4.8 Review

Beyond C3N4 pi-conjugated metal-free polymeric semiconductors for photocatalytic chemical transformations

Journal

CHEMICAL SOCIETY REVIEWS
Volume 50, Issue 3, Pages 2147-2172

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d0cs00445f

Keywords

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Funding

  1. National Key R&D Program of China [2018YFE0208500]
  2. Doctor Foundation of Southwest University of Science and Technology [18zx7137]
  3. Opening Project of State Key Laboratory of Polymer Materials Engineering (Sichuan University) [sklpme2019-4-33]
  4. National Natural Science Foundation of China [51573109]
  5. Project of State Key Laboratory of Environment-friendly Energy Materials, Southwest University of Science and Technology [17FKSY0115]

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This review article introduces the development of metal-free polymeric photocatalysts with large pi-conjugated units for various chemical transformations. The focus is on the rational manipulation of pi-conjugation enlargement, charge separation, electronic structures, and band structures in the design of these catalysts. The strategies provide potential avenues to address challenges in catalyst activity, selectivity, and stability for further development in this field.
Photocatalysis with stable, efficient and inexpensive metal-free catalysts is one of the most promising options for non-polluting energy production. This review article covers the state-of-the-art development of various effective metal-free polymeric photocatalysts with large pi-conjugated units for chemical transformations including water splitting, CO2 and N-2 reduction, organic synthesis and monomer polymerisation. The article starts with the catalytic mechanisms of metal-free photocatalysts. Then a particular focus is on the rational manipulation of pi-conjugation enlargement, charge separation, electronic structures and band structures in the design of metal-free polymeric photocatalysts. Following the design principles, the selection and construction of functional units are discussed, as well as the connecting bonds and dimensions of pi-conjugated polymeric photocatalysts. Finally the hot and emerging applications of metal-free polymeric photocatalysts for photocatalytic chemical transformations are summarized. The strategies provide potential avenues to address the challenges of catalyst activity, selectivity and stability in the further development of highly effective metal-free polymeric photocatalysts.

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