A Codoped Polymeric Photocatalyst with Prolonged Carrier Lifetime and Extended Spectral Response up to 600 nm for Enhanced Hydrogen Evolution

The intrinsic properties of photocatalysts, such as electron state and energy band structure, contribute significantly to their catalytic performance. However, it is difficult to alter these properties of semiconductors by conventional modifications. To adjust the intrinsic properties while preserving long-term conjugation of the polymeric photocatalysts, a post-thermal treatment is proposed to codope P and Na into polymeric carbon nitride in this work. After codoping, the absorption of visible irradiation is strongly extended up to 639 nm. Additionally, the lifetime of charge carriers is almost tripled from 1.09 to 2.93 ns. The photocatalytic hydrogen evolution performance under visible light is improved to 2032 μmol·h^-1 g^-1 in the optimized sample, corresponding to apparent quantum efficiencies of 6.79% and 0.09% at 420 and 600 nm, respectively. The enhanced catalytic activity is ascribed to the synergistic effects of prolonged lifetime and increased charge density that resulted from lattice distortion and extended visible utilization due to the formation of subgap state. Our work provides new pathways for the modification of polymeric catalysts toward high-performance and full-spectrum photocatalysis.