Facile Chemical Vapor Modification Strategy to Construct Surface Cyano-Rich Polymer Carbon Nitrides for Highly Efficient Photocatalytic H2 Evolution.

The surface grafting of electro-negative cyano groups on polymer carbon nitrides (PCNs) is an effective way to tail their electronic structure. Despite the significant progress in the synthesis of cyano group-enriched PCN, developing a simple and efficient method remains challenging. Here, a facile strategy was developed for fabricating surface cyano-rich PCN (PCN-DM) with a porous structure via chemical vapor modification using diaminomaleonitrile. The cyano groups of diaminomaleonitrile substituted the amino groups on PCN surface via a deamination. The hydrogen production rate of the PCN-DM was approximately 17 times higher than that of pristine PCN. This significant increase in photocatalytic performance could be assigned to the fusion of cyano groups in the surface of PCN, forming new gap states that broadened the visible-light harvesting and accelerated charge separation for photoredox reactions. This study unveils a promising approach for incorporating functional units in the design of novel photocatalysts for efficient hydrogen production.