Ag-Ti<sup>3+</sup>-TiO<sub>2</sub>纳米锥的制备及光电催化性能研究

doi:10.19965/j.cnki.iwt.2023-0173

摘要/Abstract

摘要：

抗生素的过度使用对环境造成了持久性的污染，光电催化是降解抗生素的环保、高效技术，其中光电极的设计尤为重要。为提高抗生素降解速率，采用电化学还原和光还原法制备了Ag-Ti³⁺-TiO₂纳米锥复合光电极，并用于模拟可见光照射下光电催化降解四环素的过程，考察其光电催化性能。结果表明，由于Ti³⁺自掺杂和Ag纳米颗粒的局域表面等离子体共振效应，复合电极有效地抑制了光生电子-空穴对的复合，并表现出更低的电荷转移电阻，提高了光电催化性能。复合光电极在可见光照射下，90 min后可降解87.9%的四环素，且5个循环后降解率保持在82.5%。这些结果表明，Ag-Ti³⁺-TiO₂纳米锥复合光电极具有高降解效率、良好的稳定性和可持续的循环利用性，有望实现高效环保地光电催化降解抗生素。

关键词: 光电催化, TiO₂, 四环素, 可见光

Abstract:

The overuse of antibiotics has caused persistent pollution to the environment，and photo-electrocatalysis is an environmentally friendly and efficient technology for degrading antibiotics，in which the design of photoelectrodes is particularly important. To improve the rate of antibiotic degradation，Ag-Ti³⁺-TiO₂ nanocone composite photoelectrode was prepared by electrochemical reduction and photoreduction methods. Then it was used to simulate the photo-electrocatalytic degradation of tetracycline under visible light irradiation to investigate its photocatalytic performance. The results showed that the composite electrode effectively suppressed the complexation of photogenerated electron-hole pairs and exhibited a lower charge transfer resistance to improve the photo-electrocatalytic performance due to the Ti³⁺ self-doping and the local surface plasmon resonance effect of Ag nanoparticles. The composite photoelectrode degraded 87.9% of tetracycline after 90 min under visible light irradiation，and the degradation rate was maintained at 82.5% after 5 cycles. These results indicated that the Ag-Ti³⁺-TiO₂ nanocone composite photoelectrode had high degradation efficiency，good stability and sustainable recyclability，and was expected to achieve efficient and environmentally friendly photo-electrocatalytic degradation of antibiotics.

Key words: photo-electrocatalysis, TiO₂, tetracycline, visible light

中图分类号:

X703

张会霞, 谢陈鑫, 周立山, 任春燕, 赵慧, 雷太平, 朱令之. Ag-Ti³⁺-TiO₂纳米锥的制备及光电催化性能研究[J]. 工业水处理, 2024, 44(3): 159-167.

Huixia ZHANG, Chenxin XIE, Lishan ZHOU, Chunyan REN, Hui ZHAO, Taiping LEI, Lingzhi ZHU. Preparation and photo-electrocatalytic performance of Ag-Ti³⁺-TiO₂ nanocone[J]. Industrial Water Treatment, 2024, 44(3): 159-167.

https://www.iwt.cn/CN/Y2024/V44/I3/159

图/表 11

图1 不同光阳极的XRD

Fig.1 XRD patterns of different photoanodes

图2 ATT2的XPS

Fig.2 XPS spectra of ATT2

图3 不同光阳极的SEM

Fig.3 SEM images of different photoanodes

图4 ATT2的EDX（a）和元素映射图（b~d）

Fig.4 EDX spectra （a） and element mapping （b-d）of ATT2

图5 不同光阳极的光电性能

Fig.5 Photoelectric performances of different photoanodes

图6 ATT2光阳极在不同的偏置电压（a）、pH（b）、实验体系（c）下对TC的降解效果，以及不同光阳极对TC降解的影响（d）

Fig.6 Effects of ATT2 photoanode on TC degradation under different bias voltage（a），pH（b），experimental system（c），and effects of different photoanodes on degradation of TC（d）

图7 ATT2光阳极5次循环实验的TC降解率（a）和5次循环实验前后的XRD比较（b）

Fig.7 Degradation rates of TC in five cycles experiment（a） and XRD comparison（b） before and after cycling of ATT2 photoanode

图8 ATT2降解TC可能的途径

Fig.8 The possible degradation pathways of TC by ATT2

图9 自由基捕获实验（a）和ATT2 TEMPO-h⁺的ESR光谱（b）

Fig.9 Radicals trapping experiments（a） and ESR spectra for TEMPO-h⁺ with ATT2（b）

图10 TT光电极带隙能（a）及VB-XPS价带谱（b）

Fig.10 The band gap energies（a） and VB-XPS spectra（b） of TT photoanode

图11 光生电子-空穴对分离与转移机理示意

Fig.11 photo-generated electron-hole pairs separation and transfer mechanism

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Ag-Ti³⁺-TiO₂纳米锥的制备及光电催化性能研究

Preparation and photo-electrocatalytic performance of Ag-Ti³⁺-TiO₂ nanocone

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Ag-Ti³⁺-TiO₂纳米锥的制备及光电催化性能研究

Preparation and photo-electrocatalytic performance of Ag-Ti³⁺-TiO₂ nanocone