Polymeric or organic semiconductors are promising candidates for photocatalysis but mostly only show moderate activity owing to strongly bound excitons and insufficient optical absorption. Herein, we report a facile bottom-up strategy to improve the activity of a carbon nitride to a level in which a majority of photons are really used to drive photoredox chemistry. Co-condensation of urea and oxamide followed by post-calcination in molten salt is shown to result in highly crystalline species with a maximum π-π layer stacking distance of heptazine units of 0.292 nm, which improves lateral charge transport and interlayer exciton dissociation. The addition of oxamide decreases the optical band gap from 2.74 to 2.56 eV, which enables efficient photochemistry also with green light. The apparent quantum yield (AQY) for H evolution of optimal samples reaches 57 % and 10 % at 420 nm and 525 nm, respectively, which is significantly higher than in most previous experiments.
Polymeric carbon nitride (PCN), in either triazine or heptazine form, has been regarded as a promising metal-free, environmentally benign, and sustainable photocatalyst for solar hydrogen production. However, PCN in most cases only exhibits moderate activity owing to its inherent properties, such as rapid charge carrier recombination. Herein we present a triazine-heptazine copolymer synthesized by simple post-calcination of PCN in eutectic salts, that is, NaCl/KCl, to modulate the polymerization process and optimize the structure. The construction of an internal triazine-heptazine donor-acceptor (D-A) heterostructure was affirmed to significantly accelerate interface charge transfer (CT) and thus boost the photocatalytic activity (AQY=60 % at 420 nm). This study highlights the construction of intermolecular D-A copolymers in NaCl/KCl molten salts with higher melting points but in the absence of lithium to modulate the chemical structure and properties of PCN.
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