无机/有机异质结中S型电荷分离增强光芬顿降解抗生素及抑菌性能

doi:10.1016/S1872-2067(24)60265-2

催化学报 ›› 2025, Vol. 72: 106-117.DOI: 10.1016/S1872-2067(24)60265-2

无机/有机异质结中S型电荷分离增强光芬顿降解抗生素及抑菌性能

秦浩天^,¹, 黄雨欣^,¹, 程强, 严素定, 王楷^*()

湖北师范大学城市与环境学院, 黄石市土壤污染防治重点实验室, 湖北黄石 435002

收稿日期:2024-11-22 接受日期:2025-01-06 出版日期:2025-05-18 发布日期:2025-05-20
通讯作者: *电子信箱: wangkai@hbnu.edu.cn (王楷).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(22378104);国家自然科学基金(52104254);湖北省教育厅科学研究计划重点项目(D20232502);湖北省自然科学基金(2022CFB504);湖北省高等学校优秀中青年科技创新团队(T2023021)

Boosting charge transfer at inorganic/organic S-scheme interface for photo-Fenton degradation of antibiotics and bacterial inactivation

Haotian Qin^,¹, Yuxin Huang^,¹, Qiang Cheng, Suding Yan, Kai Wang^*()

College of Urban and Environmental Sciences, Huangshi Key Laboratory of Prevention and Control of Soil Pollution, Hubei Normal University, Huangshi 435002, Hubei, China

Received:2024-11-22 Accepted:2025-01-06 Online:2025-05-18 Published:2025-05-20
Contact: *E-mail: wangkai@hbnu.edu.cn (K. Wang).
About author:¹ These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22378104);National Natural Science Foundation of China(52104254);Research Project of Hubei Provincial Department of Education(D20232502);Natural Science Foundation of Hubei Province(2022CFB504);Program for Innovative Teams of Outstanding Young, and the Middle-aged Researchers in the Higher Education Institutions of Hubei Province(T2023021)

摘要/Abstract

摘要：

天然水体中残留抗生素及耐药性细菌对水生环境和人类健康构成了严重威胁. 光芬顿氧化法作为一类新兴的高级氧化技术, 通过太阳光激发生成活性物种如电子、空穴、羟基和超氧等自由基与污染物反应, 使污染物降解为小分子物质或完全矿化, 在抗生素降解及抑菌领域具有广阔的应用前景. 合适的光芬顿催化剂是高效降解抗生素及抑菌的关键. 针对单一铁基催化剂比表面积小所导致的表面活性位点少、易产生铁泥、循环性差等问题, 构建铁基异质结光芬顿催化剂用于高效降解抗生素及抑菌势在必行. 相较于传统Ⅱ型异质结, 梯型(S型)异质结可以有效促进光生电子-空穴对的分离和转移, 催化体系具有更强的氧化和还原能力, 在有效降低电子空穴对的复合速率的同时提升光芬顿反应过程中的电子传输动力学, 增强光芬顿催化剂的活性和稳定性.

本文以溶剂热法合成的Fe₂TiO₅ (FTO)中间体为基底, 通过一步煅烧处理方法制备了无机/有机Fe₂TiO₅@g-C₃N₄ (FTOCN) S型异质结光芬顿催化剂. X射线粉末衍射、傅里叶红外光谱、透射电子显微镜、热重分析以及X射线光电子能谱等表征证实了系列FTOCN光芬顿催化剂的成功合成, 并分析其物化性质. 紫外-可见漫反射分析结合密度泛函理论计算表明, FTOCN异质结的构建显著提高了可见光利用率; 结合莫特-肖特基分析, 确定了FTO和CN的价导带位置, FTO和CN的能带结构满足S型电荷传输路径. 利用瞬态光电流、电化学阻抗谱及表面光电压技术证明了FTOCN异质结的构建显著促进了体系的电荷分离. 利用原位辐照开尔文探针力显微镜及原位辐照X射线光电子能谱验证了无机/有机FTOCN异质结的电荷转移路径遵从S型机理, 结合飞秒瞬态吸收光谱探明其载流子动力学. 在可见光照射下, 最佳配比的FTOCN异质结对四环素的降解速率常数分别为单一FTO和CN的1.6和5.2倍; 同步分析了催化剂投加量、抗生素初始浓度、H₂O₂浓度、阴离子干扰、环境pH值对光芬顿反应的影响. 此外, 该光芬顿催化剂具有较好的环境普适性, 对环丙沙星、头孢及偶氮染料均保持良好的光芬顿活性, 且对天然水体具有良好的抑菌活性. 结合电子自旋共振谱分析光芬顿体系中的活性物种.

综上, 本文提出了采用设计具有强界面电荷传输的无机/有机S型异质结策略能够有效提升材料的光芬顿催化降解抗生素及抑菌性能, 为构筑新型高级氧化催化材料用于环境治理提供参考.

关键词: 光芬顿反应, 无机/有机异质结, 抗生素降解, 抑菌, S型机理

Abstract:

Solar-driven Fenton-like reactions are promising strategies for degrading pharmaceutical wastewater to address environmental challenges and antibiotic pollution. However, its efficacy is limited by suboptimal light absorption efficiency, rapid charge recombination, and inadequate interfacial charge transfer. In this study, an inorganic/organic S-scheme photo-Fenton system of pseudobrookite/carbon nitride (FTOCN) was synthesized via a hydrothermally coupled calcination process for the effective purification of tetracycline antibiotics under visible-light irradiation. The optimized FTOCN-2 heterostructure exhibits a significantly enhanced TC degradation capacity of 90% within 60 min. The rate constant of FTOCN-2 is 1.6 and 5.2 times greater than those of FTO and CN, respectively. Furthermore, FTOCN exhibits high antibacterial efficacy, highlighting its potential application in the purification of natural water. Measurements via a range of analytical techniques, including Kelvin probe force microscopy, density functional theory calculations, in situ X-ray photoelectron spectroscopy, and femtosecond transient absorption spectroscopy, corroborate the S-scheme mechanism. This study provides a novel perspective for the development of photo-Fenton systems with S-scheme heterojunctions for water purification.

Key words: Photo-Fenton reaction, Inorganic/organic heterojunction, Antibiotics degradation, Bacterial inactivation, S-scheme mechanism

秦浩天, 黄雨欣, 程强, 严素定, 王楷. 无机/有机异质结中S型电荷分离增强光芬顿降解抗生素及抑菌性能[J]. 催化学报, 2025, 72: 106-117.

Haotian Qin, Yuxin Huang, Qiang Cheng, Suding Yan, Kai Wang. Boosting charge transfer at inorganic/organic S-scheme interface for photo-Fenton degradation of antibiotics and bacterial inactivation[J]. Chinese Journal of Catalysis, 2025, 72: 106-117.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60265-2

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图/表 8

Fig. 1. (a) Synthesis procedure for FTOCN composites. TEM images of FTO (b) and FTOCN-2 (c). HRTEM (d) and elemental mapping (e) images of FTOCN-2.

Fig. 2. XRD patterns (a), TG curves (b), and UV-vis DRS spectra (c) of FTO, CN, and FTOCN-X (X = 1, 2, or 3) composites. (d) Calculated PDOS plots of FTO, CN, and FTOCN. (e) Zoomed-in PDOS plots of FTOCN. (f) Band structure diagrams of FTO and CN.

Fig. 3. Photocatalytic degradation curves (a) and pseudo-first-order kinetics (b) of TC over various catalysts under visible light irradiation. Influence of catalyst dosage (c), anions (d), pH (e), and recycling runs (f) on the TC degradation efficiency of FTOCN-2. (g) Photo-Fenton degradation of different pollutants over FTOCN-2. (h) Photocatalytic antibacterial properties of FTO, CN, and FTOCN-2 on samples from the Yangtze River.

Fig. 4. Photocurrent curves (a) and EIS plots (b) of FTO, CN, and FTOCN-2. (c) Photoluminescence spectra of FTO, CN, and FTOCN-X (X = 1, 2, or 3) samples. AFM images, KPFM potential images, and corresponding potential difference curves along the lines in under dark conditions and illumination for FTO (d) and FTOCN-2 (e).

Fig. 5. Work functions of FTO (a) and CN (b). 3D (c) and planar (d) averaged charge for the FTOCN composite (Fe: gold; Ti: blue; O: red; C: brown; and N: silver).

Fig. 6. High-resolution XPS spectra of Fe 2p (a), Ti 3d (b), C 1s (c), and N 1s (d) for FTO, CN, and FTOCN-2. In situ XPS measurements were performed under UV light illumination. (e) Schematic illustration of the charge transfer and separation mechanisms over FTOCN heterojunctions.

Fig. 7. 2D pseudocolor TA spectra of FTO (a) and FTOCN-2 (b) using a 400-nm pump pulse. TA spectra of FTO (c) and FTOCN-2 (d) at indicated time delays. (e) TA kinetics of FTO and FTOCN-2 probed at 650 nm. (f) Schematic of electron quenching pathways in a FTOCN heterojunction.

Fig. 8. (a) Effects of scavengers on photo-Fenton degradation over FTOCN-2. EPR spectra of DMPO-?O2- (b) and DMPO-?OH (c) for FTO, CN, and FTOCN-2. (d) Mechanism of the photo-Fenton reaction at the FTOCN heterojunction.

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无机/有机异质结中S型电荷分离增强光芬顿降解抗生素及抑菌性能

Boosting charge transfer at inorganic/organic S-scheme interface for photo-Fenton degradation of antibiotics and bacterial inactivation

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