Insights into the Mechanism of a Covalently Linked Organic Dye–Cobaloxime Catalyst System for Dye-Sensitized Solar Fuel Devices

Palas Baran Pati, Lei Zhang, Bertrand Philippe, Ricardo Fernández-Terán, Sareh Ahmadi, Lei Tian, Håkan Rensmo, Leif Hammarström, Haining Tian

Research output: Contribution to journalArticle

34 Citations (Scopus)

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 languageEnglish
Pages (from-to)2480-2495
Number of pages16
JournalChemSusChem
Volume10
Issue number11
DOIs
Publication statusPublished - Jun 9 2017

Fingerprint

dye
Coloring Agents
Dyes
catalyst
Catalysts
Photocathodes
Excitation energy
Photocatalysis
atomic absorption spectroscopy
Photoelectron spectroscopy
Hydrogen production
Absorption spectroscopy
Excited states
Energy transfer
ligand
Density functional theory
energy
Protons
Chlorides
irradiation

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

Pati, P. B., Zhang, L., Philippe, B., Fernández-Terán, R., Ahmadi, S., Tian, L., ... Tian, H. (2017). Insights into the Mechanism of a Covalently Linked Organic Dye–Cobaloxime Catalyst System for Dye-Sensitized Solar Fuel Devices. ChemSusChem, 10(11), 2480-2495. https://doi.org/10.1002/cssc.201700285

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 journalArticle

Pati, PB, Zhang, L, Philippe, B, Fernández-Terán, R, Ahmadi, S, Tian, L, Rensmo, H, Hammarström, L & Tian, H 2017, 'Insights into the Mechanism of a Covalently Linked Organic Dye–Cobaloxime Catalyst System for Dye-Sensitized Solar Fuel Devices', ChemSusChem, vol. 10, no. 11, pp. 2480-2495. https://doi.org/10.1002/cssc.201700285
Pati, Palas Baran ; Zhang, Lei ; Philippe, Bertrand ; Fernández-Terán, Ricardo ; Ahmadi, Sareh ; Tian, Lei ; Rensmo, Håkan ; Hammarström, Leif ; Tian, Haining. / Insights into the Mechanism of a Covalently Linked Organic Dye–Cobaloxime Catalyst System for Dye-Sensitized Solar Fuel Devices. In: ChemSusChem. 2017 ; Vol. 10, No. 11. pp. 2480-2495.
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