VB
S3p
Energy level diagram of transition metal oxide, nitride and sulfide
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15UV-Vis diffuse reflection spectra for Sm2Ti2O7 and Sm2Ti2S2O5
A. Ishikawa et al, J. Am. Chem. Soc., 2002, 124, 13547.
Recent development of water splitting
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A. Ishikawa et al, J. Am. Chem. Soc., 2002, 124, 13547.
Time course of O2 evolution from Sm2Ti2S2O5 and CdS under visible light irridiation (Condition catalyst: 0.2g, La2O3, 0.2g, 0.0
1M AgNO3 solution 200ml)
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A. Ishikawa et al, J. Am. Chem. Soc., 2002, 124, 13547.
Time course of H2 evolution from 1.0 wt %Pt- Sm2Ti2S2O5 under visible light irradiation( > 440nm, catalyst, 0.2g; solution volume, 200ml)
0.01M Na2SO3
+ 0.01M Na2S
20ml CH3OH +180ml H2O
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A. Ishikawa et al, J. Am. Chem. Soc., 2002, 124, 13547.
Estimated band position of Sm2Ti2S2O5 at pH = 0 and 8
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A. Kudo et al, Chem. Comm., 2002, 1958.
Diffuse reflection spectra of AgInZn7S9 (a), ZnS (b) and AgInS2 (c).
AgInS2AgInZn7S9ZnS
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A. Kudo et al, Chem. Comm., 2002, 1958.
Photocatalytic H2 evolution over AgInZn7S9(a) and 3wt%-Pt /AgInZn7S9 under visible light irradiation(>420nm, catalyst, 0.3g; 0.25 M K2SO3- 0.35 M Na2S solution 300 ml.
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21 The set up for photocatalytic water splitting
My preliminary work and next plan
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0 2000 4000 6000 8000 100000.0
0.5
1.0
1.5
2.0
2.5
3.0
S<9120A
mou
nt o
f H
2 / m
ol
Area
Low yield part (S<9120) hydrogen evolution standard curve for System-1 and System-2(S-1, S-2)
Y = 2.60E-4*X+0. 29
R = 0.99676
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0 20 40 60 80 100 120 140 160
0
50
100
150
200
250
300
9120<S<1400000A
mou
nt o
f H
2 / m
ol
Area / X 10000
Middle yield part (9120<S<1400000) hydrogen evolution standard curve for S-1 and S-2
Y = 1.92-4*X+2.31
R = 0.99978
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Y = 3.18E-4*X-159.6
R = 0.99787
0 400 800 1200 1600 20000
1000
2000
3000
4000
5000
6000
7000
S>1400000A
mou
nt o
f H
2 / m
ol
Area / X 10000
High yield part (S>1400000) hydrogen evolution standard curve for S-1 and S-2
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25
0 200 400 600 800 1000 1200 1400 16000
500
1000
1500
2000
2500
3000A
mo
un
t o
f O
2 / m
ol
Area
Y = 1.92E-3*X-2.63
R = 0.99951
Oxygen evolution standard curve for S-1 and S-2
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0 200 400 600 800 1000 1200 1400 16000
500
1000
1500
2000
2500
3000
3500
4000A
mo
un
t o
f N
2 /
mo
l
Area / X1000
Y =2.56E-3*X-3.50
R = 0.99951
Nitrogen evolution standard curve for S-1 and S-2
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0 5 10 15 20 25
0
40
80
120
160
200
B
Am
ou
nt
of
O2
/ m
ol
Time / hours
0 5 10 15 20 25
5
10
15
20
25
30
35
A
Am
ou
nt
of
H2
/ m
ol
Time / hours
Time course of H2(A) and O2(B) evolution over CdO-360 (condition catalyst, 0.5g; 300W xenon lamp)
CH3OH 30ml,
H2O 170ml 0.01M AgNO3
200ml, >420nm
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0 2 4 6 8 10 12 14 16 18
0
20
40
60
80
100
120
140
500
600
360
400
Am
ou
nt
of
O2
evo
luti
on
/ m
ol
Time / hours
Photocatalytic O2 evolution over CdO calcinated at varying te
mperature(Condition: catalyst 0.5g, 0.01M AgNO3 200ml)
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0 5 10 15 20 25 30 35 40 45 50
0
50
100
150
200
250
300
350
400
450
CdO-400+La2O
3
CdO-400Am
ou
nt
of
O2
/ m
ol
Time / hours
Effect of La2O3 on the activity of the CdO calcinated at 400°C
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30
0 10 20 30 40 50
0
100
200
300
400
Am
ou
nt
of
O2
/ m
ol
Time / hours
CdO-500-la2O3
CdO-400-la2O3
Photocatalytic O2 evolution over CdO calcinated at 400 and 500
C(Condition: catalyst 0.5g; 0.01M AgNO3 200ml; la2O3, 0.2g)
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0 5 10 15 20 25 30 35 40 45 50
0
50
100
150
200
250
300
350
400
CdO-400-La2O
3
1% RuO2-CdO-400A
mo
un
t o
f O
2 /
mo
l
Time / hours
Photocatalytic O2 evolution over CdO-400 and 1% RuO2 loaded Cd
O-400(Condition: catalyst 0.5g; 0.01M AgNO3 200ml; La2O3, 0.2g)
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0 5 10 15 20 25 30
0
50
100
150
200
250
300
350
Am
ou
nt
of
O2
/ m
ol
Time / hours
Photocatalytic O2 evolution over CdO calcinated at 400°C (Co
ndition: catalyst 0.5g, 0.01M AgNO3 200ml, La2O3 0.2g)
R = 11.2mol/h
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0 5 10 15 20 25 30
0
40
80
120
160
200
240
3%-RuO2-(CdO-500)
2%-RuO2-(CdO-500)
CdO-500
Am
ou
nt
of
O2
/ m
ol
Time / hours
Photocatalytic O2 evolution over CdO-500 and RuO2 loaded CdO-5
00(Condition: catalyst 0.5g; 0.01M AgNO3 200ml; La2O3, 0.2g)
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200 300 400 500 600 700 800
0.0
0.2
0.4
0.6
0.8
1.0
AB
S
wavelengthen / nm
B C D
Uv-Vis diffuse reflection spectra for CdO prepared
at different temperature
360400500
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10 20 30 40 50 60 700
100
200
300
400In
ten
sity
(a.
u.)
degree / 2
XRD pattern of CdO calcinated at 360C
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200 300 400 500 600 700 800
0.0
0.2
0.4
0.6
0.8
1.0
Inte
ns
ity
(a.u
.)
wavelengthen / nm
CdIn2S4 CdS
UV-Vis diffuse reflection spectra for CdS and CdIn2S4 pre
pared by the solvothermal method.
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10 20 30 40 50 60 70
0
200
400
600
800
1000
1200
1400
1600
1800
2000
CdIn2S
4-2
CdIn2S
4-1
Inte
nsit
y
/ degree
XRD pattern of CdIn2S4 prepared by solvothermal method
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Next Plans
1 To investigate the influence of other electron acceptor such as Fe3+ and its concentration on the activity of CdO system.
2 To explore how the different loading species with varying amount will influence the O2 evolution.
3 To synthesize Cr or Ni doped CdO to enhance the position of VB of CdO.
4 To synthesize other sulfide with better activity.