Robust interaction of ZnO and TiO2 nanoparticles with layered graphitic carbon nitride for enhanced photocatalytic oxidative desulfurization of fuel oil: mechanism, performance and stability

RSC Adv. 2024 Aug 14;14(35):25586-25597. doi: 10.1039/d4ra04357j. eCollection 2024 Aug 12.

Abstract

Sulfur compounds in fuel such as thiophene, benzothiophene and dibenzothiophene are the primary source of SO x emissions, leading to environmental pollution and acid rain. In this study, we synthesized a layered oxygen-doped graphitic carbon nitride (OCN) structure and integrated ZnO and TiO2 nanoparticles onto the OCN surface through a microwave-assisted sol-gel method. The X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) results confirmed a robust interaction between the ZnO and TiO2 nanoparticles and the oxygen-doped g-C3N4 (OCN) surface, as indicated by the formation of C-N-Ti and C-O-Ti bonds. This interaction notably improved the optoelectronic properties of the ZnO-TiO2/OCN composite, yielding increased visible light absorption, reduced charge recombination rate, and enhanced separation and transfer of photogenerated electron-hole pairs. The oxygen doping into the CN network could alter the band structure and expand the absorption range of visible light. The ZnO-TiO2/OCN photocatalyst demonstrated remarkable desulfurization capabilities, converting 99.19% of dibenzothiophene (DBT) to dibenzothiophene sulfone (DBT-O2) at 25 °C, and eliminating 92.13% of DBT from real-world fuel oil samples. We conducted in-depth analysis of the factors impacting the redox process of DBT, including the ZnO ratio, initial DBT concentration, catalyst dosage, stability, and O/S molar ratio. Radical trapping experiments established that ˙O2 -, ˙OH and h+ radicals significantly influence the reaction rate. The obtained results indicated that the ZnO-TiO2/OCN photocatalyst represents a promising tool for future fuel oil desulfurization applications.