Influence of Electron Donors on the Charge Transfer Dynamics of Carbon Nanodots in Photocatalytic Systems.
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Abstract
Carbon nanodots (CNDs) are nanosized light-harvesters emerging as next-generation photosensitizers in photocatalytic reactions. Despite their ever-increasing potential applications, the intricacies underlying their photoexcited charge carrier dynamics are yet to be elucidated. In this study, nitrogen-doped graphitic CNDs (NgCNDs) are selectively excited in the presence of methyl viologen (MV2+, redox mediator) and different electron donors (EDs), namely ascorbic acid (AA) and ethylenediaminetetraacetic acid (EDTA). The consequent formation of the methyl viologen radical cation (MV•+) is investigated, and the excited charge carrier dynamics of the photocatalytic system are understood on a 0.1 ps-1 ms time range, providing spectroscopic evidence of oxidative or reductive quenching mechanisms experienced by optically excited NgCNDs (NgCNDs*) depending on the ED implemented. In the presence of AA, NgCNDs* undergo oxidative quenching by MV2+ to form MV•+, which is short-lived due to dehydroascorbic acid, a product of photoinduced hole quenching of oxidized NgCNDs. The EDTA-mediated reductive quenching of NgCNDs* is observed to be at least 2 orders of magnitude slower due to screening by EDTA-MV2+ complexes, but the MV•+ population is stable due to the irreversibly oxidized EDTA preventing a back reaction. In general, our methodology provides a distinct solution with which to study charge transfer dynamics in photocatalytic systems on an extended time range spanning 10 orders of magnitude. This approach generates a mechanistic understanding to select and develop suitable EDs to promote photocatalytic reactions.
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Publication status: Published
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2155-5435
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Engineering and Physical Sciences Research Council (1948662)
EPSRC (EP/T02030X/1)
Royal Society (UF150033)
Leverhulme Trust (RPG-2018-256)
European Research Council (756962)
European Commission Horizon 2020 (H2020) ERC (957513)
Engineering and Physical Sciences Research Council (EP/L015978/1)