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Photocatalytically Active Ladder Polymers

preprint
submitted on 26.11.2018 and posted on 26.11.2018 by Anastasia Vogel, Mark forster, Liam Wilbraham, Charlotte Smith, Alexander Cowan, Martijn Zwijnenburg, Seb Sprick, Andrew I. Cooper

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 cLaP2 (18 μmol h−1 g−1) under broadband illumination (λ >295 nm) in presence of a hole-scavenger is attributed to a higher yield of long-lived charges (µs–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.

Funding

European Union's Horizon 2020 research and innovation programme No 796322; The UK Engineering and Physical Sciences Research Council EP/N004884/1 and EP/P034497/1.

History

Email Address of Submitting Author

ssprick@liverpool.ac.uk

Institution

University of Liverpool

Country

United Kingdom

ORCID For Submitting Author

0000-0002-5389-2706

Declaration of Conflict of Interest

No conflict of interest

Version Notes

First version of the manuscript (V1)

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