Construction of Z-type ZnWO4/Co3O4 Composite with Zn-O-Co Interface Bonds and Its Photocatalytic Degradation of Tetracycline

doi:10.15541/jim20250506

Abstract

Abstract: Co₃O₄ material holds a significant position among cobalt-based semiconductor materials, and enhancing the photogenerated carrier separation efficiency of Co₃O₄ materials remains a crucial research topic. ZnWO₄/Co₃O₄ composite material was constructed via a hydrothermal method based on two precursor materials including ZnWO₄ nanoparticles and Co₃O₄ microspheres. Morphology, structure and opto-electronic properties of ZnWO₄/Co₃O₄ composite materials were characterized using different techniques. Moreover, the performance of the composite materials in the photocatalytic degradation of tetracycline (TC) was investigated. Photocatalytic mechanism of the material was elucidated by combining radical trapping experiments and Mott-Schottky fitting results with the material’s bandgap. The results indicate that heterojunctions are constructed at the interface between ZnWO₄ nanoparticles and Co₃O₄ microspheres through the formation of Zn-O-Co bonds. When the loading of ZnWO₄ is 15% (in mass), the degradation rate of the ZnWO₄/Co₃O₄ composite material in a 10 mg∙L^-1 TC solution can reach 80.52%, which is 6.2 times higher than that of the single Co₃O₄ material. The improvement of the photocatalytic performance of the ZnWO₄/Co₃O₄ composite material is attributed to the fact that the photogenerated electrons e^- on the conduction band of ZnWO₄ material can recombine with the photogenerated holes h⁺ on the valence band of Co₃O₄ at the interface heterojunction via the Zn-O-Co bonds. The photogenerated e^- accumulate on the conduction band of Co₃O₄, and the photogenerated h⁺ accumulate on the valence band of ZnWO₄. This endows the ZnWO₄/Co₃O₄ composite material with a Z-type photogenerated carrier transport mechanism and effectively enhances the separation efficiency of photogenerated carriers. The loading site of ZnWO₄ is the main active center for the photocatalytic degradation reaction, while ·OH radicals acting the main active species. The synergistic effect of ·O₂^- radicals and photogenerated h⁺ enhances the photocatalytic performance of the ZnWO₄/Co₃O₄ composite material.

Key words: ZnWO₄/Co₃O₄, Zn-O-Co bond, Z-type, tetracycline, degradation mechanism

CLC Number:

O649

LI Jinglin, YIN Guangming, ZHENG Jianhua, YANG Hongguang, GUAN Fangfang, HUANG Xinyu, CAO Xinyu. Construction of Z-type ZnWO₄/Co₃O₄ Composite with Zn-O-Co Interface Bonds and Its Photocatalytic Degradation of Tetracycline[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250506.

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Construction of Z-type ZnWO₄/Co₃O₄ Composite with Zn-O-Co Interface Bonds and Its Photocatalytic Degradation of Tetracycline

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