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

doi:10.15541/jim20250506

无机材料学报 ›› 2026, Vol. 41 ›› Issue (9): 1294-1302.DOI: 10.15541/jim20250506

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 齐齐哈尔大学化学与化学工程学院, 齐齐哈尔 161006
² 齐齐哈尔大学分析测试中心, 齐齐哈尔 161006

收稿日期:2025-12-18 修回日期:2026-02-10 出版日期:2026-09-20 网络出版日期:2026-02-28
通讯作者: 殷广明, 正高级实验师. E-mail: qdyingm@163.com
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 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 Published:2026-09-20 Online:2026-02-28
Contact: YIN Guangming, professor. E-mail:qdyingm@163.com
About author:LI Jinglin (1999-), female, Master candidate. E-mail: 2261735804@qq.com
Supported by:
Heilongjiang Provincial Natural Science Foundation of China(LH2024B028)

摘要/Abstract

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 act as 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

中图分类号:

O649

李婧琳, 殷广明, 郑建华, 杨红光, 关芳芳, 黄欣宇, 曹欣雨. 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[J]. 无机材料学报, 2026, 41(9): 1294-1302.

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, 2026, 41(9): 1294-1302.

图/表 9

图1 材料的表征结果

Fig. 1 Characterization results of materials (a) SEM image, (b) EDS spectrum, and (c) element mappings of 15-Zn-Co; (d) XRD patterns of ZnWO4, Co3O4 and ZnWO4/Co3O4 composite materials

图2 材料的FT-IR和XPS谱图

Fig. 2 FT-IR and XPS spectra of materials (a) FT-IR spectra; (b) Survey spectra; (c) Co2p; (d) O1s; (e) Zn2p; (f) W4f

图3 材料的(a) UV-Vis DRS图、(b)带隙图、(c) I-t曲线和(d) EIS图

Fig. 3 (a) UV-Vis DRS spectra, (b) bandgap plots, (c) I-t curves, and (d) EIS plots of materials

图4 (a)不同材料的光催化降解率对比图和(b)15-Zn-Co的循环降解率对比图

Fig. 4 Comparisons of (a) photocatalytic degradation rates of different materials and (b) cyclic degradation rate of 15-Zn-Co

图5 光催化机理分析

Fig. 5 Analysis of photocatalytic mechanism (a) Photocatalytic degradation with different capture agents; (b, c) Mott-Schottky curves of (b) Co3O4 and (c) ZnWO4; (d) Schematic diagram of photodegradation process

图S1 (a) ZnWO4、(b) Co3O4、(c) 10-Zn-Co和(d) 20-Zn-Co的SEM照片

Fig. S1 SEM images of (a) ZnWO4, (b) Co3O4, (c) 10-Zn-Co and (d) 20-Zn-Co

表S1 Co2p、O1s、Zn2p和W4f的电子结合能峰值

Table S1 Peak electronic binding energies of Co2p, O1s, Zn2p and W4f

Sample	Co2p				O1s		W4f		Zn2p
Sample	Co³⁺2p_1/2	Co³⁺2p_3/2	Co²⁺2p_1/2	Co²⁺2p_3/2	Co-O	Zn-O	W4f_5/2	W4f_7/2	Zn2p_1/2	Zn2p_3/2
Co₃O₄	793.45	778.40	794.90	779.75	529.35	--
10-Zn-Co	793.45	778.28	794.78	779.63	529.24	530.91	35.42	37.51	1044.85	1021.73
15-Zn-Co	793.19	778.17	794.67	779.50	529.11	531.04	35.55	37.63	1044.96	1021.84
20-Zn-Co	793.08	778.05	794.55	779.50	528.98	531.14	35.67	37.75	1045.08	1021.96
ZnWO₄	--					530.80	35.13	37.49	1044.70	1021.60

图S2 不同条件下15-Zn-Co对TC的光催化降解曲线

Fig. S2 Photocatalytic degradation curves of 15-Zn-Co on TC under different conditions (a) Dosages of 15-Zn-Co; (b) pH; (c) Mass concentrations of TC solution

表S2 部分文献与本研究光催化降解TC对比[30-37]

Table S2 Comparison of partial literature and this work on photocatalytic degradation of TC[30-37]

Photocatalyst	Dosage/mg	TC/(mg·L^-1)	Time/min	Degradation rate/%	Ref.
Co₃O₄/Nb₂O₅	50	15	150	72.6	[30]
Co₃O₄/g-C₃N₄	50	10	120	73.8	[31]
Co₃O₄/Bi₂O₃/rGO	50	50	90	97.0	[32]
BiOIO₃/BiOBr	80	20	80	74.9	[33]
NiFe₂O₄/Ag₂WO₄	60	40	90	92.3	[34]
CuO/CePO₄	100	10	180	84.58	[35]
LaCoO₃/Bi₂WO₆	30	20	150	85.5	[36]
BiFeO₃/ZIF-67	30	30	120	72.1	[37]
ZnWO₄/Co₃O₄	30	10	120	80.52	This work

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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

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

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