Premium
Insights into the Mechanism of a Covalently Linked Organic Dye–Cobaloxime Catalyst System for Dye‐Sensitized Solar Fuel Devices
Author(s) -
Pati Palas Baran,
Zhang Lei,
Philippe Bertrand,
FernándezTerán Ricardo,
Ahmadi Sareh,
Tian Lei,
Rensmo Håkan,
Hammarström Leif,
Tian Haining
Publication year - 2017
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201700285
Subject(s) - photochemistry , catalysis , non blocking i/o , photocatalysis , x ray photoelectron spectroscopy , materials science , photocathode , dye sensitized solar cell , chemistry , chemical engineering , electrolyte , organic chemistry , electrode , physics , quantum mechanics , electron , engineering
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.