{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,2]],"date-time":"2026-07-02T22:49:22Z","timestamp":1783032562250,"version":"3.54.6"},"reference-count":33,"publisher":"AIP Publishing","issue":"4","funder":[{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/S017623\/1"],"award-info":[{"award-number":["EP\/S017623\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/T517938\/1"],"award-info":[{"award-number":["EP\/T517938\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000288","name":"Royal Society","doi-asserted-by":"publisher","award":["RSRP\/S2\/232003"],"award-info":[{"award-number":["RSRP\/S2\/232003"]}],"id":[{"id":"10.13039\/501100000288","id-type":"DOI","asserted-by":"publisher"}]},{"name":"International Science Partnerships Fund","award":["ID 1203758747"],"award-info":[{"award-number":["ID 1203758747"]}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2025,7,28]]},"abstract":"<jats:p>Organic polymer photocatalysts have gained much interest in recent years, largely because of their photocatalytic activity toward sacrificial hydrogen production from water. Time-resolved electronic absorption spectroscopy is commonly employed to understand the photophysical processes occurring following photon absorption, which in turn is used to rationalize photocatalytic activities. The homopolymer of dibenzo[b,d]thiophene sulfone (P10) is a well-studied and high performing photocatalyst for sacrificial hydrogen evolution from water. While sacrificial reagents are well documented as a prerequisite for this reaction, their roles in the picosecond\u2013nanosecond photodynamics have yet to be determined using transient electronic signatures. By employing lifetime density analysis of time-resolved electronic absorption spectra of P10 in a variety of solvent mixtures, we show that the electron polaron (the required charge for hydrogen evolution) is produced on the 0.5\u2013100 and 50\u2013800\u00a0ps timescales via excitonic quenching by triethylamine and methanol, respectively, two common sacrificial electron donors. We conclude that there is significant pre-association of triethylamine with the P10 polymer, resulting in efficient excitonic quenching. This mechanism competes effectively with radiative excitonic relaxation, which occurs on similar timescales, reducing exciton losses and improving polaron yields.<\/jats:p>","DOI":"10.1063\/5.0274944","type":"journal-article","created":{"date-parts":[[2025,7,28]],"date-time":"2025-07-28T10:59:22Z","timestamp":1753700362000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":3,"title":["Unraveling the mechanisms of charge-separation in a dibenzo[<i>b<\/i>,<i>d<\/i>]thiophene sulfone polymer photocatalyst using time-resolved electronic absorption spectroscopy"],"prefix":"10.1063","volume":"163","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0707-4702","authenticated-orcid":false,"given":"Richard J.","family":"Lyons","sequence":"first","affiliation":[{"name":"Materials Innovation Factory and Department of Chemistry, University of Liverpool 1 , Liverpool L73NY,","place":["United Kingdom"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-9580-6311","authenticated-orcid":false,"given":"Ewan","family":"McQueen","sequence":"additional","affiliation":[{"name":"Department of Pure and Applied Chemistry, University of Strathclyde 2 , Thomas Graham Building, 295 Cathedral Street, Glasgow G1 1XL,","place":["United Kingdom"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0001-5326-3539","authenticated-orcid":false,"given":"Rhys J.","family":"Bourhill","sequence":"additional","affiliation":[{"name":"Department of Pure and Applied Chemistry, University of Strathclyde 2 , Thomas Graham Building, 295 Cathedral Street, Glasgow G1 1XL,","place":["United Kingdom"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0001-4094-5290","authenticated-orcid":false,"given":"Owen","family":"Thwaites","sequence":"additional","affiliation":[{"name":"Department of Physics and Stephenson Institute of Renewable Energy University of Liverpool 3 , Liverpool L69 7ZE,","place":["United Kingdom"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Andrew I.","family":"Cooper","sequence":"additional","affiliation":[{"name":"Materials Innovation Factory and Department of Chemistry, University of Liverpool 1 , Liverpool L73NY,","place":["United Kingdom"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5389-2706","authenticated-orcid":false,"given":"Reiner Sebastian","family":"Sprick","sequence":"additional","affiliation":[{"name":"Department of Pure and Applied Chemistry, University of Strathclyde 2 , Thomas Graham Building, 295 Cathedral Street, Glasgow G1 1XL,","place":["United Kingdom"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9032-3548","authenticated-orcid":false,"given":"Alexander J.","family":"Cowan","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Stephenson Institute of Renewable Energy University of Liverpool 4 , Liverpool L69 7ZD,","place":["United Kingdom"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2423-8799","authenticated-orcid":false,"given":"Adrian M.","family":"Gardner","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Stephenson Institute of Renewable Energy University of Liverpool 4 , Liverpool L69 7ZD,","place":["United Kingdom"]},{"name":"Early Career Laser Laboratory and Surface Science Research Centre, University of Liverpool 5 , Liverpool L69 3BX,","place":["United Kingdom"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2025,7,28]]},"reference":[{"issue":"8011","key":"2025072806591789100_c1","doi-asserted-by":"publisher","first-page":"295","DOI":"10.1038\/s41586-024-07322-2","article-title":"The refinery of the future","volume":"629","year":"2024","journal-title":"Nature"},{"issue":"9","key":"2025072806591789100_c2","doi-asserted-by":"publisher","first-page":"746","DOI":"10.1038\/s41560-019-0456-5","article-title":"Current understanding and challenges of solar-driven hydrogen generation using polymeric photocatalysts","volume":"4","year":"2019","journal-title":"Nat. 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