Simultaneously Achieving Fast Intramolecular Charge Transfer and Mass Transport in Holey D−π–A Organic Conjugated Polymers for Highly Efficient Photocatalytic Pollutant Degradation
In: JACS Au, 2023
academicJournal
Zugriff:
[Image: see text] Simultaneously realizing efficient intramolecular charge transfer and mass transport in metal-free polymer photocatalysts is critical but challenging for environmental remediation. Herein, we develop a simple strategy to construct holey polymeric carbon nitride (PCN)-based donor−π–acceptor organic conjugated polymers via copolymerizing urea with 5-bromo-2-thiophenecarboxaldehyde (PCN–5B2T D−π–A OCPs). The resultant PCN–5B2T D−π–A OCPs extended the π-conjugate structure and introduced abundant micro-, meso-, and macro-pores, which greatly promoted intramolecular charge transfer, light absorption, and mass transport and thus significantly enhanced the photocatalytic performance in pollutant degradation. The apparent rate constant of the optimized PCN–5B2T D−π–A OCP for 2-mercaptobenzothiazole (2-MBT) removal is ∼10 times higher than that of the pure PCN. Density functional theory calculations reveal that the photogenerated electrons in PCN–5B2T D−π–A OCPs are much easier to transfer from the donor tertiary amine group to the benzene π-bridge and then to the acceptor imine group, while 2-MBT is more easily adsorbed on π-bridge and reacts with the photogenerated holes. A Fukui function calculation on the intermediates of 2-MBT predicted the real-time changing of actual reaction sites during the entire degradation process. Additionally, computational fluid dynamics further verified the rapid mass transport in holey PCN–5B2T D−π–A OCPs. These results demonstrate a novel concept toward highly efficient photocatalysis for environmental remediation by improving both intramolecular charge transfer and mass transport.
Titel: |
Simultaneously Achieving Fast Intramolecular Charge Transfer and Mass Transport in Holey D−π–A Organic Conjugated Polymers for Highly Efficient Photocatalytic Pollutant Degradation
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Autor/in / Beteiligte Person: | Che, Huinan ; Wang, Jian ; Wang, Peifang ; Ao, Yanhui ; Chen, Juan ; Gao, Xin ; Zhu, Fangyuan ; Liu, Bin |
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Zeitschrift: | JACS Au, 2023 |
Veröffentlichung: | American Chemical Society, 2023 |
Medientyp: | academicJournal |
DOI: | 10.1021/jacsau.3c00088 |
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