Study on the Photocatalysis Mechanism of the Z-Scheme Cobalt Oxide Nanocubes/Carbon Nitride Nanosheets Heterojunction Photocatalyst with High Photocatalytic Performances

Highlights: • A novel Z-scheme Co₃O₄/g-C₃N₄ heterojunction photocatalyst was constructed. • Co₃O₄/g-C₃N₄ shows superior photocatalytic activity for the removal of TC and Cr⁶⁺. • The charge transfer was facilitated through build-in electric field. • Z-scheme photocatalysis mechanism is proposed based on the experiments and simulations. An efficient Z-scheme Co₃O₄/g-C₃N₄ heterojunction photocatalyst was developed via in-situ forming Co₃O₄ nanocubes on the g-C₃N₄ nanosheet in the hydrothermal process. The obtained photocatalyst exhibited high photocatalytic activity for the visible-light-driven catalytic reduction of Cr(VI) and catalytic oxidation of tetracycline (TC). Among the as-synthesized catalysts, Co₃O₄/g-C₃N₄-0.04 (the mass ratio of g-C₃N₄ to Co₃O₄ is 0.04) sample exhibits the most efficient catalytic activities. The photocatalytic reduction and photocatalytic oxidation efficiencies of Co₃O₄/g-C₃N₄-0.04 can obtain 81.3 and 92.6 %, respectively. Moreover, the TC is mineralized in the course of photocatalytic degradation, 72.2% of TOC is removed from the reaction system. In addition, the apparent quantum efficiency for the removal of Cr(VI) was also obtained and the the Co₃O₄/g-C₃N₄-0.04 could achieve the highest apparent quantum efficiency among the samples. The enhancing photocatalytic activities originated from the efficient interfacial charge migration and separation obtained in Co₃O₄/g-C₃N₄-0.04, which is preliminarily confirmed by the photoluminescence spectra, time-resolved photoluminescence spectra and the photoelectrochemical characterizations. Finally, we speculate that the Co₃O₄/g-C₃N₄ heterostructures follow a more reasonable Z-scheme charge transfer in this study, which is confirmed by analyzing the results of electron paramagnetic resonance, radical scavenging experiments, and theoretical calculations.