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材料研究学报, 2026, 40(5): 333-342 DOI: 10.11901/1005.3093.2025.303

光催化专题

Cu2O/N,S-BiOBr复合光催化剂的制备及其降解性能

刘丹阳1,2, 景苗苗1,2, 赵强,1,2, 王俊丽,1,2, 贾治芳1,2, 李作鹏1,2, 王科伟,1,2, 郭永1,2

1.山西大同大学化学与化工学院 大同 037009

2.山西省清洁能源材料联合实验室 大同 037009

Synthesis of Cu2O/N,S-BiOBr Composite Photocatalysts and Their Performance for Tetracycline Degradation

LIU Danyang1,2, JING Miaomiao1,2, ZHAO Qiang,1,2, WANG Junli,1,2, JIA Zhifang1,2, LI Zuopeng1,2, WANG Kewei,1,2, GUO Yong1,2

1.School of Chemistry and Chemical Engineering, Shanxi Datong University, Datong 037009, China

2.Shanxi Province Union Laboratory of Clean Energy Materials, Shanxi Datong University, Datong 037009, China

通讯作者: 赵强，教授，zhaoqiangtylg@126.com，研究方向为光电降解污染物；王俊丽，正高级实验师，wangjunlitylg@126.com，研究方向为低阶煤，光催化；王科伟，教授，wangkewei@sxdtdx.edu.cn，研究方向为有机多孔材料

收稿日期: 2025-10-16   修回日期: 2026-01-19  

基金资助: 国家自然科学基金(21908135)
国家自然科学基金(21975146)
国家自然科学基金(52203266)
山西省留学回国人员科技活动择优资助(20240027)
山西省省筹资金资助回国留学人员科研项目(2020-134)
山西省省筹资金资助回国留学人员科研项目(2022-173)
山西省省筹资金资助回国留学人员科研项目(2025-201)
山西省自然科学研究面上项目(202403021211022)
大同市应用基础研究项目(2025063)

Corresponding authors: ZHAO Qiang, Tel: 15934234565, E-mail:zhaoqiangtylg@126.com;WANG Junli, Tel: 15934234500, E-mail:wangjunlitylg@126.com;WANG Kewei, Tel: 15296621181, E-mail:wangkewei@sxdtdx.edu.cn

Received: 2025-10-16   Revised: 2026-01-19  

Fund supported: National Natural Science Foundation of China(21908135)
National Natural Science Foundation of China(21975146)
National Natural Science Foundation of China(52203266)
Fund Program for the Scientific Activities of Selected Returned Overseas Professionals in Shanxi Province(20240027)
Research Project Supported by Shanxi Scholarship Council of China(2020-134)
Research Project Supported by Shanxi Scholarship Council of China(2022-173)
Research Project Supported by Shanxi Scholarship Council of China(2025-201)
Natural Science Research Project of Shanxi Province(202403021211022)
Datong City Applied Basic Research Project(2025063)

作者简介 About authors

刘丹阳，女，2002年生，硕士生

摘要

用水热法合成了Z型异质结Cu2O/N,S-BiOBr复合光催化剂，并表征其组成、形貌、光电性质及其在可见光照射下对四环素(TC)的光催化降解性能，研究了Cu2O负载量对这种催化剂在可见光下催化降解TC的性能和稳定性的影响及其机制。结果表明，Cu2O掺杂量为10% (质量分数)的催化剂10%Cu2O/N,S-BiOBr催化性能最优，在100 min内可降解85.63%的TC。这种催化剂光降解效率较高的原因是，在Cu2O和N,S-BiOBr之间高效的界面电荷转移和协同作用提高了光生电子空穴对的分离效率，从而使其光催化降解性能提高。超氧自由基(⋅O2-)和羟基自由基(⋅OH)是光催化降解TC的主要活性物质。

关键词： 复合材料; Cu2O/N; S-BiOBr; 水热法; 光催化; 降解; 四环素

Abstract

In this study, Cu2O/N,S-BiOBr photocatalysts were successfully synthesized by hydrothermal method, and their performance for catalytic degradation of tetracycline (TC) under visible light irradiation was systematically evaluated. The results showed that when the doping amount of Cu2O was 10% (mass fraction), the catalyst exhibited the optimal activity with a degradation rate of approximately 85.63% for TC within 100 min. This improved performance was mainly attributed to the efficient interfacial charge transfer and synergistic effect between Cu2O and N,S-BiOBr, which enhanced the separation efficiency of photogenerated electron-hole pairs, thereby improving the photocatalytic degradation ability. The results of electron paramagnetic resonance (EPR) tests indicated that superoxide radicals (⋅O2-) and hydroxyl radicals (⋅OH) were the main active substances in the photocatalytic degradation process of TC. This study provided a valuable reference for constructing efficient visible light-driven catalysts.

Keywords： composite; Cu2O/N; S-BiOBr; hydrothermal method; photocatalysis; degradation; tetracycline

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本文引用格式

刘丹阳, 景苗苗, 赵强, 王俊丽, 贾治芳, 李作鹏, 王科伟, 郭永. Cu2O/N,S-BiOBr复合光催化剂的制备及其降解性能[J]. 材料研究学报, 2026, 40(5): 333-342 DOI:10.11901/1005.3093.2025.303

LIU Danyang, JING Miaomiao, ZHAO Qiang, WANG Junli, JIA Zhifang, LI Zuopeng, WANG Kewei, GUO Yong. Synthesis of Cu2O/N,S-BiOBr Composite Photocatalysts and Their Performance for Tetracycline Degradation[J]. Chinese Journal of Materials Research, 2026, 40(5): 333-342 DOI:10.11901/1005.3093.2025.303

环境中残留的广谱类抗生素(如四环素、磺胺类、氧氟沙星等)严重威胁人的健康[1]，用吸附、膜分离和生物降解等技术可将其净化但是效果不佳[2~4]。光催化剂能将有机污染物矿化成无害的小分子化合物或无机物且反应速率高、能耗低、环境友好和具有可持续性，有广阔的应用前景[5,6]。抗生素的结构复杂且稳定性较高，单一的光催化剂难以将其高效降解。同时，光催化降解不同类型抗生素的反应机制不同。溴氧化铋(BiOBr)是一种n型半导体，独特的层状结构和适宜的带隙宽度使其具有优异的光催化性能[7~9]。典型PbFCl型四方晶系结构的卤氧化铋材料(BiOX, X = F, Cl, Br, I)，具有良好的化学稳定性、低毒性和抗光腐蚀性能[8,9]。BiOBr晶体由[Bi2O2]2+层与双Br-层交替排列而成，层间通过van der Waals力连接形成Br-Bi-O-Bi-Br的独特层状构型。这种结构不仅有利于原子和轨道极化，产生的内建电场可促进光生电子-空穴对的分离而使其光催化活性提高。同时，BiOBr的制备简便、成本低廉和环境友好。但是，带隙约为2.8 eV的纯BiOBr相对可见光的吸收有限，且较高的光生载流子复合率使其光催化效率和稳定性降低。为了提高BiOBr的光催化效率和稳定性，可采用元素掺杂、异质结构、表面修饰以及负载等方法将其改性[10~15]。进行非金属元素掺杂(如N、C、S等)不仅能拓宽BiOBr的可见光吸收范围，还能提高空穴氧化性能，使其光催化性能显著提高[16~18]。S掺杂可在保持BiOBr层状结构的同时使其产生轻微的晶格畸变，其3p轨道形成的杂质能级可收窄带隙、增强光吸收和促进载流子分离；同时，S掺杂还能调节BiOBr的内建电场和增强介电极化使电荷迁移效率进一步提高。N掺杂能收窄BiOBr的带隙，扩展对可见光的响应范围。Su等[16]制备了一种由Mo/S共掺杂的BiOBr双金属铋硫氧溴化物(Mo/S-BiOBr)催化剂。研究表明，Mo/S共掺杂调整BiOBr能带结构制备的催化剂扩大了可见光吸收范围，其中的异价态钼和丰富的氧空位缺陷能捕获水分子和激活H-O-H键产生氢的活性位点。异价态的Mo6+/Mo4+作为光生电子的载体在Mo6+和Mo4+之间高速跳跃促进了电子转移可光催化析氢(PHER)。这种催化剂中的S3p和O2p轨道杂化提高了连续PHER的稳定性。Song等[17]用一种简单方法合成了超薄氮掺杂的BiOBr，氮掺杂降低了BiOBr纳米片的厚度并增大了比表面积。同时，光生载流子迁移效率和二氧化碳吸附性能的显著提高改善了二氧化碳的光还原性能。氮原子取代氧原子成为吸附中心，提高了对二氧化碳而非水合氧的强吸附选择性并促进了关键反应中间体的生成。Subhiksha等[18]采用水热法制备了一种高效可见光激活氮掺杂的BiOBr纳米片,并在其表面锚定了磁性Fe3O4纳米球,用于降解溴氧辛林(BRX)除草剂。研究结果表明，N-BiOBr@Fe3O4纳米异质结形成了p-n异质结机制，N掺杂和p-n异质结的形成增强了电荷载流子的分离和可见光吸收而使降解率显著提高，在140 min内对BRX的降解率达到93.9%。这表明，N,S共掺杂有望进一步提高BiOBr的光催化性能。氧化亚铜(Cu2O)作为一种p型半导体其带隙约为2.17 eV，具有良好的可见光吸收能力、优异的光催化活性和高载流子迁移率，可降解有机污染物[19~21]。研究表明，Cu2O作为可见光响应组分与n型BiOBr复合形成p-n异质结，可促进界面电荷分离、拓宽光谱利用范围和提高光催化稳定性[22,23]。鉴于此，本文用水热法合成N,S共掺杂BiOBr (N,S-BiOBr)并将Cu2O负载于其表面构建出Cu2O/N,S-BiOBr复合光催化剂，研究Cu2O的负载量对其在可见光下催化降解四环素(TC)的性能和稳定性的影响及其机理。

1 实验方法

1.1 实验用试剂

氯化铜、盐酸羟胺、丙酮、无水乙醇、溴化钾、五水合硝酸铋(Ⅲ)、氢氧化钠、无水硫代硫酸钠、二乙醇胺、盐酸四环素。其中溴化钾为光谱纯，其余的均为分析纯。

1.2 十二面体氧化亚铜的制备

实验前配置0.5 mol/L的CuCl2溶液，1 mol/L的NaOH溶液和0.5 mol/L NH2·HCl溶液。

将83.4 mL的蒸馏水放入容积为500 mL的烧杯中，然后依次加入20 mL的无水乙醇和5 mL的CuCl2溶液，将烧杯置于温度为40 ℃的集热式恒温磁力搅拌器中，适当调节搅拌速率持续搅拌30 min。在搅拌期间，将30 mL的无水乙醇和9 mL的1 mol/L NaOH溶液装入两支恒压滴液漏斗中。搅拌结束后，同步开始滴加上述两种溶液：无水乙醇的滴加速度为3~4秒/滴，NaOH溶液的滴加速度为6~7秒/滴。然后继续搅拌并保持滴速，直至滴完。滴完后迅速加入9.8 mL 0.5 mol/L盐酸羟胺溶液，继续搅拌10 min。反应结束后将烧杯密封，在40 ℃静置陈化3 h。静置陈化结束后，将溶液真空抽滤，用乙醇-蒸馏水(体积比1∶1)的混合溶液反复洗涤得到的滤饼。将滤饼即氧化亚铜(Cu2O，图1a)移至培养皿中并置于温度为40 ℃的烘箱内充分干燥，然后测试其质量。

图1

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图1   Cu2O/N,S-BiOBr复合光催化剂的制备示意图

Fig.1   Schematic diagram for the preparations of Cu2O/N,S-BiOBr composite


1.3 N,S掺杂溴氧化铋与氧化亚铜的复合光催化剂的制备

图1b给出了制备Cu2O/N,S-BiOBr的示意图。在室温下将1.94 g五水合硝酸铋(Bi(NO3)3·5H2O)和0.476g溴化钾(KBr)置于250 mL烧杯中并加入120 mL无水乙醇，再分别加入0.1 g无水硫代硫酸钠(S源)和0.1 mL二乙醇胺(N源)，然后分别加入0.01、0.02、0.03、0.04和0.05 g的不同质量比的Cu2O粉末，将其以较高转速持续搅拌2 h。搅拌完成后，将混合溶液移至容积为200 mL的聚四氟乙烯内衬不锈钢高压反应釜中，将其置于160℃的鼓风干燥箱内反应16 h。反应结束后，使反应釜自然冷却至室温。将所得产物沉淀真空抽滤后依次用蒸馏水和无水乙醇充分洗涤，然后放入80 ℃烘箱中干燥24 h，得到分别记为5%Cu2O/N,S-BiOBr、10%Cu2O/N,S-BiOBr、15%Cu2O/N,S-BiOBr、20%Cu2O/N,S-BiOBr和25% Cu2O/N,S-BiOBr的复合光催化剂。

1.4 光催化剂的表征

用D/ max 2500型粉末X射线衍射仪(XRD)测试光催化剂的XRD谱，用Cu Kα辐射源，工作电压为60 kV，工作电流为300 mV，扫描范围2θ = 10°~90°。用TESCANMAIA 3 LMH型扫描电子显微镜(SEM)和高分辨率透射电镜(HRTEM, JEOL, JEM2999FMII apparatus)观察样品的形貌。用紫外可见漫反射(UV‐Vis DRS)光谱、光电流响应和电化学阻抗(EIS)表征样品的光电性质。测试光电流响应所用溶液为Na2SO4 (0.2 mol·L-1)，使用三电极体系和CHI760E电化学工作站进行EIS测试，样品电极为工作电极，Pt片为对电极，Ag/AgCl电极为参比电极，所用溶液为KCl (0.1 mol·L-1)和[Fe(CN)6]3-/[Fe(CN)6]4- (2.5 mmol·L-1)的混合溶液，测试频率范围为105~10-2 Hz。用Escalab 250Xi型X射线光电子能谱仪(XPS)分析样品表面的元素种类和元素形态。

在可见光(CEL-S500 500W氙灯)照射下，在夹层石英杯中加入90 mL (30 mg/L)的TC溶液和100 mg的光催化剂，然后关闭光源将其搅拌进行暗反应使溶液达到吸脱附平衡。暗反应结束后取4 mL试样并将其高速离心5 min，然后取上层清液测定其吸光度。最后打开光源在光照下进行光催化反应，每隔10 min取一次样并将其离心分离，用722E分光光度计测定357nm处的吸光度值。降解率为

D=C0-CtC0×100%=(1-CtC0)×100%

其中D为降解率(%)；C0为反应开始时溶液中TC的浓度(mg·L-1)；Ct 为光照时间为t时溶液中TC的浓度(mg·L-1)。

2 结果和讨论

2.1 催化剂的组成

图2给出了Cu2O、N,S-BiOBr和10%Cu2O/N,S-BiOBr的XRD谱。出现在2θ为29.5°、36.3°、42.4°、61.3°和73.6°处的峰分别对应Cu2O的(110)、(111)、(200)、(220)和(311)晶面[20]。与BiOBr的标准卡片(JCPDS No.73-2061)对比表明，2θ为32.26°、46.16°和57.14°处的峰分别对应BiOBr的(110)、(200)和(212)晶面[24]。由于N和S掺杂剂的含量低，在N,S-BiOBr的谱中没有出现其衍射峰，但是XPS表明其存在。在10%Cu2O/N,S-BiOBr复合光催化剂的XRD谱中出现了N,S-BiOBr的峰和Cu2O的峰，表明已经成功地制备出复合光催化剂Cu2O/N,S-BiOBr。

图2

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图2   10%Cu2O/N、S-BiOBr, N,S-BiOBr和Cu2O的XRD谱

Fig.2   XRD patterns of 10%Cu2O/N,S-BiOBr, N,S-BiOBr and Cu2O


从图3a、b可见，BiOBr具有层状结构，Cu2O具有十二面体结构。从图3c可以看出，N和S的掺杂没有改变BiOBr的形貌。从图3d可见，Cu2O比较均匀地分布在N,S-BiOBr的三维层状结构表面，表明Cu2O与N,S-BiOBr之间良好复合。值得注意的是，复合后材料的结构仍然是N,S-BiOBr原有的花状形态。进一步观察可见，10%Cu2O/N,S-BiOBr中的Cu2O仍然保持着十二面体的几何构型，其粒径为260~300 nm。从图3e、f可以看出，Cu2O负载在N,S-BiOBr表面，Cu2O纳米颗粒与N,S-BiOBr基底之间形成了清晰的异质结界面。这种结构有利于光生电子-空穴对的分离，从而使材料的光催化性能提高。

图3

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图3   BiOBr、Cu2O、N,S-BiOBr以及10%Cu2O/N,S-BiOBr的SEM照片和10%Cu2O/N,S-BiOBr的HRTEM图

Fig.3   SEM images of BiOBr (a), Cu2O (b), N,S-BiOBr (c), and 10%Cu2O/N,S-BiOBr (d), and HRTEM images of 10%Cu2O/N,S-BiOBr (e, f)


图4a给出了不同质量分数的Cu2O/N,S-BiOBr，N,S-BiOBr和Cu2O的UV-Vis DRS图。可以看出，Cu2O的加入使Cu2O/N,S-BiOBr发生了明显的变化，有利于对可见光的吸收。根据漫反射光谱用Tauc方程得到的Cu2O和N,S-BiOBr的带隙(Eg)以及图4b给出的Cu2O和N,S-BiOBr对应的Tauc图，计算出Cu2O和N,S-BiOBr的带隙分别为2.07和2.83 eV。

图4

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图4   Cu2O/N,S-BiOBr, N,S-BiOBr和Cu2O的紫外-可见漫反射光谱和Cu2O、N,S-BiOBr的带隙

Fig.4   UV-Vis DRS characterization of Cu2O/N,S-BiOBr, N,S-BiOBr and Cu2O (a), and band gap diagrams of Cu2O and N,S-BiOBr (b)


图5给出了Cu2O和N,S-BiOBr的Mott-Schottky曲线，其正斜率证实这两种材料均属于n型半导体。由图5可见，Cu2O和N,S-BiOBr的平带电位(Efb)分别为-0.85 V和-0.56 V (相对于Ag/AgCl)，其相对于标准氢电极(NHE)的电势值为

图5

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图5   Cu2O和N,S-BiOBr的Mott-Schottky曲线

Fig.5   Mott-Schottky plots of Cu2O (a) and N,S-BiOBr (b)


E=E'+0.059pH+E⊖

式中E′为相对于Ag/AgCl的电极电位，E⊖为Ag/AgCl参比电极的标准电位。需要说明的是，0.5 mol·L-1 Na2SO4溶液的pH值为6.8，标准电极电势E⊖ = 0.197 V。因此，Cu2O和N,S-BiOBr的Efb分别为-0.25 V (vs. NHE)和0.03 V (vs. NHE)。n型半导体的最低导带电位(ECB)比Efb负移0.3 V，故可计算出Cu2O和N,S-BiOBr的ECB分别为-0.55 V (vs. NHE)和-0.26 V (vs. NHE)。基于Tauc图给出的带隙，可进一步推算出Cu2O和N,S-BiOBr的价带电位分别为1.52 V (vs. NHE)和2.57 V (vs. NHE)。

图6给出了Cu2O/N,S-BiOBr复合光催化剂，N,S-BiOBr以及Cu2O的光电性能。从光电流响应曲线可见，Cu2O的添加量为10%的Cu2O/N,S-BiOBr复合催化剂其光电流响应最显著(图6a)。这种复合催化剂的光电流值比纯N,S-BiOBr显著提高，充分证明Cu2O的引入增强了N,S-BiOBr的导电性。图6b给出了催化剂的EIS，可见10%Cu2O/N,S-BiOBr复合催化剂的半圆半径最小，表明其电荷转移阻抗最低和电荷迁移速率较高。这一结果，与光电流响应的实验结果一致。以上结果表明，这种复合光催化剂促进了光生电子-空穴对的分离，使其光催化性能显著提高。

图6

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图6   Cu2O/N,S-BiOBr, N,S-BiOBr和Cu2O的光电流响应曲线和电化学阻抗谱

Fig.6   Photocurrent analysis (a) and EIS (b) of Cu2O/N,S-BiOBr, N,S-BiOBr, and Cu2O


图7给出了10%Cu2O/N,S-BiOBr复合催化剂的XPS谱。从XPS总谱(图7a)可以看出，这种复合催化剂中有Bi、O、Br、Cu、S元素，未见N元素因其掺杂量较小。图7c、g给的N 1s和S 2p的高分辨率XPS光谱进一步证明了复合光催化剂中有N和S元素。图7b给出了Bi 4f的XPS谱，其中结合能为159.27 eV和164.57 eV的峰分别对应Bi 4f7/2和Bi 4f5/2。图7c给出了复合光催化剂中N 1s的谱和拟合结果，其中位于~394.10 eV的N 1s峰可归因于掺入BiOBr晶格中的N，而400.03 eV处的峰可归因于y-N2[25]。另外，图7d给出了Br 3d的谱和拟合结果，其中结合能为68.414 eV和69.346 eV的峰分别对应Br 3d5/2和Br 3d3/2，是催化剂中Br-的特征峰[26]。从图7e可以看出，在O 1s的光谱中约530 eV、531.33 eV和532.55 eV处出现三个信号峰，分别对应复合光催化剂中的晶格氧、缺陷氧和吸附氧[12]。图7f中Cu 2p在932.29 eV和952.11 eV处的两个峰分别对应Cu 2p3/2和Cu 2p1/2[20]。在图6g给出的S 2p的高分辨XPS光谱中结合能为159.1 eV和164.42 eV的峰，归因于S和Bi形成Bi-S键[25]。以上结果表明，本文成功地制备出复合光催化剂Cu2O/N,S-BiOBr。

图7

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图7   10%Cu2O/N,S-BiOBr复合光催化剂的XPS总谱以及Bi 4f，N 1s，Br 3d，O 1s，Cu 2p和S 2p的高分辨XPS谱

Fig.7   XPS spectrum of 10%Cu2O/N,S-BiOBr composite (a), and high-resolution XPS of Bi 4f (b), N 1s (c), Br 3d (d), O 1s (e), Cu 2p (f), and S 2p (g)


2.2 催化剂光降解TC的性能

图8给出了Cu2O/N,S-BiOBr复合催化剂的降解性能。可以看到，Cu2O/N,S-BiOBr复合催化剂的降解性能比纯Cu2O和纯N,S-BiOBr的都高。Cu2O掺杂量为10%的复合光催化剂降解性能最高，在100 min内可降解85.63%的TC。其原因是，Cu2O的掺杂量较低时Cu2O与N,S-BiOBr形成的耦合界面数量有限，降解性能没有显著的提高。随着Cu2O掺杂量的提高异质结界面不断增多，Cu2O掺杂量为10%时异质结界面最多，电荷分离效率最高，协同效应最显著。但是，Cu2O的掺杂量过高，使Cu2O覆盖在N,S-BiOBr表面发生团聚或形成较厚的层而影响N,S-BiOBr对光的吸收，从而使Cu2O/N,S-BiOBr复合材料的降解性能降低。Cu2O/N,S-BiOBr催化剂与其它溴氧铋基催化剂降解TC的催化性能比较，如表1所示。由表1可知，本文制备的新型Cu2O/N,S-BiOBr复合材料具有较高的光催化降解性能。

图8

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图8   N,S-BiOBr、Cu2O 和Cu2O/N,S-BiOBr光催化剂的光催化性能

Fig.8   Photocatalytic performance curves of N,S-BiOBr, Cu2O and Cu2O/N,S-BiOBr photocatalysts


表1   溴氧铋基光催化剂降解四环素光催化性能的比较

Table 1  Comparison of photocatalytic performance of TC degradation over BiOBr-based photocatalysts

PhotocatalystExperiment condition*Time/minDegrading efficiency/%Ref.
Cl-BiOBr50 mg, 50 mL, 20 mg/L12076.2[27]
BiOBr@C-AgBr30 mg, 30 mL, 90 mg/L6085.1[28]
BiOBr/rGO50 mg, 100 mL, 5 mg/L12073[29]
N-COF/BiOBr5 mg, 50 mL, 60 mg/L12081.2[10]
BiOBr/MnFe2O4100 mg, 100 mL, 20 mg/L12076.5[30]
Cu2O/N,S-BiOBr100 mg, 90 mL, 30 mg/L10085.63This work

Note: *The three parameters in the experimental conditions refers to the sample mass, the concentration and the volume of the target pollutant

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2.3 光催化机理

2.3.1 自由基检测

为了研究光催化降解机理，用EPR检测了10%Cu2O/N,S-BiOBr复合光催化剂降解TC的活性物质，结果在图9中给出。结果表明，使用复合光催化剂Cu2O/N,S-BiOBr暗反应时，没有明显的光电流信号；在光照条件下电流信号显著且光照时间越长信号越显著，其原因是产生了大量的⋅OH和⋅O2-。这表明，⋅OH和⋅O2-是光催化降解TC过程中起主要作用的活性物质。光生电子与Cu2O表面的吸附氧反应生成⋅O2-，空穴将水中的羟基转化成⋅OH，⋅O2-和⋅OH均具有强氧化性而能将废水中的TC降解。

图9

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图9   10%Cu2O/N,S-BiOBr复合光催化剂在黑暗和光照条件下的EPR谱

Fig.9   EPR signals of DMPO-·OH (a) and DMPO-·O2- (b) over 10%Cu2O/N,S-BiOBr


从图10可以看出，加入⋅OH清除剂异丙醇(IPA)后对TC的降解率明显降低，表明⋅OH是光催化降解的重要活性物种。而在N2气氛中催化活性明显降低，说明⋅O2-也是参与光催化降解的主要物种。由此可见，反应体系中的主要活性物质为⋅OH和⋅O2-，与EPR光谱给出的结果一致。

图10

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图10   10%Cu2O/N,S-BiOBr复合光催化剂在可见光照射下活性物种捕获实验(IPA：异丙醇)

Fig.10   Active species trapping experiments with 10% Cu2O/N,S-BiOBr composite under visible light irradiation (IPA: Isopropyl alcohol)


2.3.2 光催化机理

基于对光催化剂的光电表征、光催化降解性能以及活性物种的检测结果，提出在可见光照射下复合光催化剂Cu2O/N,S-BiOBr降解TC的光催化降解机理，其示意图如图11所示。图11表明，在可见光照射下半导体N,S-BiOBr和Cu2O价带上的电子分别吸收足够的能量跃迁到各自的导带，生成大量的光生电子和空穴。根据Z型异质结机理，半导体Cu2O的光生电子与半导体N,S-BiOBr的光生空穴复合，从而在半导体Cu2O的导带(CB)保留了还原能力较强的光生电子，而在半导体N,S-BiOBr上保留了氧化能力较强的光生空穴。复合光催化剂中Cu2O的导带标准电位(-0.55 V vs. NHE)比O2/⋅O2-的标准电位(-0.33 V vs. NHE)更负，因此能将催化剂表面的O2还原为活性组分⋅O2-，而N,S-BiOBr的价带标准电位(2.57 V vs. NHE)比H2O/⋅OH的标准电位(1.99 V vs. NHE)更高，可将H2O氧化为活性组分⋅OH[31]，进而生成⋅O2-和⋅OH将TC分解为CO2、H2O或其它小分子。Cu2O/N,S-BiOBr Z型异质结复合光催化剂保留了还原能力较强的光生电子和氧化能力较强的光生空穴，促进了光生电子-空穴的空间分离，从而大大提高了催化剂的光催化性能。

图11

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图11   在可见光下Cu2O/N,S-BiOBr光催化降解四环素的机理

Fig.11   Photocatalytic mechanism of the TC degradation over Cu2O/N,S-BiOBr under visible light


3 结论

(1) 先用水热法制备花状N,S-BiOBr，然后用共沉淀法将不同质量的十二面体Cu2O与N,S-BiOBr复合，可制备Z型异质结Cu2O/N,S-BiOBr复合催化剂。Cu2O与N,S-BiOBr的复合促进了光生电子-空穴对的高效分离。

(2) 在可见光的照射下10%Cu2O/N,S-BiOBr复合光催化剂的光催化性能最佳。光催化性能的提高，可归因于Cu2O与N,S-BiOBr之间形成的Z型异质结促进了光生电子-空穴的空间分离和延长了光生载流子的寿命。⋅O2-、和⋅OH是光催化反应中的主要活性物质。

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Metal oxide semiconductor-activated photocatalysis has become a promising sustainable technology for the mitigation of emerging organic pollutants. The rational design of a photocatalyst heterojunction allows the degradation of a broad range of organic contaminants. Herein, we optimized hydrothermal approaches for the facial synthesis of well-defined BiOBr/CuO heterojunction photocatalysts. Tuning the synthesis condition enhanced the interfacing of BiOBr and CuO nanostructures in the heterojunction photocatalyst, as confirmed by STEM, TEM, XPS, XRD, and BET analysis. The optimized BiOBr/CuO heterostructured photocatalyst demonstrated substantial activity in the degradation of both anionic and cationic dyes compared to the individual components. The enhanced nanocomposite exhibited complete degradation of glyphosate in 10 min of light irradiation and demonstrated high stability after five photocatalytic cycles. Our mechanistic and photoelectrochemical studies suggest that establishing an S-scheme heterojunction between BiOBr and CuO enhances the separation of photogenerated charge carriers and expands the redox potentials of the nanocomposite to allow high catalytic efficiency. These findings indicate that tuning the design of metal oxide heterojunctions promises applications in the remediation of a wide range of organic contaminants.© 2024 The Authors. Published by American Chemical Society.

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