Download Supporting Information Biomimetic Polymeric

Supporting Information
Biomimetic Polymeric Semiconductor Based Hybrid Nanosystems
for Artificial Photosynthesis towards Solar Fuels Generation via
CO2 reduction
Han Zhou*, Peng Li, Jian Liu*, Zupeng Chen, Lequan Liu, Dariya Dontsova, Runyu Yan,
Tongxiang Fan, Di Zhang and Jinhua Ye
Dr. H. Zhou, Dr. J. Liu, Dr. Z. Chen, Dr. D. Dontsova
Department of Colloid chemistry, Max-planck institute of colloids and interfaces, Research
campus golm, Potsdam, 14476, Germany.
E-mail: [email protected], [email protected]
Dr. H. Zhou, Dr. R. Yan, Prof. T. Fan, Prof. D. Zhang
State key lab of metal matrix composites, Shanghai Jiaotong University, Shanghai, 200240,
China
Dr. P. Li, Prof. L. Liu, Prof. J. Ye
International center for materials nanoarchitectonics (WPI-MANA) and environmentao
remediation materials unit, National Institute for materials science (NIMS), 1-1, Namiki,
Tsukuba, Ibaraki, 305-0044, Japan
TU-NIMS Joint research center, school of materials science and engineering, Tianjin
University, 92 weijin Road, Nankai district, Tianjin, 300072, China
Figure S1. Reaction setup for evaluation of conversion rate of CO2.
Figure S2. TEM image of the ultrathin g-C3N4 nanosheet
Figure S3 N2 adsorption/desorption isotherms of CNS.
Figure S4. XRD pattern of ZIF-9.
Figure S5. FTIR spectra of the ZIF-9 and benzimidazole.
Figure S6. SEM (a) and TEM (b) images of the synthesized ZIF-9 particles.
Figure S7. TEM image of Au(1wt%)-CNS.
Figure S8. TEM image of Au(1wt%)-CNS-ZIF9(1wt%) system.
Figure S9. Some comparative experiments were done to understand the roles of Co2+,
benzimidazole, ZIF-9 in the photocatalytic CO2 reduction, respectively.
Figure S10. CO2 adsorption property of a series of samples
Figure S11. Oxygen evolution by CNS-ZIF9 (1wt%).
Figure S12. Cyclic voltammograms of glassy carbon background (black line) and ca. 200 μg
catalyst cm
−2
of ZIF-9/glassy carbon electrode (blue line) in 0.1 M potassium phosphate
buffer (pH = 7.0) at a scanning rate of 5mV/s.
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Figure S13. CO2 adsorption property of ZIF-9 before and after irradiation.
Figure S14 Co2p and N1s XPS spectrum of the catalysts Co-ZIF-9 before and after
irradiation for 8hrs.
Figure S15. Mass spectra (m/z = 29) analyses in the photocatalytic reduction of
ZIF9 (1%)-Au-CNS under irradiation for 12h without any sacrificial agents.
Figure S1 Reaction setup for the evaluation of conversion rates of CO2.
Figure S2. TEM image of the ultrathin g-C3N4 nanosheet
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CO2 on
Figure S3 N2 adsorption/desorption isotherms of CNS.
Figure S4. XRD pattern of ZIF-9.
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Figure S5. FTIR spectra of the ZIF-9 and benzimidazole. Typical FT-IR spectra of H-PhIM
and ZIF-9 are shown in Fig. S4. For benzimidazole, the aromatic C-H stretching vibrations
absorbs 3100–3000 cm−1. Compared with the spectra of H-PhIM, the strong and broad N-H
bands between 3250–2500 cm−1 completely disappear. Meanwhile, some medium bend
vibration peaks of N-H group near 1650–1580 cm−1 disappear in the spectra of ZIF-9.
Figure S6. SEM (a) and TEM (b) images of the synthesized ZIF-9 particles.
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Figure S7. TEM image of Au(1wt%)-CNS.
Figure S8. TEM image of Au(1wt%)-CNS-ZIF9(1wt%) system.
Figure S9. Some comparative experiments were done to understand the roles of Co2+, benzimidazole,
ZIF-9 in the photocatalytic CO2 reduction, respectively.
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Figure S10. CO2 adsorption property of a series of samples 1# CNS, 2# CNS-ZIF9(1%), 3#
CNS-ZIF9(2%),4# CNS-ZIF9(5%),5# CNS-ZIF9(10%),6# CNS-ZIF9(20%)
Figure S11. O2 evolution from water on CNS-ZIF9 (1wt%) using 0.01M AgNO3 as an electron
acceptor under visible light. By contrast, bare CNS evolved negligible O2 under the same
measurement conditions, which indicates that ZIF9 may serve as an oxygen evolution cocatalyst.
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Figure S12. Cyclic voltammograms of glassy carbon background (black line) and ca. 200 μg
catalyst cm −2 of ZIF-9/glassy carbon electrode (blue line) in 0.1 M potassium phosphate
buffer (pH = 7.0) at a scanning rate of 5mV/s.The catalyst was uniformly cast onto a 5 mm
glassy carbon electrode with a total loading of ca. 200 μg catalyst cm−2. During the
measurements, the working electrode was rotating at 2000 rpm to remove the generated
oxygen bubbles. The cyclic voltammetry (CV) scans demonstrated that ZIF-9 has greater
current density and earlier onset of catalytic current density as compared to its background
glassy carbon. The onset of the catalytic current (1.6 V vs. reversible hydrogen electrode,
RHE) occurs ~ 0.4 V beyond the thermodynamic potential for water oxidation (1.23 V vs.
RHE). As pure ZIF-9 is not conductive, so CNTs were coupled with ZIF-9 to increase the
conductivity.
Figure S13. CO2 adsorption property of ZIF-9 before and after irradiation.
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Figure S14 Co2p and N1s XPS spectrum of the catalysts Co-ZIF-9 before and after irradiation for
8hrs. The data shows that ZIF-9 is stable under UV-Visible light irradiation.
Figure S15. Mass spectra (m/z = 29) analyses for photocatalytic reduction of 13CO2 on ZIF9
(1%)-Au-CNS under irradiation for 12h without any sacrificial agents.
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