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A conductive metal-organic framework photoanode.

Brian Pattengale1, Jessica G Freeze1, Matthew J Guberman-Pfeffer2

  • 1Department of Chemistry and Yale Energy Sciences Institute, Yale University New Haven Connecticut 06520-8107 USA brian.pattengale@yale.edu victor.batista@yale.edu.

Chemical Science
|June 7, 2021
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Summary

Conductive metal-organic frameworks (MOFs) act as efficient photosensitizers, enhancing charge separation for artificial photosynthesis. These novel MOF arrays facilitate rapid electron injection into TiO2, paving the way for improved photocatalytic reactions.

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Area of Science:

  • Materials Science
  • Photochemistry
  • Nanotechnology

Background:

  • Metal-organic frameworks (MOFs) offer tunable electronic properties for energy applications.
  • Efficient charge separation is crucial for photocatalytic processes like water-splitting.
  • Titanium dioxide (TiO2) is a widely used semiconductor in photocatalysis.

Purpose of the Study:

  • To develop and characterize conductive MOF-based photosensitizing arrays.
  • To investigate the photoinduced charge transfer dynamics at MOF/TiO2 interfaces.
  • To explore the potential of these MOFs in artificial photosynthesis.

Main Methods:

  • Deposition of Zn2TTFTB MOFs onto TiO2 photoanodes.
  • Structural characterization using powder X-ray diffraction (pXRD) and extended X-ray absorption fine structure (EXAFS).
  • Time-resolved terahertz (THz) spectroscopy and quantum dynamics simulations to study charge transfer.

Main Results:

  • Sub-600 femtosecond (fs) electron injection into TiO2 was observed for Zn2TTFTB-TiO2.
  • Enhanced electron injection due to rapid hole migration through the MOF's tetrathiafulvalene cores.
  • Comparison with TTFTB-TiO2 analogues lacking the extended MOF architecture.

Conclusions:

  • Conductive MOFs demonstrate potential as effective photosensitizing arrays.
  • Facile hole migration within the MOF structure is key to efficient charge separation.
  • These findings support the use of conductive MOFs in artificial photosynthesis for challenging photocatalytic reactions.