II/Z型Bi2MoO6/Ag2O/Bi2O3异质结可见光催化降解四环素

doi:10.15541/jim20230408

无机材料学报 ›› 2024, Vol. 39 ›› Issue (3): 321-329.DOI: 10.15541/jim20230408 CSTR: 32189.14.10.15541/jim20230408

II/Z型Bi₂MoO₆/Ag₂O/Bi₂O₃异质结可见光催化降解四环素

叶茂森¹(), 王耀¹(), 许冰¹, 王康康¹, 张胜楠², 冯建情²

1.西安建筑科技大学化学与化工学院, 西安 710055
2.西北有色金属研究院, 西安 710016

收稿日期:2023-09-08 修回日期:2023-11-20 出版日期:2024-03-20 网络出版日期:2023-11-22
通讯作者: 王耀, 副教授. E-mail: wyspacestar@aliyun.com
作者简介:叶茂森(1998-), 男, 硕士. E-mail: 1076712450@qq.com
基金资助:
陕西省重点研发计划(2023-YBGY-502);陕西省秦创原“科学家+工程师”团队建设项目(2023KXJ-185);西安市碑林区科技计划项目(GX2318);陕西省教育厅专项研究项目(18JK0443)

II/Z-type Bi₂MoO₆/Ag₂O/Bi₂O₃ Heterojunction for Photocatalytic Degradation of Tetracycline under Visible Light Irradiation

YE Maosen¹(), WANG Yao¹(), XU Bing¹, WANG Kangkang¹, ZHANG Shengnan², FENG Jianqing²

1. School of Chemistry and Chemical Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China
2. Northwest Institute for Nonferrous Metal Research, Xi’an 710016, China

Received:2023-09-08 Revised:2023-11-20 Published:2024-03-20 Online:2023-11-22
Contact: WANG Yao, associate professor. E-mail: wyspacestar@aliyun.com
About author:YE Maosen (1998-), male, Master. E-mail: 1076712450@qq.com
Supported by:
Key R&D Plan of Shaanxi Province(2023-YBGY-502);QinChuangYuan “Scientist + Engineer” Team Construction Project of Shaanxi Province(2023KXJ-185);Science and Technology Plan Project of Beilin District in Xi’an(GX2318);Special research Project of Education Department of Shaanxi Province(18JK0443)

摘要/Abstract

摘要：

构建异质结能够有效抑制光催化剂中光生电子和空穴的快速复合。本研究采用水热法、煅烧法以及溶剂热法合成了II/Z型Bi₂MoO₆/Ag₂O/Bi₂O₃异质结光催化剂, 利用不同研究手段分析材料的组成、形貌以及光电化学性能。结果发现, 复合材料的最佳组成为25%ABOBM (Ag₂O/Bi₂O₃和Bi₂MoO₆的质量比为1 : 4)。在可见光照射下25%ABOBM对四环素(TC)的降解效率可达85.6%, 明显高于Ag₂O/Bi₂O₃和Bi₂MoO₆, 而且三次循环实验后仍具有良好的稳定性。25%ABOBM光催化性能的提高可归因于Ag₂O、Bi₂O₃以及Bi₂MoO₆之间异质结的构建和特殊形貌的形成。自由基捕获实验和电子顺磁共振谱(EPR)结果表明, h⁺和·O₂^-在TC的降解过程中发挥着主要作用, 而·OH和¹O₂发挥着次要作用。实验还探索了相关光催化机理, 并利用液相色谱-质谱联用仪(LC-MS)对TC可能的降解路径进行了分析。本研究为双异质结光催化剂的制备及其在有机污染物降解应用方面提供了新的思路。

关键词: Bi₂MoO₆, Ag₂O, Bi₂O₃, 光催化降解, 四环素, 异质结

Abstract:

Construction of heterojunction can effectively suppress the swift recombination of photogenerated electrons and holes in photocatalyst. In this study, a II/Z-type Bi₂MoO₆/Ag₂O/Bi₂O₃heterojunction photocatalyst was synthesized using a solvothermal method combined with calcination. Various techniques were ultilized to examine the composition, morphology and photoelectrochemical properties of the as-prepared materials. The findings revealed that the optimal composition of the composite material was 25%ABOBM (with a mass ratio of Ag₂O/Bi₂O₃ and Bi₂MoO₆ of 1 : 4). Under visible light irradiation, the degradation efficiency of tetracycline (TC) by 25%ABOBM reached 85.6%, which was significantly higher than that of Ag₂O/Bi₂O₃ and Bi₂MoO₆, and maintained its good stability after three cycles of experiments. The enhanced photocatalytic performance of 25%ABOBM is attributed to the formation of heterojunctions and the unique morphologies among Ag₂O, Bi₂O₃ and Bi₂MoO₆. Both h⁺ and ·O₂^- are significant contributors, while ·OH and ¹O₂ have secondary roles in the degradation process of TC, as indicated by free radical capture experiment and electron paramagnetic resonance spectroscopy (EPR). Furthermore, the related photocatalytic mechanisms were explored, and the potential degradation pathways of TC were analyzed using liquid chromatography-mass spectrometry (LC-MS). This study offers a novel approach to the preparation of photocatalysts with dual heterojunctions and demonstrates their application in the degrading organic pollutants.

Key words: Bi₂MoO₆, Ag₂O, Bi₂O₃, photocatalytic degradation, tetracycline, heterojunction

中图分类号:

O643

叶茂森, 王耀, 许冰, 王康康, 张胜楠, 冯建情. II/Z型Bi₂MoO₆/Ag₂O/Bi₂O₃异质结可见光催化降解四环素[J]. 无机材料学报, 2024, 39(3): 321-329.

YE Maosen, WANG Yao, XU Bing, WANG Kangkang, ZHANG Shengnan, FENG Jianqing. II/Z-type Bi₂MoO₆/Ag₂O/Bi₂O₃ Heterojunction for Photocatalytic Degradation of Tetracycline under Visible Light Irradiation[J]. Journal of Inorganic Materials, 2024, 39(3): 321-329.

图/表 12

图1 不同样品的XRD图谱(a)及XPS表征(b~f)

Fig. 1 XRD patterns (a) and XPS characterization (b-f) of different samples (b) Survey; (c) Bi4f; (d) O1s; (e) Ag3d; (f) Mo3d

图2 AgBiO3 (a)、BO (b)、ABO (c)、BM (d)以及25%ABOBM (e, f)的SEM照片; 25%ABOBM的HRTEM照片(g, h)和元素分布图(i)

Fig. 2 SEM images of AgBiO3 (a), BO (b), ABO (c), BM (d), and 25%ABOBM (e, f); HRTEM images (g, h) and elemental mappings (i) of 25%ABOBM

图3 BO、ABO、BM以及25%ABOBM的紫外-可见漫反射光谱(a); BO和BM的Tauc曲线(b)

Fig. 3 UV-Vis DRS of BO, ABO, BM, and 25%ABOBM (a); Tauc curves of BO and BM (b) Colorful figures are available on website

图4 不同材料对TC的降解曲线

Fig. 4 Degradation curves of TC over different materials (a) ABO, BM, and different ratios of ABOBM composites; (b) Different materials systems

图5 TC可能的降解途径

Fig. 5 Possible degradation paths of TC

图6 自由基捕获实验(a), EPR光谱中DMPO-•O2-的信号(b)和DMPO-•OH的信号(c)

Fig. 6 Free radical capture experiments (a), signals of DMPO-•O2- (b) and DMPO-•OH (c) in EPR spectra

图7 ABO、BM和25%ABOBM的光电流响应曲线(a)、EIS图谱(b)及其PL曲线(c), BO(d)和BM(e)的M-S图谱

Fig. 7 Photocurrent response curves (a), EIS plots (b) and PL curves (c) of ABO, BM, and 25%ABOBM, M-S diagrams of BO (d) and BM (e) Colorful figures are available on websites

图8 25%ABOBM降解TC的光催化机理

Fig. 8 Possible photocatalytic mechanisms of 25%ABOBM in degradation of TC (a) Traditional II/I type heterojunction; (b) Ⅱ/Z-type tandem heterojunction

方案S1 Bi2MoO6/Ag2O/Bi2O3的制备过程

Scheme S1 Preparation process of Bi2MoO6/Ag2O/Bi2O3

图S1 25%ABOBM在可见光下降解TC的循环实验(a)和循环测试前后的XRD图谱(b)

Fig. S1 Cyclic experiment of 25%ABOBM degradation of TC under visible light irradiation (a) and XRD patterns of 25%ABOBM before and after cycling test (b)

图S2 TC中间产物的LC-MS谱图

Fig. S2 LC-MS results of intermediate products of TC

表S1 可见光照射下25%ABOBM光催化降解TC的中间产物

Table S1 Intermediate products in the TC photocatalytic degradation by 25%ABOBM under visible light irradiation

TPs	Retention time/min	m/z
TC	6.73	445
P1	6.83	417
P2	4.52	342
P3	1.88	227
P4	1.35	158
P5	11.02	413
P6	5.8	399
P7	15.68	346
P8	0.71	192
P9	11.02	476
P10	12.67	340
P11	7.99	171
P12	4.89	114
P13	9.07	111
P14	2.63	85
P15	2.63	60

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II/Z型Bi₂MoO₆/Ag₂O/Bi₂O₃异质结可见光催化降解四环素

II/Z-type Bi₂MoO₆/Ag₂O/Bi₂O₃ Heterojunction for Photocatalytic Degradation of Tetracycline under Visible Light Irradiation

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