Benzene Bridged Carbon Nitride for Efficient Photocatalytic Hydrogen Evolution

Turing the electronic structure by inserting certain functional groups in graphitic carbon nitride (g-C₃N₄, CN for short) skeleton through molecular doping is an effective way to improve its photocatalytic performance. Herein, we prepare a benzene bridged carbon nitride (BCN) by calcining urea and 1,3,5-tribromobenzene at elevated temperature. The introduction of benzene ring in g-C₃N₄ layers improves the separation efficiency and lifetime of photogenerated carriers, inhibits the recombination rate of electron/hole pairs, thus the performance of photocatalytic hydrogen evolution improves. The optimal hydrogen evolution rate of 1.5BCN reaches 1800 µmol/h·g, which is nine times that of the pure g-C₃N₄. DFT calculation proved the benzene bridged CN increased the distance of charge transfer (DCT) and the push-pull electronic effect of intramolecular electrons. This work may provide a pathway for preparing molecular doped g-C₃N₄ with improved photocatalytic performance.