A theoretical study of novel orthorhombic group-IVB nitride halide monolayers for photocatalytic overall water splitting.

Hydrogen energy is very important as a new clean energy source to combat the growing environmental problems. In this regard, novel photocatalyst materials for water splitting have a wide range of applications. Using first principles calculations, we theoretically studied three orthorhombic group-IVB nitride halide monolayers, Hf 2 N 2 Br 2 , Janus HfZrN 2 Br 2 and Janus Hf 2 N 2 ClBr. The energy, dynamic and thermal stabilities are demonstrated for all three monolayers. Using the HSE hybrid functional, the calculations reveal that they are direct band gap semiconductors with suitable band edge positions, good optical absorptions, and anisotropic carrier mobilities, which makes them promising for water splitting applications. Importantly, the photogenerated carriers provide enough driving force to trigger the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) within wide pH ranges, and then overall water splitting can be achieved spontaneously. We conclude that orthorhombic group-IVB nitride halide monolayers have potential applications in photocatalytic nanodevices.