An electron-hole separation mechanism caused by the pseudo-gap formed at the interfacial Co-N bond between cobalt porphyrin metal organic framework and boron-doped g-CN for boosting photocatalytic H production.

Photocatalytic hydrogen evolution from water splitting presents an attractive prospect in dealing with the energy crisis, but the low efficiency of charge separation and migration still seriously hinders its further practical application. Here, an acidified boron-doped g-CN (HBCNN) and cobalt porphyrin metal organic frameworks (CoPMOF) self-assembled two-dimensional and two-dimensional (2D/2D) hybrid photocatalyst is fabricated successfully. The resultant HBCNN/CoPMOF with optimum ratio exhibits a superior H evolution rate of 33.17 mmol g h, which is 3.04 and 100.50 times higher than the single HBCNN and CoPMOF, respectively. It is found that a coordination connection has formed between CoPMOF and HBCNN through Co-N bond, and the interfacial Co-N bond then forms a pseudo-gap in the up-spin channel of electronic states, establishing an electron-hole separation mechanism. It is this electron-hole separation mechanism that contributes to a Z-scheme transport mode of photogenerated carriers, which greatly promotes the photocatalytic H2 production performance of HBCNN/CoPMOF heterostructure. This work may provide an idea for the design of heterojunction to improve the photocatalytic performance by constructing electron-hole separation through interfacial bond.