4.8 Article

Fully Condensed Poly (Triazine Imide) Crystals: Extended π-Conjugation and Structural Defects for Overall Water Splitting

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 2, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202113389

Keywords

overall water splitting; photocatalysis; poly triazine imide; structure defects; p-conjugation

Funding

  1. National Natural Science Foundation of China [22032002, 22172029, U1905214, 21961142019, 21861130353, 21761132002, 21425309]
  2. National Basic Research Program of China [2013CB632405]
  3. Chang Jiang Scholars Program of China [T2016147]
  4. 111 Project [D16008]

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A fully condensed poly(triazine imide) crystal with extended pi-conjugation and deficient structural defects was successfully synthesized by conducting polycondensation in a mild molten salt of LiCl/NaCl. The optimized polymeric carbon nitride crystal exhibits high apparent quantum efficiency for hydrogen production in overall water splitting due to efficient exciton dissociation and fast transfer of charge carriers.
Conventional polymerization for the synthesis of carbon nitride usually generates amorphous heptazine-based melon with an abundance of undesired structural defects, which function as charge carrier recombination centers to decrease the photocatalytic efficiency. Herein, a fully condensed poly (triazine imide) crystal with extended pi-conjugation and deficient structure defects was obtained by conducting the polycondensation in a mild molten salt of LiCl/NaCl. The melting point of the binary LiCl/NaCl system is around 550 degrees C, which substantially restrain the depolymerization of triazine units and extend the pi-conjugation. The optimized polymeric carbon nitride crystal exhibits a high apparent quantum efficiency of 12% (lambda = 365 nm) for hydrogen production by one-step excitation overall water splitting, owing to the efficient exciton dissociation and the subsequent fast transfer of charge carriers.

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