Low charge-separation transport efficiency resulting from structural defects largely limits photocatalytic hydrogen production over polymeric graphitic carbon nitride (PCN) photocatalyst. Herein, an electron-donating group, namely p-phenylene, is incorporated into PCN by a polycondensation reaction between carbon nitride and p-phenylenediamine (or p-benzoquinone) to repair the structural defects. The p-phenylene-modified PCN exhibits an almost fivefold increase in H2 evolution, a threefold increase in photocurrent density, and higher nonradiative rate (0.285 ns-1 ). Spectroscopic studies confirm that p-phenylene tends to bridge the heptazine-based oligomers through a polycondensation reaction. Theoretical calculations reveal that anchoring of the heptazine units by p-phenylene induces localization of h+ and e- on the phenylene and melem moieties, respectively, which effectively separates the charge carriers. This strategy provides an opportunity to overcome structural defects in carbon nitride for efficient photocatalytic solar energy conversion.
Keywords: carbon; nitrides; photocatalysis; photochemistry; water splitting.
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