Abstract
A covalently linked organic dye–cobaloxime catalyst system based on mesoporous NiO is synthesized by a facile click reaction for mechanistic studies and application in a dye-sensitized solar fuel device. The system is systematically investigated by photoelectrochemical measurements, density functional theory, time-resolved fluorescence, transient absorption spectroscopy, and photoelectron spectroscopy. The results show that irradiation of the dye–catalyst on NiO leads to ultrafast hole injection into NiO from the excited dye, followed by a fast electron transfer process to reduce the catalyst. Moreover, the dye adopts different structures with different excited state energies, and excitation energy transfer occurs between neighboring molecules on the semiconductor surface. The photoelectrochemical experiments also show hydrogen production by this system. The axial chloride ligands of the catalyst are released during photocatalysis to create the active sites for proton reduction. A working mechanism of the dye–catalyst system on the photocathode is proposed on the basis of this study.
| Original language | English |
|---|---|
| Pages (from-to) | 2480-2495 |
| Number of pages | 16 |
| Journal | ChemSusChem |
| Volume | 10 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - Jun 9 2017 |
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Keywords
- click chemistry
- dye-sensitized solar cells
- hydrogen
- photocatalysis
- reaction mechanisms
ASJC Scopus subject areas
- Environmental Chemistry
- Chemical Engineering(all)
- Materials Science(all)
- Energy(all)
Cite this
Insights into the Mechanism of a Covalently Linked Organic Dye–Cobaloxime Catalyst System for Dye-Sensitized Solar Fuel Devices. / Pati, Palas Baran; Zhang, Lei; Philippe, Bertrand; Fernández-Terán, Ricardo; Ahmadi, Sareh; Tian, Lei; Rensmo, Håkan; Hammarström, Leif; Tian, Haining.
In: ChemSusChem, Vol. 10, No. 11, 09.06.2017, p. 2480-2495.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Insights into the Mechanism of a Covalently Linked Organic Dye–Cobaloxime Catalyst System for Dye-Sensitized Solar Fuel Devices
AU - Pati, Palas Baran
AU - Zhang, Lei
AU - Philippe, Bertrand
AU - Fernández-Terán, Ricardo
AU - Ahmadi, Sareh
AU - Tian, Lei
AU - Rensmo, Håkan
AU - Hammarström, Leif
AU - Tian, Haining
PY - 2017/6/9
Y1 - 2017/6/9
N2 - A covalently linked organic dye–cobaloxime catalyst system based on mesoporous NiO is synthesized by a facile click reaction for mechanistic studies and application in a dye-sensitized solar fuel device. The system is systematically investigated by photoelectrochemical measurements, density functional theory, time-resolved fluorescence, transient absorption spectroscopy, and photoelectron spectroscopy. The results show that irradiation of the dye–catalyst on NiO leads to ultrafast hole injection into NiO from the excited dye, followed by a fast electron transfer process to reduce the catalyst. Moreover, the dye adopts different structures with different excited state energies, and excitation energy transfer occurs between neighboring molecules on the semiconductor surface. The photoelectrochemical experiments also show hydrogen production by this system. The axial chloride ligands of the catalyst are released during photocatalysis to create the active sites for proton reduction. A working mechanism of the dye–catalyst system on the photocathode is proposed on the basis of this study.
AB - A covalently linked organic dye–cobaloxime catalyst system based on mesoporous NiO is synthesized by a facile click reaction for mechanistic studies and application in a dye-sensitized solar fuel device. The system is systematically investigated by photoelectrochemical measurements, density functional theory, time-resolved fluorescence, transient absorption spectroscopy, and photoelectron spectroscopy. The results show that irradiation of the dye–catalyst on NiO leads to ultrafast hole injection into NiO from the excited dye, followed by a fast electron transfer process to reduce the catalyst. Moreover, the dye adopts different structures with different excited state energies, and excitation energy transfer occurs between neighboring molecules on the semiconductor surface. The photoelectrochemical experiments also show hydrogen production by this system. The axial chloride ligands of the catalyst are released during photocatalysis to create the active sites for proton reduction. A working mechanism of the dye–catalyst system on the photocathode is proposed on the basis of this study.
KW - click chemistry
KW - dye-sensitized solar cells
KW - hydrogen
KW - photocatalysis
KW - reaction mechanisms
UR - http://www.scopus.com/inward/record.url?scp=85018293171&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85018293171&partnerID=8YFLogxK
U2 - 10.1002/cssc.201700285
DO - 10.1002/cssc.201700285
M3 - Article
C2 - 28338295
AN - SCOPUS:85018293171
VL - 10
SP - 2480
EP - 2495
JO - ChemSusChem
JF - ChemSusChem
SN - 1864-5631
IS - 11
ER -