BiOX(X=Cl,Br,I)复合光催化材料降解水体中抗生素研究进展

doi:10.19894/j.issn.1000-0518.200318

摘要/Abstract

摘要： 抗生素大量使用致使其在水环境中普遍存在,对生态环境和人类健康造成一定威胁。卤氧化铋BiOX(X=Cl,Br,I)具有独特二维层状结构、适宜的禁带宽度等优点而被用作光催化剂来降解水中残留的抗生素。但单一BiOX(X=Cl,Br,I) 存在可见光吸收能力偏弱、稳定性不佳等问题,往往需要对其进行复合改性(如金属负载、碳材料修饰及构建异质结)来提升去除水中抗生素的性能。本文主要介绍了用于水体中抗生素类污染物降解的BiOX(X=Cl,Br,I)复合光催化材料的设计合成、活性增强机制以及光催化反应机理。相比于金属负载及碳材料修饰,构建半导体异质结是常用且经济有效地增强BiOX(X=Cl,Br,I)光催化降解水中抗生素性能的方法。指出该领域以后的研究需要评估BiOX(X=Cl,Br,I)复合光催化材料降解水环境中不同类型抗生素的效果,同时还需揭示自然水体的背景成分(如溶解性有机质、无机离子等)对该类复合光催化剂去除水中抗生素活性和稳定性的影响。最后提出引入过氧化物来提升BiOX复合光催化体系矿化水中抗生素的效果以及构建磁性BiOX光催化材料来解决降解反应后的固-液分离问题。

关键词: 卤氧化铋, 催化剂, 抗生素, 降解, 反应机制

Abstract: The large-scale use of antibiotics makes them ubiquitous in the water environment, which poses a certain threat to the ecological environment and human health. Bismuth oxychloride (BiOX (X=Cl, Br, I)) can be used as a photocatalyst to degrade residual antibiotics in water due to its unique two-dimensional layered structure and suitable bandgap. However, BiOX (X=Cl, Br, I) has problems including weak visible light absorption capacity and poor stability, which often requires composite modification (such as metal loading, carbon material modification, and construction of heterojunctions) to improve their performance for removing antibiotics in water. This paper mainly introduces the design, synthesis, mechanism of activity enhancement and photocatalytic reaction mechanisms of BiOX (X=Cl, Br, I) composite photocatalysts for the degradation of antibiotics in water. Compared with metal loading and carbon material modification, the construction of semiconductor heterojunction is a common and cost-effective method to enhance the performance of BiOX (X=Cl, Br, I) photocatalytic degradation of antibiotics in water. It is pointed out that the future research in this field need to evaluate the performance of BiOX (X=Cl, Br, I) composite photocatalytic materials by degrading the different types of antibiotics in water, and it is also necessary to reveal the effect of the background components of natural water bodies (such as dissolved organic matter, inorganic ions, etc.) on the removal of antibiotics using BiOX (X=Cl, Br, I) composite photocatalysts. Finally, it is proposed to introduce peroxide to enhance the effect of BiOX composite photocatalytic system to mineralize antibiotics in water and constructing the magnetic BiOX photocatalytic materials could solve the problem of solid-liquid separation after degradation reaction.

Key words: Bismuth oxychloride, Catalyst, Antibiotics, Degradation, Reaction mechanism

中图分类号:

O643

贺全宝, 胡征, 葛明. BiOX(X=Cl,Br,I)复合光催化材料降解水体中抗生素研究进展[J]. 应用化学, 2021, 38(7): 754-766.

HE Quan-Bao, HU Zheng, GE Ming. Research Progress on Photo-degradation of Antibiotics in Water by BiOX(X=Cl,Br,I) Composite Photocatalytic Materials[J]. Chinese Journal of Applied Chemistry, 2021, 38(7): 754-766.

参考文献

[1] 罗玉, 黄斌, 金玉, 等. 污水中抗生素的处理方法研究进展[J]. 化工进展, 2014, 33(9): 2471-2477.
LUO Y, HUANG B, JIN Y, et al. Research progress in the degradation of antibiotics wastewater treatment[J]. Chem Ind Eng Prog, 2014, 33(9): 2471-2477
[2] 张国栋, 董文平, 刘晓晖, 等. 我国水环境中抗生素赋存、归趋及风险评估研究进展[J]. 环境化学, 2018, 37(7): 1491-1500.
ZHANG G D, DONG W P, LIU X H, et al. Occurrence, fate and risk assessment of antibiotics in water environment of China[J]. Environ Chem, 2018, 37(7): 1491-1500.
[3] ZHANG Q Q, YING G G, PAN C G, et al. Comprehensive evaluation of antibiotics emission and fate in the river basins of China: source analysis, multimedia modeling, and linkage to bacterial resistance[J]. Environ Sci Technol, 2015, 49(11): 6772-6782.
[4] LI D, SHI W. Recent developments in visible-light photocatalytic degradation of antibiotics[J]. Chinese J Catal, 2016, 37(6): 792-799.
[5] 王燕琴, 瞿梦, 冯红武, 等. 卤氧化铋光催化剂的研究进展[J]. 化工进展, 2014(3): 660-667.
WANG Y Q, QU M, FENG H W, et al. Research progress in bismuth oxyhalide compouds photocatalysts[J]. Chem Ind Eng Prog, 2014(3): 660-667.
[6] SHARMA K, DUTTA V, SHARMA S, et al. Recent advances in enhanced photocatalytic activity of bismuth oxyhalides for efficient photocatalysis of organic pollutants in water: a review[J]. J Ind Eng Chem, 2019, 78: 1-20.
[7] LYU J, HU Z, LI Z, et al. Removal of tetracycline by BiOBr microspheres with oxygen vacancies: combination of adsorption and photocatalysis[J]. J Phys Chem Solids, 2019, 129: 61-70.
[8] YU H, SHI R, ZHAO Y, et al. Smart utilization of carbon dots in semiconductor photocatalysis[J]. Adv Mater, 2016, 28(43): 9454-9477.
[9] LI M, LIU Y, ZENG G, et al. Graphene and graphene-based nanocomposites used for antibiotics removal in water treatment: a review[J]. Chemosphere, 2019, 226: 360-380.
[10] DONG S, PI Y, LI Q, et al. Solar photocatalytic degradation of sulfanilamide by BiOCl/reduced graphene oxide nanocomposites: mechanism and degradation pathways[J]. J Alloys Compd, 2016, 663: 1-9.
[11] ZHANG J, WANG Z, FAN M, et al. Ultra-light and compressible 3D BiOCl/ RGO aerogel with enriched synergistic effect of adsorption and photocatalytic degradation of oxytetracycline[J]. J Mater Res Technol, 2019, 8(5): 4577-4587.
[12] MOU Z, ZHANG H, LIU Z, et al. Ultrathin BiOCl/nitrogen-doped graphene quantum dots composites with strong adsorption and effective photocatalytic activity for the degradation of antibiotic ciprofloxacin[J]. Appl Surf Sci, 2019, 496: 143655.
[13] ZHANG J, GUO Y, XIONG Y, et al. Environment-friendly 0D/2D Ag/CDots/BiOCl heterojunction with enhanced photocatalytic tetracycline degradation and mechanism insight[J]. J Photochem Photobiol A, 2018, 356: 411-417.
[14] LIANG Z, YANG J, ZHOU C, et al. Carbon quantum dots modified BiOBr microspheres with enhanced visible light photocatalytic performance[J]. Inorg Chem Commun, 2018, 90: 97-100.
[15] DI J, XIA J, JI M, et al. Nitrogen-doped carbon quantum Dots/BiOBr ultrathin nanosheets: in situ strong coupling and improved molecular oxygen activation ability under visible light irradiation[J]. ACS Sustainable Chem Eng, 2016, 4(1): 136-146.
[16] 郑乐媚, 关亦玮, 文定, 等. BiOBr/GO复合纳米光催化剂的制备及可见光下降解环丙沙星废水[J]. 环境化学, 2020, 39(8): 2137-2146.
ZHENG L M, GUAN Y W, WEN D, et al.Preparation of BiOBr /GO composition nanocatalysts and application of degradation of ciprofloxacin wastewater in visible light[J]. Environ Chem, 2020, 39(8): 2137-2146.
[17] NIU J, DAI P, WANG K, et al. Enhanced visible-light photocatalytic activity of BiOI-MWCNT composites synthesised via rapid and facile microwave hydrothermal method[J]. Mater Technol, 2019, 34: 506-514.
[18] MAIMAITIZI H, ABULIZI A, KADEER K, et al. In situ synthesis of Pt and N co-doped hollow hierarchical BiOCl microsphere as an efficient photocatalyst for organic pollutant degradation and photocatalytic CO₂ reduction[J]. Appl Surf Sci, 2020, 502: 144083.
[19] WU S S, SU Y M, ZHU Y, et al. In-situ growing Bi/BiOCl microspheres on Ti₃C₂ nanosheets for upgrading visible-light-driven photocatalytic activity[J]. Appl Surf Sci, 2020, 502: 146339.
[20] GAO Z, YAO B, YANG F, et al. Preparation of BiOBr-Bi heterojunction composites with enhanced photocatalytic properties on BiOBr surface by in-situ reduction[J]. Mater Sci Semicond Process, 2020, 108: 104882.
[21] 葛明, 李振路. 基于银系半导体材料的全固态Z型光催化体系[J]. 化学进展, 2017, 29(8): 846-858.
GE M, LI Z L. All-solid-state Z-scheme photocatalytic systems based on silver-containing semiconductor materials[J]. Prog Chem, 2017, 29(8): 846-858.
[22] ZHOUP, YU J, JARONIEC M. All-solid-state Z-scheme photocatalytic systems[J]. Adv Mater, 2014, 26(29): 4920-4935.
[23] MA X, MA Z, LIAO T, et al. Preparation of BiVO₄/BiOCl heterojunction photocatalyst by in-situ transformation method for norfloxacin photocatalytic degradation[J]. J Alloys Compd, 2017, 702: 68-74.
[24] LIANG Z, ZHOU C, YANG J, et al. Visible light responsive Bi₂WO₆/BiOCl heterojunction with enhanced photocatalytic activity for degradation of tetracycline and rohdamine B[J]. Inorg Chem Commun, 2018, 93: 136-139.
[25] LI S, CHEN J, LIU Y, et al. In situ anion exchange strategy to construct flower-like BiOCl/BiOCOOH p-n heterojunctions for efficiently photocatalytic removal of aqueous toxic pollutants under solar irradiation[J]. J Alloys Compd, 2019, 781: 582-588.
[26] GUPTA G, KANSAL S K. Novel 3-D flower like Bi₃O₄Cl/BiOCl p-n heterojunction nanocomposite for the degradation of levofloxacin drug in aqueous phase[J]. Process Saf Environ Prot, 2019, 128: 342-352.
[27] WANG H X, LIAO B, LU T, et al.Enhanced visible-light photocatalytic degradation of tetracycline by a novel hollow BiOCl@CeO₂ heterostructured microspheres: structural characterization and reaction mechanism[J]. J Hazard Mater, 2020, 385: 121552.
[28] ZHOU F, YAN C, LIANG T, et al. Photocatalytic degradation of Orange G using sepiolite-TiO₂ nanocomposites: optimization of physicochemical parameters and kinetics studies[J]. Chem Eng Sci, 2018, 183: 231-239.
[29] HU X, SUN Z, SONG J, et al. Synthesis of novel ternary heterogeneous BiOCl/TiO₂/sepiolite composite with enhanced visible-light-induced photocatalytic activity towards tetracycline[J]. J Colloid Interface Sci, 2019, 533: 238-250.
[30] PRIYA B, RAIZADA P, SINGH N, et al. Adsorptional photocatalytic mineralization of oxytetracycline and ampicillin antibiotics using Bi₂O₃/BiOCl supported on graphene sand composite and chitosan[J]. J Colloid Interface Sci, 2016, 479: 271-283.
[31] REN X, WU K, QIN Z, et al. The construction of type II heterojunction of Bi₂WO₆/BiOBr photocatalyst with improved photocatalytic performance[J]. J Alloys Compd, 2019, 788: 102-109.
[32] RASHID J, ABBAS A, CHANG L C, et al. Butterfly cluster like lamellar BiOBr/TiO₂ nanocomposite for enhanced sunlight photocatalytic mineralization of aqueous ciprofloxacin[J]. Sci Total Environ, 2019, 665: 668-677.
[33] FU S, YUAN W, LIU X, et al. A novel 0D/2D WS₂/BiOBr heterostructure with rich oxygen vacancies for enhanced broad-spectrum photocatalytic performance[J]. J Colloid Interface Sci, 2020, 569: 150-163.
[34] GUO C, GAO S, LV J, et al. Assessing the photocatalytic transformation of norfloxacin by BiOBr/iron oxides hybrid photocatalyst: kinetics, intermediates, and influencing factors[J]. Appl Catal , B, 2017, 205: 68-77.
[35] ZHU S R, QI Q, ZHAO W N, et al. Enhanced photocatalytic activity in hybrid composite combined BiOBr nanosheets and Bi₂S₃ nanoparticles[J]. J Phys Chem Solids, 2018, 121: 163-171.
[36] SU X, WU D. Controllable synthesis of plate BiOBr loaded plate Bi₂O₂CO₃ with exposed {001} facets for ciprofloxacin photo-degradation[J]. J Ind Eng Chem, 2018, 64: 256-265.
[37] SU X, WU D. Facile construction of the phase junction of BiOBr and Bi₄O₅Br₂ nanoplates for ciprofloxacin photodegradation[J]. Mater Sci Semicond Process, 2018, 80: 123-130.
[38] SHI Z, ZHANG Y, SHEN X F, et al.Fabrication of g-C₃N₄/BiOBr heterojunctions on carbon fibers as weaveable photocatalyst for degrading tetracycline hydrochloride under visible light[J]. Chem Eng J, 2020, 386: 124010.
[39] PI Y, LI X, XIA Q, et al. Adsorptive and photocatalytic removal of persistent organic pollutants (POPs) in water by metal-organic frameworks (MOFs)[J]. Chem Eng J, 2018, 337: 351-371.
[40] HU Q, CHEN Y, LI M, et al. Construction of NH₂-UiO-66/BiOBr composites with boosted photocatalytic activity for the removal of contaminants[J]. Colloids Surf A, 2019, 579: 123625.
[41] CHEN Y, LIU Y, XIE X, et al. Synthesis flower-like BiVO₄/BiOI core/shell heterostructure photocatalyst for tetracycline degradation under visible-light irradiation[J]. J Mater Sci: Mater Electron, 2019, 30: 9311-9321.
[42] NIU J, ZHANG Z, DAI P, et al. Facile synthesis of γ-Fe₂O₃/BiOI microflowers with enhanced visible light photocatalytic activity[J]. Mater Des, 2018, 150: 29-39.
[43] LI S, XUE B, WANG C, et al. Facile fabrication of flower-like BiOI/BiOCOOH p-n heterojunctions for highly efficient visible-light-driven photocatalytic removal of harmful antibiotics[J]. Nanomaterials, 2019, 9(11): 1571.
[44] PARAMANIK L, REDDY K H, PARIDA K M. Stupendous photocatalytic activity of p-BiOI/n-PbTiO₃ heterojunction: the significant role of oxygen vacancies and interface coupling[J]. J Phys Chem C, 2019, 123(35): 21593-21606.
[45] WEN X J, NIU C G, ZHANG L, et al. An in depth mechanism insight of the degradation of multiple refractory pollutants via a novel SrTiO₃/BiOI heterojunction photocatalysts[J]. J Catal, 2017, 356: 283-299.
[46] ARUMUGAM M, LEE S J, BEGILDAYEVA T, et al. Enhanced photocatalytic activity at multidimensional interface of 1D-Bi₂S₃@2D-GO/3D-BiOI ternary nanocomposites for tetracycline degradation under visible-light[J]. J Hazard Mater, 2021, 404: 123868.
[47] JIANG X, LAI S, XU W, et al. Novel ternary BiOI/g-C₃N₄/CeO₂ catalysts for enhanced photocatalytic degradation of tetracycline under visible-light radiation via double charge transfer process[J]. J Alloys Compd, 2019, 809: 151804.
[48] ZHANG Q, BAI J, LI G, et al. Synthesis and enhanced photocatalytic activity of AgI-BiOI/CNFs for tetracycline hydrochloride degradation under visible light irradiation[J]. J Solid State Chem, 2019, 270: 129-134.
[49] WANG Q, LI Y, HUANG L, et al. Enhanced photocatalytic degradation and antibacterial performance by GO/CN/BiOI composites under LED light[J]. Appl Surf Sci, 2019, 497: 143753.
[50] YAN M, HUA Y, ZHU F, et al. Fabrication of nitrogen doped graphene quantum dots-BiOI/MnNb₂O₆ p-n junction photocatalysts with enhanced visible light efficiency in photocatalytic degradation of antibiotics[J]. Appl Catal B, 2017, 202: 518-527.
[51] DONGH, XIAO M, LI J, et al. Construction of H-TiO₂/BiOCl heterojunction with improved photocatalytic activity under the visible and near-infrared light[J]. J Photochem Photobiol A, 2020, 392: 112369.
[52] LI Q, GUAN Z, WU D, et al. Z-scheme BiOCl-Au-CdS heterostructure with enhanced sunlight-driven photocatalytic activity in degrading water dyes and antibiotics[J]. ACS Sustainable Chem Eng, 2017, 5(8): 6958-6968.
[53] WANG S, YANG X, ZHANG X, et al. A plate-on-plate sandwiched Z-scheme heterojunction photocatalyst: BiOBr-Bi₂MoO₆ with enhanced photocatalytic performance[J]. Appl Surf Sci, 2017, 391: 194-201.
[54] YU H, HUANG B, WANG H, et al. Facile construction of novel direct solid-state Z-scheme AgI/BiOBr photocatalysts for highly effective removal of ciprofloxacin under visible light exposure: mineralization efficiency and mechanisms[J]. J Colloid Interface Sci, 2018, 522: 82-94.
[55] ZHOU K H, LIU Y, HAO J Y.One-pot hydrothermal synthesis of dual Z-scheme BiOBr/g-C₃N₄/Bi₂WO₆ and photocatalytic degradation of tetracycline under visible light[J]. Mater Lett, 2020, 281: 128463.
[56] LYU J, LI Z, GE M. Novel Bi/BiOBr/AgBr composite microspheres: ion exchange synthesis and photocatalytic performance[J]. Solid State Sci, 2018, 80: 101-109.
[57] LIU H, ZHOU H, LIU X, et al. Engineering design of hierarchical g-C₃N₄@Bi/BiOBr ternary heterojunction with Z-scheme system for efficient visible-light photocatalytic performance[J]. J Alloys Compd, 2019, 798: 741-749.
[58] CHEN J, XIAO X, WANG Y, et al. Novel AgI/BiOBr/reduced graphene oxide Z-scheme photocatalytic system for efficient degradation of tetracycline[J]. J Alloys Compd, 2019, 800: 88-98.
[59] ZHANG M, LAI C, LI B, et al. Rational design 2D/2D BiOBr/CDs/g-C₃N₄ Z-scheme heterojunction photocatalyst with carbon dots as solid-state electron mediators for enhanced visible and NIR photocatalytic activity: kinetics, intermediates, and mechanism insight[J]. J Catal, 2019, 369: 469-481.
[60] CHEN M, DAI Y, GUO J, et al. Solvothermal synthesis of biochar@ZnFe₂O₄/BiOBr Z-scheme heterojunction for efficient photocatalytic ciprofloxacin degradation under visible light[J]. Appl Surf Sci, 2019, 493: 1361-1367.
[61] LI H, LI J, AI Z, JIA F, et al. Oxygen vacancy-mediated photocatalysis of BiOCl: reactivity, selectivity, and perspectives[J]. Angew Chem Int Ed, 2018, 57(1):122-138.
[62] DING J, DAI Z, QIN F, et al. Z-scheme BiO_1-xBr/Bi₂O₂CO₃ photocatalyst with rich oxygen vacancy as electron mediator for highly efficient degradation of antibiotics[J]. Appl Catal B, 2017, 205: 281-291.
[63] YANG Y, ZENG Z, ZHANG C, et al. Construction of iodine vacancy-rich BiOI/Ag@AgI Z-scheme heterojunction photocatalysts for visible-light-driven tetracycline degradation: transformation pathways and mechanism insight[J]. Chem Eng J, 2018, 349: 808-821.
[64] JIANG R S, YANG J S, LI S T, et al. Construction of PDDA functionalized black phosphorus nanosheets/BiOI Z-scheme photocatalyst with enhanced visible light photocatalytic activity[J]. J Colloid Interface Sci, 2020, 576: 34-46.