4.8 Article

Designing fluorene-based conjugated microporous polymers for blue light-driven photocatalytic selective oxidation of amines with oxygen

Journal

APPLIED CATALYSIS B-ENVIRONMENTAL
Volume 285, Issue -, Pages -

Publisher

ELSEVIER
DOI: 10.1016/j.apcatb.2020.119796

Keywords

Conjugated microporous polymers; Blue light; Semiconductor photocatalysis; Aerobic oxidation; Imines

Funding

  1. National Natural Science Foundation of China [22072108, 21773173]
  2. Wuhan University

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This study designed and synthesized two novel fluorene-based CMPs with carbazole as an electron donor, demonstrating that subtle variation of substituent at the methylene bridge of fluorene precursor leads to different photocatalytic performance. The results suggest that tweaking in electron acceptors could enhance the photocatalytic activity of CMPs in selective chemical conversions.
Conjugated microporous polymers (CMPs) have been showcased with a brilliant prospect in organic semiconductor photocatalysis, attributing to accessible molecular design, chemical stability and environmental friendliness. Here, two novel fluorene-based CMPs were designed and conveniently synthesized with carbazole as an electron donor. Importantly, subtle variation of substituent at the methylene bridge (9-position) of fluorene precursor results in different performances in which dimethyl substituent was proven to be more efficient than difluoro substituent for blue light photocatalysis. MFC [9,9'-(9,9-dimethyl-9H-fluorene-2,7-diyl)bis(9H-carbazole)]-CMP has a much larger specific surface area, a more favourable redox position, and resultantly a superior photocatalytic performance during blue light-driven selective oxidation of amines into imines with oxygen (O-2) in an environmentally benign solvent ethanol (C2H5OH). This work suggests that subtle tweaking in electron acceptors could give rise to superior photocatalytic activity for CMPs in selective chemical conversions.

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