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Table of contents
Experimental Section ................................................................................................... 2
1. Preparation of photocatalysts .............................................................................. 2
2. Characterization of photocatalysts ...................................................................... 2
3. Mott-Schottky measurement ............................................................................... 3
4. Photocatalytic reactions ...................................................................................... 3
Figures S1-S9 ................................................................................................................ 5
Tables S1-S4 ................................................................................................................ 10
Calculation details of the depletion layer depth (ddl) .............................................. 12
Calculation details of the apparent quantum yield (A.Q.Y.) ................................. 13
References ................................................................................................................... 14
Experimental Section
1. Preparation of photocatalysts
Cd0.6Zn0.4S: x% La photocatalysts were prepared via a solvothermal method (x is
the molar percent of La in the starting materials). In a typical experiment of
synthesizing
Cd0.6Zn0.4S:
2%
La
photocatalyst,
Zn(Ac)22H2O
(0.219
g),
which was equipped with an AM1.5 filter and a UV-cut filter (>400 nm) to simulate
sunlight irradiation and cut off the light in the ultraviolet region. Apparent quantum
yields were tested under identical condition, except the AM1.5 filter and UV-cut filter
was substituted for band-pass filter separately (=350 nm and =420 nm, half
width=15 nm). The amount of produced H2 was measured by gas chromatography
(Agilent 7890) with a thermal conductivity detector (TCD) and Ar was used as the
carrier gas.
Figures S1-S9
Fig. S3 MottSchottky plots for a) CZS, b) CZS: 1% La, c) CZS: 2% La and d) CZS:
3% La photocatalysts.
6
6
a ; Roctahedral=
a ; a=BondS-S=0.401 nm
12
6
6
Tables S1-S4
Table S1 Bulk and surface compositions of CZS: x% La photocatalysts.
Atom percentage (%)
Samples
Cda
Zna
Laa
Cdb
Znb
Lab
CZS
57.23
42.77
61.13
38.87
CZS:1%La
57.46
42.37
0.17
61.36
37.77
0.87
CZS:2%La
56.88
42.86
0.26
60.19
36.87
2.94
CZS:3%La
58.14
41.49
0.37
60.05
34.62
5.33
: measured by ICP-AES
: measured by XPS
Table S2 The depths of the depletion layer of CZS: 0-3% La photocatalysts and the
values of slope and flat band potential calculated from the MottSchottky plots.
Slope k
Samples
(108 F2cm4V1)
Efb (V)
ddl (nm)
CZS
7.13
-0.67
10.8
CZS:1%La
7.06
-0.70
11.0
CZS:2%La
16.9
-0.69
16.9
CZS:3%La
87.5
-0.72
39.3
10
inc (nm)
Irradiation area
(cm2)
Amount of H2
production (mmol)
Apparent quantum
yield (%)
CZS
CZS:2%La
CZS
CZS:2%La
0.53a
0.019
0.051
34.8
93.3
6.67b
0.091
0.3
11.0
36.3
Power density
(mWcm-2)
3507.5
19.6
4207.5
a
ZnS:2%La
CdS
CdS:2%La
3507.5
8.5
21.3
5.5
11.0
4207.5
2.3
5.1
11
12
hc
inc
where h (Js) is Plancks constant, c (ms-1) is the speed of light and inc (m) is the
wavelength of the incident monochromatic light. And the total energy of the incident
monochromatic light (Etotal) is calculated using the following equation:
Etotal PSt
where P (Wm-2) is the power density of the incident monochromatic light, S (m2) is
the irradiation area and t (s) is the the duration of the incident light exposure. The
number of incident photons can be obtained through the following equation:
Number of incident photons
Etotal
PS inct
Ephoton
hc
Finally, the apparent quantum yield is calculated using the following equation:
A.Q.Y.(%)
2nH2 , t N A hc
PS inct
100
where nH2 , t (mol) is the amount of H2 evolved over the duration t of the incident
light exposure, NA (mol-1) is Avogadros constant.
13
References
1
N. Korozlu, K. Colakoglu and E. Deligoz, Phys. Status Solidi, 2010, 247, 1214.
H. J. Yun, H. Lee, N. D. Kim, D. M. Lee, S. Yu and J. Yi, ACS Nano, 2011, 5, 4084.
X. B. Chen, S. H. Shen, L. J. Guo and S. S. Mao, Chem. Rev., 2010, 110, 6503.
14