Photocatalytically active ladder polymers.

Vogel, Anastasia, Forster, Mark, Wilbraham, Liam, Smith, Charlotte L, Cowan, Alexander J, Zwijnenburg, Martijn A, Sprick, Reiner Sebastian and Cooper, Andrew I
(2019) Photocatalytically active ladder polymers. Faraday discussions, 215. pp. 84-97.

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Conjugated ladder polymers (cLaPs) are introduced as organic semiconductors for photocatalytic hydrogen evolution from water under sacrificial conditions. Starting from a linear conjugated polymer (cLiP1), two ladder polymers are synthesized via post-polymerization annulation and oxidation techniques to generate rigidified, planarized materials bearing dibenzo[b,d]thiophene (cLaP1) and dibenzo[b,d]thiophene sulfone subunits (cLaP2). The high photocatalytic activity of cLaP1 (1307 μmol h-1 g-1) in comparison to that of cLaP2 (18 μmol h-1 g-1) under broadband illumination (λ > 295 nm) in the presence of a hole-scavenger is attributed to a higher yield of long-lived charges (μs to ms timescale), as evidenced by transient absorption spectroscopy. Additionally, cLaP1 has a larger overpotential for proton reduction and thus an increased driving force for the evolution of hydrogen under sacrificial conditions.

Item Type: Article
Uncontrolled Keywords: 3403 Macromolecular and Materials Chemistry, 34 Chemical Sciences, 3406 Physical Chemistry, 7 Affordable and Clean Energy
Depositing User: Symplectic Admin
Date Deposited: 08 May 2019 10:30
Last Modified: 20 Jun 2024 16:59
DOI: 10.1039/c8fd00197a
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