Rational Design of Black Phosphorus-Based Direct Z‑Scheme Photocatalysts for Overall Water Splitting: The Role of Defects

Black phosphorus (BP) has received increasing interest as a promising photocatalyst for water splitting. Nevertheless, exploring the underlying hydrogen evolution reaction (HER) mechanism and improving the water oxidizing ability remains an urgent task. Here, using first-principles calculations, we uncover the role of point defects in improving the HER activity of BP photocatalysts. We demonstrate that the defective phosphorene can be effectively activated by the photoinduced electrons under solar light, exhibiting high HER catalytic activity in a broad pH range (0–10). Besides, we propose that the direct Z-scheme in the defective BP/SnSe2 heterobilayer is quite feasible for photocatalytic overall water splitting. This mechanism could be further verified based on the excited state dynamics method. The role of point defects in the photocatalytic mechanism provides useful insights for the development of BP photocatalysts