Exploring the 'Goldilocks Zone' of Semiconducting Polymer Photocatalysts via Donor-Acceptor Interactions
| Autor: | Jaroslav Vacek, Johannes Schmidt, Dana Schwarz, Arun Ichangi, Pavla Eliášová, Arne Thomas, Yaroslav S. Kochergin, Ranjit Kulkarni, Amitava Acharjya, Michael J. Bojdys |
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| Rok vydání: | 2018 |
| Předmět: |
chemistry.chemical_classification
Materials science Hydrogen Band gap donor-acceptor systems conjugated microporous polymers chemistry.chemical_element Polymer Microporous material Conjugated microporous polymer fluorescence sensing chemistry Chemical engineering Photocatalysis Water splitting triazine Quantum efficiency photocatalysis |
| DOI: | 10.26434/chemrxiv.6210110 |
| Popis: | Water splitting using polymer photocatalysts is a key technology to a truly sustainable hydrogen-based energy economy. Synthetic chemists have intuitively tried to enhance photocatalytic activity by tuning the length of π-conjugated domains of their semiconducting polymers, but the increasing flexibility and hydrophobicity of ever-larger organic building blocks leads to adverse effects such as structural collapse and inaccessible catalytic sites. To reach the ideal optical bandgap of ~2.3 eV, we synthesised a library of eight sulphur and nitrogen containing porous polymers (SNPs) with similar geometries but with optical bandgaps ranging from 2.07 to 2.60 eV using Stille coupling. These polymers combine π-conjugated electron-withdrawing triazine- (C3N3) and electron donating, sulphur-containing moieties as covalently-bonded donor-acceptor frameworks with permanent porosity. The remarkable optical properties of SNPs enable fluorescence on-off sensing of volatile organic compounds and illustrate intrinsic charge-transfer effects. Moreover, obtained polymers effectively evolve H2 gas from water under visible light irradiation with hydrogen evolution rates up to 3158 µmol h-1 g-1 and high apparent quantum efficiency which is the highest value obtained for microporous organic polymers to-date. The design principles demonstrated here are transferable to a new field of high-performance polymer photocatalysts based on efficient donor-acceptor dyads. |
| Databáze: | OpenAIRE |
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