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dc.contributor.authorSachs, Michael
dc.contributor.authorCha, Hyojung
dc.contributor.authorKosco, Jan
dc.contributor.authorAitchison, Catherine M
dc.contributor.authorFrancàs, Laia
dc.contributor.authorCorby, Sacha
dc.contributor.authorChiang, Chao-Lung
dc.contributor.authorWilson, Anna A
dc.contributor.authorGodin, Robert
dc.contributor.authorFahey-Williams, Alexander
dc.contributor.authorCooper, Andrew I
dc.contributor.authorSprick, Reiner Sebastian
dc.contributor.authorMcCulloch, Iain
dc.contributor.authorDurrant, James R.
dc.date.accessioned2020-08-23T08:06:04Z
dc.date.available2020-08-23T08:06:04Z
dc.date.issued2020-08-14
dc.date.submitted2020-06-05
dc.identifier.citationSachs, M., Cha, H., Kosco, J., Aitchison, C. M., Francàs, L., Corby, S., … Durrant, J. R. (2020). Tracking Charge Transfer to Residual Metal Clusters in Conjugated Polymers for Photocatalytic Hydrogen Evolution. Journal of the American Chemical Society. doi:10.1021/jacs.0c06104
dc.identifier.issn0002-7863
dc.identifier.pmid32786800
dc.identifier.doi10.1021/jacs.0c06104
dc.identifier.doi10.1021/jacs.0c12455
dc.identifier.urihttp://hdl.handle.net/10754/664753
dc.description.abstractSemiconducting polymers are versatile materials for solar energy conversion and have gained popularity as photocatalysts for sunlight-driven hydrogen production. Organic polymers often contain residual metal impurities such as palladium (Pd) clusters that are formed during the polymerization reaction, and there is increasing evidence for a catalytic role of such metal clusters in polymer photocatalysts. Using transient and operando optical spectroscopy on nanoparticles of F8BT, P3HT, and the dibenzo[b,d]thiophene sulfone homopolymer P10, we demonstrate how differences in the time scale of electron transfer to Pd clusters translate into hydrogen evolution activity optima at different residual Pd concentrations. For F8BT nanoparticles with common Pd concentrations of >1000 ppm (>0.1 wt %), we find that residual Pd clusters quench photogenerated excitons via energy and electron transfer on the femto-nanosecond time scale, thus outcompeting reductive quenching. We spectroscopically identify reduced Pd clusters in our F8BT nanoparticles from the microsecond time scale onward and show that the predominant location of long-lived electrons gradually shifts to the F8BT polymer when the Pd content is lowered. While a low yield of long-lived electrons limits the hydrogen evolution activity of F8BT, P10 exhibits a substantially higher hydrogen evolution activity, which we demonstrate results from higher yields of long-lived electrons due to more efficient reductive quenching. Surprisingly, and despite the higher performance of P10, long-lived electrons reside on the P10 polymer rather than on the Pd clusters in P10 particles, even at very high Pd concentrations of 27000 ppm (2.7 wt %). In contrast, long-lived electrons in F8BT already reside on Pd clusters before the typical time scale of hydrogen evolution. This comparison shows that P10 exhibits efficient reductive quenching but slow electron transfer to residual Pd clusters, whereas the opposite is the case for F8BT. These findings suggest that the development of even more efficient polymer photocatalysts must target materials that combine both rapid reductive quenching and rapid charge transfer to a metal-based cocatalyst.
dc.description.sponsorshipM.S. is grateful to Imperial College for a President’s Ph.D. Scholarship and to the EPSRC for a Doctoral Prize Fellowship. J.R.D. and I.M. acknowledge support from KAUST (project numbers OSR-2015-CRG4-2572 and OSR-2018-CRG7-3749.2). C.M.A., A.I.C., and R.S.S. acknowledge the Engineering and Physical Sciences Research Council (EPSRC, EP/N004884/1). L.F. thanks the EU for a Marie Curie fellowship(658270). S.C. thanks Imperial College London for a Schrödinger Scholarship. R.G. is grateful to the FRQNT for a postdoctoral award and NSERC Discovery Grant funding. C.-L.C. appreciates his colleague, Dr. Bing-Jian Su, for his kind support and assistance. All plotted data have been deposited on the open-access repository Zenodo and can be accessed via dx. doi.org/10.5281/zenodo.3932340.
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttps://pubs.acs.org/doi/10.1021/jacs.0c06104
dc.relation.urlhttps://pubs.acs.org/doi/pdf/10.1021/jacs.0c06104
dc.rightsThis is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
dc.rightsThis file is an open access version redistributed from: https://pubs.acs.org/doi/pdf/10.1021/jacs.0c06104
dc.rights.urihttp://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html
dc.titleTracking Charge Transfer to Residual Metal Clusters in Conjugated Polymers for Photocatalytic Hydrogen Evolution.
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.contributor.departmentKAUST Solar Center (KSC)
dc.identifier.journalJournal of the American Chemical Society
dc.rights.embargodate2021-08-14
dc.eprint.versionPublisher's Version/PDF
dc.contributor.institutionDepartment of Chemistry and Centre for Processable Electronics, Imperial College London, 80 Wood Lane, London W12 0BZ, U.K.
dc.contributor.institutionDepartment of Chemistry and Materials Innovation Factory, University of Liverpool, 51 Oxford Street, Liverpool L7 3NY, U.K.
dc.contributor.institutionNational Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu 30076, Taiwan
kaust.personKosco, Jan
kaust.personMcCulloch, Iain
kaust.grant.numberOSR-2015-CRG4-2572
dc.relation.issupplementedbyDOI:10.5281/zenodo.3932339
refterms.dateFOA2020-12-07T12:35:02Z
display.relations<b>Is Supplemented By:</b><br/> <ul><li><i>[Dataset]</i> <br/> Sachs, M., Hyojung Cha, Kosco, J., Aitchison, C. M., Francàs, L., Corby, S., Chao-Lung Chiang, Wilson, A. A., Godin, R., Fahey-Williams, A., Cooper, A. I., Sprick, R. S., McCulloch, I., &amp; Durrant, J. R. (2020). <i>Data for article "Tracking Charge Transfer to Residual Metal Clusters in Conjugated Polymers for Photocatalytic Hydrogen Evolution"</i> [Data set]. Zenodo. https://doi.org/10.5281/ZENODO.3932339. DOI: <a href="https://doi.org/10.5281/zenodo.3932339" >10.5281/zenodo.3932339</a> Handle: <a href="http://hdl.handle.net/10754/664924" >10754/664924</a></a></li></ul>
kaust.acknowledged.supportUnitOSR
dc.date.published-online2020-07-28
dc.date.published-print2020-08-26


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