Fabrication of ZnIn ₂S ₄/CeO ₂ S-Scheme Heterojuntion for the Enhanced Removal of Tetracycline Under Visible Light Irradiation

Abstract

A series of S-scheme ZnIn2S4/x-CeO2 heterojunction were designed and fabricated through in-situ precipitation and hydrothermal method. XRD, SEM, TEM, EDX, XPS, UV-vis DRS and adsorption-photocatalytic techniques were employed to investigate its crystal phase structure, morphology, size, elemental composition, photo-response property and elimination ability for tetracycline. XRD analysis revealed CeO2 and ZnIn2S4 in ZnIn2S4/x-CeO2 sample presented cubic and hexagonal phase structure, respectively. SEM and TEM images indicated that CeO2 particles with irregular-shaped of around 20 nm were attached on the smooth surface of ZnIn2S4 microparticles with ca. 4 μm. All the as-synthesized ZnIn2S4/x-CeO2 samples could harvest more visible-light and the absorption edges were red-shifted in comparison with pure CeO2. ZnIn2S4/0.3-CeO2 sample exhibited remarkably enhanced photocatalytic performance and its removal efficiency for tetracycline reached 86.84% within 100 min. The detailed experimental and DFT calculation indicated that the enhanced photocatalytic property was mainly ascribed to the synergistic effect of wide light-response range, suitable band position and successful fabrication of S-scheme heterostructure, which was in favor of rapid transfer and available separation of photo-generated e-/h+ pairs. The scavenger experiments and the ESR data revealed that the •O2– and h+ active species played the dominant role in tetracycline removal over ZnIn­2S4/0.3-CeO2 system. In addition, the as-synthesized ZnIn­2S4/0.3-CeO2 samples had excellent stability and the removal efficiency still reached 70.08% after being repeatedly used for 4 times. Furthermore, the possible enhanced photocatalytic mechanism over ZnIn2S4/x-CeO2 was proposed to get a better understanding of photocatalytic process. This work provided the guidance to fabricate CeO2-based heterojunction with promising prospect for the efficient elimination of antibiotic residues from wastewater.

Keywords: ZnIn2S4, CeO2, S-scheme heterostructure, Photocatalysis