Bi4O5I2/Bi7O9I3 异质结光催化剂对水中环丙沙星的降解性能

doi:10.11901/1005.3093.2025.187

材料研究学报

2026, Vol. 40

Issue (5): 321-332 DOI: 10.11901/1005.3093.2025.187

光催化专题

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Bi₄O₅I₂/Bi₇O₉I₃ 异质结光催化剂对水中环丙沙星的降解性能

于瀚博¹^,²^,³, 胡妍¹, 徐婷婷¹^,², 张一文¹, 张弛¹^,², 谭杰文¹, 李永翔¹^,², 王晗⁴(

)

^1.长沙理工大学水利与海洋工程学院长沙 410114
^2.洞庭湖水环境治理与生态修复湖南省重点实验室长沙 410114
^3.长沙理工大学土木与环境工程学院长沙 410114
^4.中南大学冶金与环境学院长沙 410083

Degradation Performance of Heterojunction Photocatalyst Bi₄O₅I₂/Bi₇O₉I₃ for Ciprofloxacin Solution

YU Hanbo¹^,²^,³, HU Yan¹, XU Tingting¹^,², ZHANG Yiwen¹, ZHANG Chi¹^,², TAN Jiewen¹, LI Yongxiang¹^,², WANG Han⁴(

)

^1.School of Hydraulic and Ocean Engineering, Changsha University of Science & Technology, Changsha 410114, China
^2.Key Laboratory of Dongting Lake Aquatic Eco-Environmental Control and Restoration of Hunan Province, Changsha 410114, China
^3.School of Civil and Environmental Engineering, Changsha University of Science & Technology, Changsha 410114, China
^4.School of Metallurgy and Environment, Central South University, Changsha 410083, China

引用本文:

于瀚博, 胡妍, 徐婷婷, 张一文, 张弛, 谭杰文, 李永翔, 王晗. Bi₄O₅I₂/Bi₇O₉I₃ 异质结光催化剂对水中环丙沙星的降解性能[J]. 材料研究学报, 2026, 40(5): 321-332.
Hanbo YU, Yan HU, Tingting XU, Yiwen ZHANG, Chi ZHANG, Jiewen TAN, Yongxiang LI, Han WANG. Degradation Performance of Heterojunction Photocatalyst Bi₄O₅I₂/Bi₇O₉I₃ for Ciprofloxacin Solution[J]. Chinese Journal of Materials Research, 2026, 40(5): 321-332.

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摘要:

用溶剂碱度调控法和煅烧制备一种富铋型碘氧化铋异质结光催化剂(Bi₄O₅I₂/Bi₇O₉I₃, Bi4/Bi7)并进行活性物种捕获实验、表征其物相和光电化学性能，研究了其对水中环丙沙星(CIP)的降解性能。结果表明，结构优化的Bi4/Bi7-3异质结光催化剂对CIP的吸附和光降解性能优异，在60 min内其吸附率为88.1%，在其后的30 min内使CIP完全降解。Bi4/Bi7具有由纳米颗粒和纳米片共团聚而成的微球结构，较大的比表面积为催化反应提供了丰富的活性位点，交错排列的能带形成的II型异质结加速了电荷转移。空穴(h⁺)是Bi4/Bi7异质结降解CIP的主要活性物质，超氧自由基( $⋅$ O $2 -$ )和羟基自由基( $⋅$ OH)几乎不参与反应，使其在缺氧环境或自由基竞争环境中也具有较高的活性。

关键词 ：复合材料, Bi₄O₅I₂/Bi₇O₉I₃, 光催化, 环丙沙星

Abstract：

A novel heterojunction photocatalyst of Bi-rich bismuth oxyiodides (Bi₄O₅I₂/Bi₇O₉I₃) was synthesized via regulation of the alkalinity of solvent and followed by calcination, while its degradation performance was examined for ciprofloxacin (CIP) solution. The results showed that the structurally optimized composite heterogeneous catalyst Bi₄O₅I₂/Bi₇O₉I₃-3 exhibits excellent adsorption and photodegradation performance for CIP 20 mg/L solution. Its adsorption rate reaches 88.1% in dark conditions for 60 min, and then subsequently under a simulated sunlight irradiation for 30 min, the CIP is completely degraded. The Bi₄O₅I₂/Bi₇O₉I₃ presents a microsphere morphology composed of nanoparticles and nanosheets. Meanwhile, its large specific surface area provides abundant active sites for the catalytic reaction, and the formed type-II heterojunction with band cross-arrangement can accelerate the charge transfer. Furthermore, the holes (h⁺) are the main active substances for the degradation of CIP in the heterojunction Bi₄O₅I₂/Bi₇O₉I₃, while superoxide free radicals ( $⋅$ O $2 -$ ) and hydroxyl free radicals ( $⋅$ OH) hardly participated in the reaction, thus making them high activity even in an oxygen-depleted environment or in an environment with free radical competition.

Key words： composite Bi₄O₅I₂/Bi₇O₉I₃ photocatalysis ciprofloxacin

收稿日期: 2025-06-03

ZTFLH:

TB331

基金资助:国家自然科学基金(52400202);国家自然科学基金(22306204);湖南省教育厅资助科研项目(24C0149);湖南省大学生创新创业训练计划项目(S202510536125)

通讯作者: 王晗，讲师，han.wang@csu.edu.cn，研究方向为新污染物治理

Corresponding author: WANG Han, Tel: 13548699620, E-mail: han.wang@csu.edu.cn

作者简介: 于瀚博，男，1995年生，博士

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	于瀚博
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https://www.cjmr.org/CN/10.11901/1005.3093.2025.187 或 https://www.cjmr.org/CN/Y2026/V40/I5/321

图1 样品的制备流程

图2 Bi4/Bi7-3、Bi4-S1、Bi4-S2、SP和Bi7的XRD谱

图3 Bi4/Bi7-3的XPS谱

图4 前驱体SP和Bi4/Bi7-3的SEM照片以及Bi4/Bi7-3中的元素映射图

图5 Bi4/Bi7-3复合物和Bi4-S1单体的TEM照片

图6 Bi4/Bi7-3、Bi4-S1和Bi4-S2的N2吸附-脱附图

图7 不同样品的紫外-可见吸收光谱和Tauc Plot图

图8 制备条件不同的样品在可见光下对CIP的降解和吸附

表1 铋系光催化剂降解CIP性能的对比

图9 共存离子和水体对CIP降解的影响

图10 Bi4/Bi7-3对CIP降解的循环实验结果以及用过的催化剂的电镜照片和XRD谱

图11 催化剂的瞬态光电流、交流阻抗和瞬态荧光光谱

图12 催化剂的Mott-Schottky图

图13 捕获剂对CIP降解的影响以及材料的TOC去除效果

图14 光催化降解CIP的机理

[1]	Wang J, Ma M J, Xie P F, et al. Degradation products and toxicity analysis of ciprofloxacin by activation of peroxymonosulfate using CoFe₂O₄@MoS₂ [J]. China Environ. Sci., 2025, 45(5): 2865
[1]	王杰, 马梦杰, 谢鹏飞等. CoFe₂O₄@MoS₂活化PMS降解环丙沙星的产物及毒性分析 [J]. 中国环境科学, 2025, 45(5): 2865
[2]	Li J L, Wang M, Hu F W, et al. Antibiotic pollution characteristics and ecological risk assessment in jinjiang river basin, Jiangxi Province [J]. Environ. Sci., 2022, 43(8): 4064 doi: 10.13227/j.hjkx.202111078 pmid: 35971704
[2]	李佳乐, 王萌, 胡发旺等. 江西锦江流域抗生素污染特征与生态风险评价 [J]. 环境科学, 2022, 43(8): 4064
[3]	Nguyen T D, Itayama T, Ramaraj R, et al. Chronic ecotoxicology and statistical investigation of ciprofloxacin and ofloxacin to Daphnia magna under extendedly long-term exposure [J]. Environ. Pollut., 2021, 291: 118095 doi: 10.1016/j.envpol.2021.118095
[4]	Jin M K, Zhang Q, Zhao W L, et al. Fluoroquinolone antibiotics disturb the defense system, gut microbiome, and antibiotic resistance genes of Enchytraeus crypticus [J]. J. Hazard. Mater., 2022, 424: 127509 doi: 10.1016/j.jhazmat.2021.127509
[5]	Tominaga F K, Boiani N F, Silva T T, et al. Acute and chronic ecotoxicological effects of pharmaceuticals and their mixtures in Daphnia similis [J]. Chemosphere, 2022, 309: 136671 doi: 10.1016/j.chemosphere.2022.136671
[6]	Gao P, Yang Y N, Yin Z, et al. A critical review on bismuth oxyhalide based photocatalysis for pharmaceutical active compounds degradation: modifications, reactive sites, and challenges [J]. J. Hazard. Mater., 2021, 412: 125186 doi: 10.1016/j.jhazmat.2021.125186
[7]	Gao X M, Gao K L, Fu F, et al. Synergistic introducing of oxygen vacancies and hybrid of organic semiconductor: realizing deep structure modulation on Bi₅O₇I for high-efficiency photocatalytic pollutant oxidation [J]. Appl. Catal., 2020, 265B: 118562
[8]	Xia J X, Ji M X, Di J, et al. Improved photocatalytic activity of few-layer Bi₄O₅I₂ nanosheets induced by efficient charge separation and lower valence position [J]. J. Alloy. Compd., 2017, 695: 922 doi: 10.1016/j.jallcom.2016.10.203
[9]	Ding C H, Ye L Q, Zhao Q, et al. Synthesis of Bi _x O _y I _z from molecular precursor and selective photoreduction of CO₂ into CO [J]. J. CO₂ Util., 2016, 14: 135
[10]	Lee W W, Lu C S, Chuang C W, et al. Synthesis of bismuth oxyiodides and their composites: characterization, photocatalytic activity, and degradation mechanisms [J]. RSC Adv., 2015, 5(30): 23450 doi: 10.1039/C4RA15072D
[11]	Zhou H, Du B, Yang P B, et al. Sodium gluconate assisted synthesis of nest-like Bi/β-Bi₂O₃ heterojunction and its visible-light driven photocatalytic activities [J]. Chin. J. Mater. Res., 2024, 38(7): 549
[11]	周慧, 杜彬, 杨鹏斌等. 鸟巢状Bi/β-Bi₂O₃异质结的制备及其可见光催化性能 [J]. 材料研究学报, 2024, 38(7): 549
[12]	Liu X T, Chen S, Tantai X J, et al. Regulating defects in sulfur-doped Bi₄O₅I₂ and constructing S-scheme heterojunctions with g-C₃N₄ to enhance photocatalytic antibiotic degradation [J]. Sep. Purif. Technol., 2025, 363: 132001 doi: 10.1016/j.seppur.2025.132001
[13]	Zhang Y, Zhang M, Luo C, et al. S-scheme heterojunction efficient extraction of hot carriers in CsPbBr₃/Bi₄O₅I₂ for enhanced photocatalytic H₂ evolution and CO₂ reduction [J]. ACS Appl. Energy Mater., 2024, 7(24): 11988 doi: 10.1021/acsaem.4c02419
[14]	Wang W L, Li G, Wang X L, et al. Visible light-driven catalytic degradation of organic pollutants by S-scheme heterojunction Bi₄O₅I₂/NaNbO₃ enhanced by piezoelectric effect [J]. Sep. Purif. Technol., 2025, 356: 129830 doi: 10.1016/j.seppur.2024.129830
[15]	Zhu L L, Shen D K, Zhang H Y, et al. Fabrication of Z-scheme Bi₇O₉I₃/g-C₃N₄ heterojunction modified by carbon quantum dots for synchronous photocatalytic removal of Cr (VI) and organic pollutants [J]. J. Hazard. Mater., 2023, 446: 130663 doi: 10.1016/j.jhazmat.2022.130663
[16]	Liu S S, Jin X L. Preparation of novel Bi₄O₅I₂/Ag₃PO₄ with enhanced visible-light photocatalytic activities [J]. Chem. Phys., 2020, 530: 110625 doi: 10.1016/j.chemphys.2019.110625
[17]	Li Q, Pan X, Wang X G, et al. An S-scheme heterojunction BiOBr QDs/Bi₇O₉I₃ nanoflowers enabling enhanced photocatalytic oxygen evolution [J]. Catal. Commun., 2024, 187: 106843 doi: 10.1016/j.catcom.2024.106843
[18]	Sun Y W, Chen C, Qi X, et al. Synthesis of Z-scheme Ag₃PO₄/MIL-125(Ti) heterojunction and its performance in photocatalytic reduction of Cr(Ⅵ) [J]. Chin. J. Mater. Res., 2023, 37(11): 871
[18]	孙玉伟, 陈畴, 祁昕等. Ag₃PO₄/MIL-125 (Ti) Z型异质结的构建及其光催化还原Cr(Ⅵ)的性能 [J]. 材料研究学报, 2023, 37(11): 871 doi: 10.11901/1005.3093.2022.669
[19]	Yu H B, Huang J H, Jiang L B, et al. Steering photo-excitons towards active sites: intensified substrates affinity and spatial charge separation for photocatalytic molecular oxygen activation and pollutant removal [J]. Chem. Eng. J., 2021, 408: 127334 doi: 10.1016/j.cej.2020.127334
[20]	Jin C Z, Yang Y, Yang X A, et al. Visible photocatalysis of Cr(VI) at g/L level in Si/N-TiO₂ nanocrystals synthesized by one-step co-hydrolysis method [J]. Chem. Eng. J., 2020, 398: 125641 doi: 10.1016/j.cej.2020.125641
[21]	Tu H, Tian B H, Zhao Z C, et al. Research on the influence of g-C₃N₄ microstructure changes on the efficiency of visible light photocatalytic degradation [J]. Water Res. X, 2025, 28: 100315
[22]	Zhao E L, Yang S Z, Zhou Z Y, et al. Oxygen vacancy-enhanced piezo-photocatalytic for tetracycline hydrochloride degradation in wastewater and H₂ evolution [J]. J. Colloid Interface Sci., 2025, 686: 359 doi: 10.1016/j.jcis.2025.01.184
[23]	Zou X, Wang S S, Wu C B, et al. Bi‐modified Bi₂WO₆/BiOI heterojunction with enhanced visible‐light‐driven photoactivity for antibiotic degradation [J]. J. Nanomater., 2022, 2022(1): 5771628 doi: 10.1155/jona.v2022.1
[24]	Khairy M, Mohamed M M, Soliman K A, et al. Boosting ciprofloxacin and indigo carmine dye photodegradation using S-scheme plate-like BiOI@sulfated TiO₂ heterojunctions: an understanding of the performance, the degradation route, and DFT computation [J]. J. Environ. Manage., 2024, 370: 123032 doi: 10.1016/j.jenvman.2024.123032
[25]	Xu Y X, Chen Z H, Ma J, et al. Porous g-C₃N₄ nanosheets modified walnut-like Bi₄O₅I₂ for efficient degradation of antibiotic under visible light: DFT calculations, mechanism and practical application [J]. J. Water Process Eng., 2025, 71: 107180 doi: 10.1016/j.jwpe.2025.107180
[26]	Zeng X C, Zhou Y, He W H, et al. Efficient photocatalytic degradation of ciprofloxacin by doped Bi₄O₅I₂ with Gd³⁺ as an electron trap: Gd³⁺ substitutes Bi³⁺ in the lattice [J]. J. Phys. Chem. Solids, 2024, 188: 111891 doi: 10.1016/j.jpcs.2024.111891
[27]	Zeng Z, Deng Z R, Wang T, et al. Environmentally friendly synthesis of S-scheme heterojunction UiO-66-NH₂/Bi₇O₉I₃ for promoted degradation of ciprofloxacin under visible light: DFT calculation, degradation mechanism and toxicity evaluation [J]. Sep. Purif. Technol., 2023, 311: 123264 doi: 10.1016/j.seppur.2023.123264
[28]	Liu Q H, Wang H L, Huang H, et al. Erythritol assisted facile green synthesis of bismuth-rich photocatalyst Bi₇O₉I₃ with enhanced photocatalytic degradation performance [J]. J. Environ. Chem. Eng., 2023, 11(5): 110611 doi: 10.1016/j.jece.2023.110611
[29]	Yang R X, Li H J, Wang Y T, et al. A novel flower-like Z-type heterojunction CuS/Bi₇O₉I₃ composite catalyst prepared under mild conditions for degradation of antibiotics and sterilization under visible light [J]. Environ. Sci.: Nano, 2020, 7(10): 3074 doi: 10.1039/D0EN00627K
[30]	Yu H B, Chen N L, Li A X, et al. Photocatalytic degradation of tetracycline by bismuth oxybromide co-modified with biochar and oxygen vacancies [J]. China Environ. Sci., 2025, 45(1): 310
[30]	于瀚博, 陈凝露, 李奥祥等. 生物炭与氧空位共修饰溴氧化铋光催化降解四环素 [J]. 中国环境科学, 2025, 45(1): 310
[31]	Rawat A, Srivastava S K, Tiwary C S, et al. An LED-driven Hematite/Bi₄O₅I₂ nanocomposite as an S-scheme heterojunction photocatalyst for efficient degradation of phenolic compounds in real wastewater [J]. J. Mater. Chem., 2025, 13A(2) : 1271
[32]	Tang C, Zhang Y Z, Wang Y F, et al. Preparation of α-Fe₂O₃/TiO₂ photocatalytic material and its performance for phenol degradation [J]. Chin. J. Mater. Res., 2025, 39(3): 233
[32]	唐晨, 张耀宗, 王一凡等. α-Fe₂O₃/TiO₂光催化材料的制备及其降解苯酚的性能 [J]. 材料研究学报, 2025, 39(3): 233
[33]	He R A, Zheng Y Y, Feng J R, et al. In situ synthesis of flexible Bi₇O₉I₃/carbon paper with enhanced photocatalytic activity [J]. J. Mater. Sci. Technol., 2024, 178: 112 doi: 10.1016/j.jmst.2023.07.076
[34]	Sun S M, Wang W Z, Li D Z, et al. Solar light driven pure water splitting on quantum sized BiVO₄ without any cocatalyst [J]. ACS Catal., 2014, 4(10): 3498 doi: 10.1021/cs501076a
[35]	Chen Y X, Zhao C Q, Tan W, et al. Visible light-driven copper vanadate/biochar nanocomposite for heterogeneous photocatalysis degradation of tetracycline: performance, mechanism, and application of machine learning [J]. Environ. Res., 2025, 267: 120747 doi: 10.1016/j.envres.2024.120747
[36]	Jiang L B, Lu Q M, Chen H Y, et al. Visible light-activated porphyrinic zirconium metal-organic framework for ultrafast photo-Fenton-like reaction: efficient internal and external conduction mechanism of photogenerated electrons [J]. Sep. Purif. Technol., 2025, 362: 131937 doi: 10.1016/j.seppur.2025.131937
[37]	Huang L Y, Zheng J H, Ke J Q, et al. Enhancing the photodegradation of tetracycline in aquaculture wastewater via iron(III)-alginate: degradation pathway transformation and toxicity reduction [J]. Chemosphere, 2023, 341: 140021 doi: 10.1016/j.chemosphere.2023.140021
[38]	Liu G, Niu P, Yin L C, et al. α-Sulfur crystals as a visible-light-active photocatalyst [J]. J. Am. Chem. Soc., 2012, 134(22): 9070 doi: 10.1021/ja302897b pmid: 22621225

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