Side-chain tuning in conjugated polymer photocatalysts for improved hydrogen production from water

Duncan J. Woods, Sam A.J. Hillman, Drew Pearce, Liam Wilbraham, Lucas Q. Flagg, Warren Duffy, Iain McCulloch, James R. Durrant, Anne A.Y. Guilbert, Martijn A. Zwijnenburg, Reiner Sebastian Sprick, Jenny Nelson, Andrew I. Cooper

Research output: Contribution to journalArticlepeer-review

89 Scopus citations


Structure-property-activity relationships in solution processable polymer photocatalysts for hydrogen production from water were probed by varying the chemical structure of both the polymer side-chains and the polymer backbone. In both cases, the photocatalytic performance depends strongly on the inclusion of more polar groups, such as dibenzo[b,d]thiophene sulfone backbone units or oligo(ethylene glycol) side-chains. We used optical, spectroscopic, and structural characterisation techniques to understand the different catalytic activities of these systems. We find that although polar groups improve the wettability of the material with water in all cases, backbone and side-chain modifications affect photocatalytic performance in different ways: the inclusion of dibenzo[b,d]thiophene sulfone backbone units improves the thermodynamic driving force for hole transfer to the sacrificial donor, while the inclusion of oligo ethylene glycol side-chains aids the degree of polymer swelling and also extends the electron polaron lifetime. The best performing material, FS-TEG, exhibits a HER of 72.5 μmol h-1 for 25 mg photocatalyst (2.9 mmol g-1 h-1) when dispersed in the presence of a sacrificial donor and illuminated with λ > 420 nm light, corresponding to a hydrogen evolution EQE of 10% at 420 nm. When cast as a thin film, this HER was further boosted to 13.9 mmol g-1 h-1 (3.0 mmol m-2 h-1), which is among the highest rates in this field.
Original languageEnglish (US)
Pages (from-to)1843-1855
Number of pages13
JournalEnergy and Environmental Science
Issue number6
StatePublished - May 7 2020

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): OSR-2015-CRG4-2572
Acknowledgements: AIC, RSS, MAZ, LW, and DW acknowledge the UK Engineering and Physical Sciences Research Council (EPSRC) for funding via grant EP/N004884/1. JN and DP acknowledge funding from the EPSRC via grants EP/P005543/1 and EP/R023581/1. AAYG thanks the EPSRC for award of a research fellowship (EP/P00928X/1). SJH thanks the EPSRC for a Centre for Doctoral Training post-graduate studentship (EP/L016702/1). JN also thanks the European Research Council for support under the European Union’s Horizon 2020 research and innovation program (Grant Agreement No. 742708) and the Imperial College Research Computing Service for computational resources. JD and IM acknowledge financial support from the KAUST award OSR-2015-CRG4-2572. LQF acknowledges funding from the National Science Foundation (NSF DMR-1607242) and the NSF DMREF (award number 1629369).


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