CuFe2O4/BaTiO3 复合材料的制备及其降解四环素的性能

doi:10.11901/1005.3093.2025.306

材料研究学报

2026, Vol. 40

Issue (5): 361-371 DOI: 10.11901/1005.3093.2025.306

光催化专题

本期目录 | 过刊浏览

CuFe₂O₄/BaTiO₃ 复合材料的制备及其降解四环素的性能

张志凯, 雷佳双, 姚冰亚, 陈思雨, 刘硕, 孙玉伟(

), 汤茜

吉林师范大学吉林省新污染物识别与控制重点实验室吉林省靶向识别与光催化降解材料科技创新中心吉林省高校环境材料与污染控制重点实验室工程学院四平 136000

Preparation and Piezoelectric-photocatalytic Performance for Tetracycline Degradation of Z-type Heterojunction Composite CuFe₂O₄/BaTiO₃

ZHANG Zhikai, LEI Jiashuang, YAO Bingya, CHEN Siyu, LIU Shuo, SUN Yuwei(

), TANG Qian

Jilin Provincial Key Laboratory of Emerging Contaminants Identification and Control, Science and Technology Innovation Center of Jilin Province for Targeted Identification and Photocatalytic Degradation Materials, Key Laboratory of Environmental Materials and Pollution Control, the Education Department of Jilin Province, College of Engineering, Jilin Normal University, Siping 136000, China

引用本文:

张志凯, 雷佳双, 姚冰亚, 陈思雨, 刘硕, 孙玉伟, 汤茜. CuFe₂O₄/BaTiO₃ 复合材料的制备及其降解四环素的性能[J]. 材料研究学报, 2026, 40(5): 361-371.
Zhikai ZHANG, Jiashuang LEI, Bingya YAO, Siyu CHEN, Shuo LIU, Yuwei SUN, Qian TANG. Preparation and Piezoelectric-photocatalytic Performance for Tetracycline Degradation of Z-type Heterojunction Composite CuFe₂O₄/BaTiO₃[J]. Chinese Journal of Materials Research, 2026, 40(5): 361-371.

全文: PDF(12172 KB) HTML

摘要:

用溶胶-凝胶法制备CuFe₂O₄/BaTiO₃-2复合材料并使用XRD、SEM、UV-Vis DRS、XPS和PL等手段表征其晶相结构、形貌特征、光吸收性能、价带结构以及电荷分离效率，在超声和300 W氙灯条件下研究了CuFe₂O₄/BaTiO₃体系中CuFe₂O₄降解四环素(TC)的性能。结果表明，这种材料具有压电-光催化协同效应的Z型异质结，CuFe₂O₄的添加提高了BaTiO₃的光催化氧化性能。在TC溶液的浓度为30 mg/L、pH值为10.5的条件下，光照30 min后对TC的去除率可达82.3%。自由基捕获实验结果表明，h⁺和 $⋅$ O $2 -$ 是TC降解过程中的主要活性物种。根据CuFe₂O₄和BaTiO₃的带隙结构，在光照和超声共同作用下CuFe₂O₄/BaTiO₃体系中的光生载流子遵循Z型转移机制，BaTiO₃因超声诱发压电效应并产生内建电场抑制光生载流子的复合。

关键词 ：无机非金属材料, CuFe₂O₄/BaTiO₃, Z型异质结, 压电光催化, 四环素

Abstract：

A Z-scheme heterojunction composite CuFe₂O₄/BaTiO₃ with piezoelectric-photocatalytic synergistic effect was synthesized via sol-gel method. The crystal structure, morphology, optical absorption properties, valence band structure, and charge separation efficiency of the composite were systematically characterized using XRD, SEM, UV-Vis DRS, XPS, and PL spectroscopy. Under combined ultrasound vibration and 300 W xenon lamp irradiation, the influence of the composite CuFe₂O₄/BaTiO₃ with different ratio of CuFe₂O₄ to BaTiO₃ on the degradation of tetracycline (TC) was investigated. The results revealed that the incorporation of CuFe₂O₄ augmented the photocatalytic oxidation efficiency of BaTiO₃. For a solution with TC concentration of 30 mg/L by pH 10.5, a removal efficiency of 82.3% was achieved within 30 min of xenon lamp irradiation. Radical trapping experiments confirmed that h⁺ and $⋅$ O $2 -$ served as the dominant active species in the TC degradation process. Based on the band structures of CuFe₂O₄ and BaTiO₃, it is inferred that under light and ultrasound synergy, the photogenerated carriers in the CuFe₂O₄/BaTiO₃ heterojunction follow a Z-scheme transfer mechanism. The piezoelectric effect induced by ultrasound generates an intrinsic electric field within BaTiO₃, which can effectively suppress the recombination of photogenerated carriers. This work may offer new insights and directions for the synergistic application of piezoelectric and photocatalytic processes in antibiotic degradation.

Key words： inorganic non-metallic materials CuFe₂O₄/BaTiO₃ Z-type heterojunction piezoelectric-photocatalysis tetracycline

收稿日期: 2025-10-20

ZTFLH:

X703.1

基金资助:吉林省科技发展计划(YDZJ202201ZYTS368);吉林省教育厅项目(JJKH20250949KJ)

通讯作者: 孙玉伟，副教授，sunshinesky0427@163.com，研究方向为光催化

Corresponding author: SUN Yuwei, Tel: 13504347197, E-mail: sunshinesky0427@163.com

作者简介: 张志凯，男，2001年生，硕士

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图1 CuFe2O4/BaTiO3-2复合材料和纯BaTiO3、CuFe2O4的XRD谱

图2 BaTiO3的SEM照片、CuFe2O4/BaTiO3-2复合材料的SEM照片和EDS谱

图3 样品的紫外-可见漫反射光谱、(αhv)1/2与hv关系曲线、BaTiO3和CuFe2O4的VB谱以及能带结构

图4 反应前后CuFe2O4/BaTiO3-2的全谱, Ba 3d, Ti 2p, O 1s, Cu 2p和Fe 2p的高分辨率XPS光谱

图5 各样品的红外光谱

图6 各样品的压电光催化降解性能和压电光催化降解TC的一级动力学曲线

表1 各种光催化剂的总结和比较[1,11,35~37]

图7 催化剂的投加量、TC的初始浓度以及初始pH值对光催化剂降解性能的影响

图8 各样品的EIS谱和PL光谱以及活性物种的捕获性能和降解率

图9 CuFe2O4/BaTiO3-2的压电光催化降解TC的机制

图10 CuFe2O4/BaTiO3-2的压电光催化循环性能和光催化反应前后的XRD谱

图11 推测的TC光降解路径

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