Visible Light-Driven Dye-Sensitized Photocatalytic Hydrogen Production by Porphyrin and its Cyclic Dimer and Trimer: Effect of Multi-Pyridyl-Anchoring Groups on Photocatalytic Activity and Stability

Motonori Watanabe, Songmei Sun, Tatsumi Ishihara, Takuya Kamimura, Masato Nishimura, Fumito Tani

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Abstract

The monomer, dimer, and trimer of 5,15-diphenyl-10,20-di(pyridin-4-yl)porphyrin are used to investigate the multianchoring effect on TiO 2 for visible light-driven photocatalytic hydrogen production in a water medium. Further, the porphyrin trimer is prepared and analyzed by nuclear magnetic resonance (NMR) spectroscopy, absorption spectroscopy, electrochemical voltammetry, fast atom bombardment (FAB) mass spectroscopy, and density functional theory (DFT) computation. The results of this study indicate that the peak intensities of the absorption spectra increase as the number of porphyrin units increases, while changes could be barely observed in the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps. The porphyrin dimer in a 1 wt % Pt-loaded TiO 2 powder photocatalyst system exhibited optimal hydrogen production performance in a stable state over a period of 80 h and at a superior rate of 1023 μmol·g -1 ·h -1 . Further, the stability of the photocatalytic system was systematically investigated using films containing dyes on 1 wt % Pt-loaded TiO 2 /FTO. For a film containing the dimer, almost no change was observed in the hydrogen-bond coordination mode of the dimer and the photocurrent during the photocatalytic reaction. However, the photocurrents of the monomer and trimer were altered during visible light irradiation without altering the coordination mode, indicating that the arrangements and orientations of the porphyrins on TiO 2 surfaces were altered. These results indicate that the presence of multiple anchoring groups enhance the stability of the photocatalytic system and the rate of hydrogen production.

Original languageEnglish
Pages (from-to)6072-6081
Number of pages10
JournalACS Applied Energy Materials
Volume1
Issue number11
DOIs
Publication statusPublished - Nov 26 2018

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Porphyrins
Hydrogen production
Dimers
Coloring Agents
Dyes
Molecular orbitals
Photocurrents
Monomers
Optimal systems
Voltammetry
Photocatalysts
Absorption spectroscopy
Powders
Nuclear magnetic resonance spectroscopy
Density functional theory
Absorption spectra
Hydrogen bonds
Irradiation
Spectroscopy
Atoms

All Science Journal Classification (ASJC) codes

  • Energy Engineering and Power Technology
  • Chemical Engineering (miscellaneous)
  • Electrochemistry
  • Materials Chemistry
  • Electrical and Electronic Engineering

Cite this

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title = "Visible Light-Driven Dye-Sensitized Photocatalytic Hydrogen Production by Porphyrin and its Cyclic Dimer and Trimer: Effect of Multi-Pyridyl-Anchoring Groups on Photocatalytic Activity and Stability",
abstract = "The monomer, dimer, and trimer of 5,15-diphenyl-10,20-di(pyridin-4-yl)porphyrin are used to investigate the multianchoring effect on TiO 2 for visible light-driven photocatalytic hydrogen production in a water medium. Further, the porphyrin trimer is prepared and analyzed by nuclear magnetic resonance (NMR) spectroscopy, absorption spectroscopy, electrochemical voltammetry, fast atom bombardment (FAB) mass spectroscopy, and density functional theory (DFT) computation. The results of this study indicate that the peak intensities of the absorption spectra increase as the number of porphyrin units increases, while changes could be barely observed in the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps. The porphyrin dimer in a 1 wt {\%} Pt-loaded TiO 2 powder photocatalyst system exhibited optimal hydrogen production performance in a stable state over a period of 80 h and at a superior rate of 1023 μmol·g -1 ·h -1 . Further, the stability of the photocatalytic system was systematically investigated using films containing dyes on 1 wt {\%} Pt-loaded TiO 2 /FTO. For a film containing the dimer, almost no change was observed in the hydrogen-bond coordination mode of the dimer and the photocurrent during the photocatalytic reaction. However, the photocurrents of the monomer and trimer were altered during visible light irradiation without altering the coordination mode, indicating that the arrangements and orientations of the porphyrins on TiO 2 surfaces were altered. These results indicate that the presence of multiple anchoring groups enhance the stability of the photocatalytic system and the rate of hydrogen production.",
author = "Motonori Watanabe and Songmei Sun and Tatsumi Ishihara and Takuya Kamimura and Masato Nishimura and Fumito Tani",
year = "2018",
month = "11",
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doi = "10.1021/acsaem.8b01113",
language = "English",
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T1 - Visible Light-Driven Dye-Sensitized Photocatalytic Hydrogen Production by Porphyrin and its Cyclic Dimer and Trimer

T2 - Effect of Multi-Pyridyl-Anchoring Groups on Photocatalytic Activity and Stability

AU - Watanabe, Motonori

AU - Sun, Songmei

AU - Ishihara, Tatsumi

AU - Kamimura, Takuya

AU - Nishimura, Masato

AU - Tani, Fumito

PY - 2018/11/26

Y1 - 2018/11/26

N2 - The monomer, dimer, and trimer of 5,15-diphenyl-10,20-di(pyridin-4-yl)porphyrin are used to investigate the multianchoring effect on TiO 2 for visible light-driven photocatalytic hydrogen production in a water medium. Further, the porphyrin trimer is prepared and analyzed by nuclear magnetic resonance (NMR) spectroscopy, absorption spectroscopy, electrochemical voltammetry, fast atom bombardment (FAB) mass spectroscopy, and density functional theory (DFT) computation. The results of this study indicate that the peak intensities of the absorption spectra increase as the number of porphyrin units increases, while changes could be barely observed in the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps. The porphyrin dimer in a 1 wt % Pt-loaded TiO 2 powder photocatalyst system exhibited optimal hydrogen production performance in a stable state over a period of 80 h and at a superior rate of 1023 μmol·g -1 ·h -1 . Further, the stability of the photocatalytic system was systematically investigated using films containing dyes on 1 wt % Pt-loaded TiO 2 /FTO. For a film containing the dimer, almost no change was observed in the hydrogen-bond coordination mode of the dimer and the photocurrent during the photocatalytic reaction. However, the photocurrents of the monomer and trimer were altered during visible light irradiation without altering the coordination mode, indicating that the arrangements and orientations of the porphyrins on TiO 2 surfaces were altered. These results indicate that the presence of multiple anchoring groups enhance the stability of the photocatalytic system and the rate of hydrogen production.

AB - The monomer, dimer, and trimer of 5,15-diphenyl-10,20-di(pyridin-4-yl)porphyrin are used to investigate the multianchoring effect on TiO 2 for visible light-driven photocatalytic hydrogen production in a water medium. Further, the porphyrin trimer is prepared and analyzed by nuclear magnetic resonance (NMR) spectroscopy, absorption spectroscopy, electrochemical voltammetry, fast atom bombardment (FAB) mass spectroscopy, and density functional theory (DFT) computation. The results of this study indicate that the peak intensities of the absorption spectra increase as the number of porphyrin units increases, while changes could be barely observed in the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps. The porphyrin dimer in a 1 wt % Pt-loaded TiO 2 powder photocatalyst system exhibited optimal hydrogen production performance in a stable state over a period of 80 h and at a superior rate of 1023 μmol·g -1 ·h -1 . Further, the stability of the photocatalytic system was systematically investigated using films containing dyes on 1 wt % Pt-loaded TiO 2 /FTO. For a film containing the dimer, almost no change was observed in the hydrogen-bond coordination mode of the dimer and the photocurrent during the photocatalytic reaction. However, the photocurrents of the monomer and trimer were altered during visible light irradiation without altering the coordination mode, indicating that the arrangements and orientations of the porphyrins on TiO 2 surfaces were altered. These results indicate that the presence of multiple anchoring groups enhance the stability of the photocatalytic system and the rate of hydrogen production.

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SN - 2574-0962

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