Transforming Photocatalytic g-C₃ N₄ /MoSe₂ into a Direct Z-Scheme System via Boron-Doping: A Hybrid DFT Study

Z-scheme photocatalytic systems are an ideal band alignment structure for photocatalysis because of the high separation efficiency of photo-induced carriers while simultaneously preserving the strong reduction activity of electrons and oxidation activity of holes. However, the design and construction of Z-scheme photocatalysts is challenging because of the need for appropriate energy band alignment and built-in electric field. Here, we propose a novel approach to a Z-scheme photocatalytic system using density functional theory calculations with the HSE06 hybrid functional. The undesirable type-I g-C₃ N₄ /MoSe₂ heterojunction is transformed into a direct Z-scheme system through boron doping of g-C₃ N₄ (B-doped C₃ N₄ /MoSe₂ ). Detailed analysis of the total and partial density of states, work functions and differential charge density distribution of the B-doped C₃ N₄ /MoSe₂ heterojunction shows the proper band alignment and existence of a built-in electric field at the interface, with the direction from g-C₃ N₄ to MoSe₂ , demonstrating a direct Z-scheme heterojunction. Further investigation on the absorption spectra reveals a large enhancement of the light absorption efficiency after boron doping. The results consistently confirm that electronic structures and photocatalytic performance can be effectively manipulated by a facile boron doping. Modulating the band alignment of heterojunctions in this way provides valuable insights for the rational design of highly efficient heterojunction-based photocatalytic systems.