Molecular-functionalized engineering of porous carbon nitride nanosheets for wide-spectrum responsive solar fuel generation

Carbon nitride (C3N4) is a promising metal-free photocatalyst for solar-to-energy conversion, but bulk carbon nitride (BCN) shows insufficient light absorption, sluggish photocarrier transfer and moderate activity for photocatalysis. Herein, a facile strategy to significantly increase solar spectrum absorption of the functionalized porous carbon nitride nanosheets (MFPCN) via molecule self-assembly engineering coupled thermal polymerization is reported. This strategy can greatly enhance the wide-solar-spectrum absorption of MFPCN up to 1000 nm than most reported carbon nitride-based photocatalysts. Experimental characterizations and theoretical calculations together display that this strategy could introduce hydroxyl groups into the structure of MFPCN as well as the rich pores and active sites at the edges of framework, which can narrow the bandgap and accelerate the transfer and separation of photoinduced carries. As a result, the optimal MFPCN photocatalyst exhibit the excellent photocatalytic hydrogen evolution rate of 7.745 mmol g-1h-1 under simulated solar irradiation, which is ≈13 times that of BCN with remarkable durable CO2 reduction activities. New findings in this work will provide an approach to extend solar spectrum absorption of metal-free catalysts for solar fuel cascades.