NiO/TiO₂ p-n Heterojunction Induced by Radiolysis for Photocatalytic Hydrogen Evolution

Titanium dioxide (TiO₂), a widely used semiconductor in photocatalysis owing to its adequate potential for water hydrolysis, chemical stability, low toxicity, and low cost. However, its efficiency is limited by fast charge-carrier recombination and poor visible light absorption. Coupling TiO₂ with a p-type semiconductor, such as nickel oxide (NiO), forming a p-n heterojunction, decreases the recombination of charge carriers and increases photocatalytic activity. In this work, the surface of TiO₂ modified with NiO nanoparticles (NPs) induced by radiolysis for photocatalytic hydrogen production was studied. The photocatalytic activity of NiO/TiO₂ was evaluated using methanol as a hole scavenger under UV-visible light. All modified samples presented superior photocatalytic activity compared to bare TiO₂. The dynamics of the charge carriers, a key electronic phenomenon in photocatalysis, was investigated by time-resolved microwave conductivity (TRMC). The results highlight the crucial role of Ni-based NPs modification in enhancing the separation of the charge carrier and activity under UV-visible irradiation. Furthermore, the results revealed that under visible irradiation, NiO-NPs inject electrons into the conduction band of titanium dioxide.