Black phosphorus (BP) is a promising two-dimensional material with excellent carrier mobility and high co-catalytic activity for hydrogen generation. Herein, we use polycrystalline BP nanosheets as a photocatalyst and a structure of TiF₃ as a cocatalyst to produce hydrogen under ultraviolet-visible (UV–vis) light irradiation. The TiF₃-BP composite demonstrates a hydrogen evolution rate of 612 μmolh⁻¹ g⁻¹ and nearly perfect cyclic stability during 4 h irradiation. The evolution rate is about 1.7 times higher than those of pure BP and TiO₂ and 1.5 times than that of commercial P25-BP mixture. In comparison with pure BP nanosheets, the addition of TiF₃ can effectively tailor the energy levels of BP nanosheets, decrease the recombination of photogenerated electron-hole pairs, facilitate carrier transports, and improve the stability of BP exposed to water and air. Therefore, the above findings provide a new approach for designing stable and high efficiency BP composite photocatalysts for hydrogen production.

黑磷（BP）是一种很有前途的二维材料，具有优异的载流子迁移率和高的产氢共催化活性。在此，我们使用多晶 BP 纳米片作为光催化剂，使用 TiF ₃结构作为助催化剂，在紫外-可见光（UV-vis）光照射下产生氢气。TiF ₃ -BP 复合材料在 4 小时辐照期间显示出 612 μmolh ^-1 g ^-1的析氢速率和近乎完美的循环稳定性。其演化速率是纯BP和TiO _{2 的}1.7倍，是商业P25-BP混合物的1.5倍。与纯 BP 纳米片相比，添加 TiF ₃可以有效地调整BP纳米片的能级，减少光生电子-空穴对的复合，促进载流子传输，提高BP暴露在水和空气中的稳定性。因此，上述发现为设计稳定高效的BP复合光催化剂用于制氢提供了一种新方法。