4.8 Article

Tunable Photocatalytic Two-Electron Shuttle between Paired Redox Sites on Halide Perovskite Nanocrystals

Journal

ACS CATALYSIS
Volume 12, Issue 10, Pages 5903-5910

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.2c01044

Keywords

perovskite nanocrystals; heterogeneous photocatalysis; C-H functionalization; two-electron shuttle; redox cascade

Funding

  1. National Key RD Program [2021YFB4000600]
  2. National Natural Science Foundation of China [22022406]
  3. 111 project [B12015]
  4. Haihe Laboratory of Sustainable Chemical Transformations
  5. Natural Science Foundation of Tianjin [20JCJQJC00110, 20JCYBJC00590]

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This paper reports a photon-mediated electron shuttle between paired redox sites on perovskite nanocrystals for the reformation of carbon-halogen bonds, and successfully achieves the transformation of arenes and heteroarenes.
Perovskite semiconductors as advanced solar energy-converting Reducing center Oxidizing center materials are promising catalysts for photoredox organic synthesis. Despite the high concentration of charge carriers generated on the perovskite surface, efficient utilization of these nonequilibrium and shambolic energetic carriers to trigger a chemical reaction remains a hot and challenging subject. Here, we report a photonmediated electron shuttle between paired redox sites on perovskite nanocrystals for the reformation of highly stable carbon-halogen bonds, where both surface electrons and holes are utilized simultaneously. The photo-redox cascade can be effortlessly tailored by precise control of the surface-reducing/-oxidizing reaction rates, which unlocks the transformation for a wide range of (het)arenes. This work demonstrates colloidal perovskite photocatalysts for the direct installation of more than 10 different synthetically important functional groups onto arenes and heteroarenes.

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