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无机材料学报

• 研究论文 •    

界面Zn-O-Co键构建Z型ZnWO4/Co3O4复合材料及其光催化降解四环素

李婧琳1, 殷广明1,2, 郑建华1, 杨红光1, 关芳芳1, 黄欣宇1, 曹欣雨1   

  1. 齐齐哈尔大学 1.化学与化学工程学院; 2.分析测试中心, 齐齐哈尔 161006
  • 收稿日期:2025-12-18 修回日期:2026-02-10
  • 作者简介:李婧琳(1999-), 女, 硕士研究生. E-mail: 2261735804@qq.com
  • 基金资助:
    黑龙江省自然科学基金(LH2024B028)

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

LI Jinglin1, YIN Guangming1,2, ZHENG Jianhua1, YANG Hongguang1, GUAN Fangfang1, HUANG Xinyu1, CAO Xinyu1   

  1. 1. College of Chemistry and Chemistry Engineering, Qiqihar University, Qiqihar 161006, China;
    2. Analysis and Test Center, Qiqihar University, Qiqihar 161006, China
  • Received:2025-12-18 Revised:2026-02-10
  • About author:LI Jinglin (1999-), female, Master candidate. E-mail: 2261735804@qq.com
  • Supported by:
    Heilongjiang Provincial Natural Science Foundation of China (LH2024B028)

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摘要： Co3O4材料在Co基半导体材料中占据重要地位,提高Co3O4材料光生载流子分离效率依然是当前重要研究课题。本研究在分别制备ZnWO4纳米颗粒和Co3O4微球两种前驱体材料的基础上,通过水热法构筑了ZnWO4/Co3O4复合材料。利用不同表征方法分析ZnWO4/Co3O4复合材料的形貌、结构和光电化学性质,并考察了其光催化降解四环素(TC)的性能;通过自由基捕获实验和Mott-Schottky拟合结果结合材料的禁带宽度对材料的光催化机理进行了探讨。结果表明：ZnWO4纳米颗粒与Co3O4微球在界面处通过形成Zn-O-Co键构建了异质结;当ZnWO4负载量为15%(质量分数)时,ZnWO4/Co3O4复合材料对10 mg∙L-1 TC溶液的降解率可达80.52%,是单一Co3O4材料的6.2倍;ZnWO4/Co3O4复合材料增强的光催化性能源于ZnWO4导带上的光生电子e-可以通过Zn-O-Co键在界面异质结处与Co3O4价带上的光生空穴h+复合,Co3O4导带上富集光生e-,ZnWO4价带富集光生h+,使ZnWO4/Co3O4复合材料具有Z型光生载流子传输机制,有效地提高了光生载流子的分离效率。ZnWO4负载位点是光催化降解反应的主要活性中心,·OH自由基是主要的光催化反应活性物种,其与·O2-自由基、光生h+共同作用增强了ZnWO4/Co3O4复合材料的光催化性能。

关键词: ZnWO4/Co3O4, Zn-O-Co键, Z型, 四环素, 降解机理

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

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