Electronic Supplementary Information
Efficient Visible-Light Photocatalytic Degradation System
Assisted by Conventional Pd Catalysis
Yanlong Yu,a Tao He,*b Lingju Guo,b Yajun Yang,a Limei Guo,a Yue Tanga and Yaan Cao*a
a
Key laboratory of Weak-Light Nonlinear Photonics, Ministry of Education, TEDA Applied
Physics Institute and School of Physics, Nankai University, Tianjin 300457, China
b
Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and
Technology, Beijing 100190, China
Figure S1. HR-TEM images of different photocatalysts.
Figure S2. Photodegradation of different target molecules under visible-light irradiation
(λ > 400 nm) in aqueous suspension with 5 mg of photocatalyst.
Figure S3. Cl 2p XPS spectra of Pd/TiO2 and Pd/Ni-TiO2 samples before and after
photodegradation reaction.
Figure S4. Photodegradation rate of 4-ClP in aqueous suspension using different
catalysts.
Figure S5. Time-resolved photoluminescence (TR-PL) decay curves for different
catalysts, excited at 400 nm and monitored at 500 nm.
Figure S6. UV-Vis absorption spectra for photodegradation rate of 4-XP under visible
light irradiation (λ > 420 nm) for different time with Pd/Ni-TiO2 catalyst. (A) 4-IP and (B)
4-BrP.
Figure S7. Photodegradation of different target molecules using PdO as the photocatalyst
under visible-light irradiation (λ > 420 nm) in aqueous suspension.
Figure S8. Pd3d XPS spectrum after UV-light photodegradation of 4-BrP.
Figure S9. UV-vis absorption spectra of different photocatalysts prepared without the
presence of Cl species in the starting materials.
Table S1.
Calculated dissociation energy (Ed) of Pd-X in the HO-C6H4-PdCl(X)
intermediate and Ni-X in the HO-C6H4-NiCl(X) intermediate.
Pure TiO2
Pd-TiO2
Pd/Ni-TIO2
Figure S1. HR-TEM images of different photocatalysts.
a
1.0
b
C/C0
0.8
c
0.6
0.4
d
0.2
0.0
4-ClP
0
1
2
3
Irradiation time (h)
4
Figure S2. Photodegradation of different target molecules under visible-light irradiation (λ >
400 nm) in aqueous suspension with 5 mg of photocatalyst. (a) pure TiO2, (b) Ni-TiO2, (c)
Pd/TiO2, and (d) Pd/Ni-TiO2.
(A)
(B)
Pd/TiO2 before reaction
196
197
198
199
200
201
202
Pd/Ni-TiO2 after reaction
Intensity (a.u.)
Intensity (a.u.)
Pd/TiO2 after reaction
203
Pd/Ni-TiO2 before reaction
196
197
BE (eV)
198
199
200
201
202
BE (eV)
Figure S3. Cl 2p XPS spectra of (A) Pd/TiO2 and (B) Pd/Ni-TiO2 samples before and after
photodegradation reaction.
0.8
Pd/Ni5
0.6
Pd/TiO2
0.4
N-TiO2
0.2
(B)
Pd/Ni10
4-ClP
TiO2
0.0
Samples
Pd/Ni15
Pd/Ni20
Photodegradation rate (a.u.)
Photodegradation rate (a.u.)
(A)
0.8
4-ClP
Pd/Ni15
Pd/Ni5
0.6
Pd/Ni20
Pd1.3 Pd1.5
Pd1.0
0.4
Pd0.3
0.2
0.0
Samples
Figure S4. Photodegradation rate of 4-ClP in aqueous suspension using different catalysts, (A)
under visible light irradiation (λ > 420 nm) with 10 mg of photocatalyst for 2 h, and (B) under
visible-light irradiation (λ > 400 nm) with 5 mg of photocatalyst for 4 h.
TiO2
Ni-TiO2
Intensity (a.u.)
Pd/TiO2
Pd/Ni-TiO2
51.6 51.8 52.0 52.2 52.4 52.6 52.8
Time (ns)
Figure S5. Time-resolved photoluminescence (TR-PL) decay curves for different catalysts,
excited at 400 nm and monitored at 500 nm.
(B) 0.6
4-IP
0h
2h
4h
6h
8h
0.6
0.4
Absorbance (a.u.)
Absorbance (a.u.)
(A) 0.8
0.2
4-BrP
0h
2h
4h
6h
8h
0.4
0.2
0.0
0.0
200
250
300
350
200
400
250
300
350
400
Wavelength (nm)
Wavelength (nm)
Figure S6. UV-Vis absorption spectra for photodegradation rate of 4-XP under visible light
irradiation (λ > 420 nm) for different time with Pd/Ni-TiO2 catalyst. (A) 4-IP and (B) 4-BrP.
1.0
C/C0 (a.u.)
0.9
0.8
Dark
4-ClP
4-FP
4-BrP
4-IP
0.7
0.6
0.5
0
2
4
6
8
Time (h)
Figure S7. Photodegradation of different target molecules using PdO as the photocatalyst
under visible-light irradiation (λ > 420 nm) in aqueous suspension.
Intensity (a.u.)
4-BrP
332
336
340
344
348
Binding energy (eV)
Figure S8. Pd3d XPS spectrum after UV-light photodegradation of 4-BrP.
Ni-TiO2
1.5Pd/Ni-TiO2
Intensity(a.u.)
1.5Pd/TiO2
200
300
400
500
600
700
Wavelength(nm)
Figure S9. UV-vis absorption spectra of different photocatalysts prepared without the
presence of Cl species in the starting materials.
Table S1. Calculated dissociation energy (Ed) of Pd-X in the HO-C6H4-PdCl(X) intermediate
and Ni-X in the HO-C6H4-NiCl(X) intermediate. Here in the table the intermediate is
simplified as Cl-Pd-X and Cl-Ni-X. X = F, Cl, Br, and I.
Ed (eV)
Cl-Pd-F
Cl-Pd-Cl
Cl-Pd-Br
Cl-Pd-I
Cl-Ni-F
Cl-Ni-Cl
Cl-Ni-Br
Cl-Ni-I
3.486
2.776
2.438
1.937
4.518
3.501
2.941
2.433