Due to the drastic required thermodynamical requirements, a photoelectrode material that can function as both a photocathode and a photoanode remains elusive. In this work, we demonstrate for the first time that, under simulated solar light and without co-catalysts, donor-acceptor conjugated acetylenic polymers (CAPs) exhibit both impressive oxygen evolution (OER) and hydrogen evolution (HER) photocurrents in alkaline and neutral medium, respectively. In particular, poly(2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine) (pTET) provides a benchmark OER photocurrent density of ~200 μA cm−2 at 1.23 V vs. reversible hydrogen electrode (RHE) at pH 13 and a remarkable HER photocurrent density of ~190 μA cm−2 at 0.3 V vs. RHE at pH 6.8. By combining theoretical investigations and electrochemical-operando Resonance Raman spectroscopy, we show that the OER proceeds with two different mechanisms, with the electron-depleted triple bonds acting as single-site OER in combination with the C4-C5 atoms of the phenyl rings as dual sites. The HER, instead, occurs via an electron transfer from the tri-acetylenic linkages to the triazine rings, which act as the HER active sites. This work represents a novel application of organic-based materials and contributes to the development of high-performance photoelectrochemical catalysts for the solar fuels’ generation.
| Identifer | oai:union.ndltd.org:DRESDEN/oai:qucosa:de:qucosa:92768 |
| Date | 05 August 2024 |
| Creators | Borelli, Mino, An, Yun, Querebillo, Christine Joy, Morag, Ahiud, Neumann, Christof, Turchanin, Andrey, Sun, Hanjun, Kuc, Agnieszka, Weidinger, Inez M., Feng, Xinliang |
| Publisher | Wiley |
| Source Sets | Hochschulschriftenserver (HSSS) der SLUB Dresden |
| Language | English |
| Detected Language | English |
| Type | info:eu-repo/semantics/publishedVersion, doc-type:article, info:eu-repo/semantics/article, doc-type:Text |
| Rights | info:eu-repo/semantics/openAccess |
| Relation | 1864-564X, e202301170, 10.1002/cssc.202301170, info:eu-repo/grantAgreement/Deutsche Forschungsgemeinschaft/Exzellenzcluster 2008/EXC 2008/1-390540038//Unifying Systems in Catalysis /UniSysCat, info:eu-repo/grantAgreement/Deutsche Forschungsgemeinschaft/SFB 1415: Chemie der synthetischen zweidimensionalen Materialien/417590517/, info:eu-repo/grantAgreement/Deutsche Forschungsgemeinschaft/TRR 234: Lichtgetriebene molekulare Katalysatoren in hierarchisch strukturierten Materialien – Synthese und mechanistische Studien/364549901//Kohlenstoff-Nanomembranen als 2D-Plattform für die Immobilisierung, den Einbau und die Untersuchung von Photosensibilisatoren und Katalysatoren /B07, info:eu-repo/grantAgreement/Deutsche Forschungsgemeinschaft/TRR 234: Lichtgetriebene molekulare Katalysatoren in hierarchisch strukturierten Materialien – Synthese und mechanistische Studien/364549901//Zentrale Charakterisierung /Z02 |
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