Time-resolved Raman spectroscopy of polaron formation in a polymer photocatalyst

Verity L Piercy, Khezar H Saeed, Andrew W Prentice, Gaia Neri, Chao Li, Adrian M Gardner, Yang Bai, Reiner Sebastian Sprick, Igor V Sazanovich, Andrew I Cooper, Matthew J Rosseinsky, Martijn A Zwijnenburg, Alexander J Cowan

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Abstract

Polymer photocatalysts are a synthetically diverse class of materials that can be used for the production of solar fuels such as H2, but the underlying mechanisms by which they operate are poorly understood. Time-resolved vibrational spectroscopy provides a powerful structure-specific probe of photogenerated species. Here we report the use of time-resolved resonance Raman (TR3) spectroscopy to study the formation of polaron pairs and electron polarons in one of the most active linear polymer photocatalysts for H2 production, poly(dibenzo[b,d]thiophene sulfone), P10. We identify that polaron-pair formation prior to thermalization of the initially generated excited states is an important pathway for the generation of long-lived photoelectrons.

Original languageEnglish
Pages (from-to)10899-10905
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume12
Issue number44
Early online date3 Nov 2021
DOIs
Publication statusPublished - 11 Nov 2021

Keywords

  • polymer photocatalysts
  • solar fuels
  • Raman (TR3) spectroscopy

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