Photocatalytic properties of Z-scheme heterojunction BiO2-  x /ZnWO4 on antibiotics in water

doi:10.19965/j.cnki.iwt.2023-0256

Abstract

Abstract:

Heterojunction combining with two kinds of different band structures semiconductors was constructed, and its photocatalytic performance could be greatly improved with the wider optical response range. The BiO_2- _x /ZnWO₄ composite was prepared by a simple two-step hydrothermal method. The structure, morphology and optical properties of BiO_2- _x /ZnWO₄ were characterized by XRD, SEM and UV-vis diffuse reflectometry. The photocatalytic performance and cyclic stability of BiO_2- _x /ZnWO₄ were studied by degrading tetracycline under visible light. The results showed that with the synergistic action between BiO_2- _x and ZnWO₄, the photo-generated carriers of BiO_2- _x /ZnWO₄ could be effectively separated and the light absorption capacity of BiO_2- _x /ZnWO₄ could be significantly enhanced. After 90 min of visible light illumination, the photodegradation efficiency of the composite towards tetracycline reached 86.04%, and the light response range and photocatalytic activity of the composite were better than the monomer BiO_2- _x and ZnWO₄. In addition, the composite displayed good light stability. The capture experiments and ESR showed that h⁺, O₂ ^·- and ·OH were produced by the composites under light, in which h⁺ and O₂ ^·- were the main active substances in the process of photocatalysis, and ·OH was the minor active species, following the order of h⁺>O₂ ^·->·OH. It was inferred that the electron transfer mechanism of BiO_2- _x /ZnWO₄ was Z-scheme heterojunction.

Key words: photocatalysis, zinc tungstate, antibiotic, Z-scheme heterojunction

摘要：

将两种具有不同能带结构的半导体结合起来构建异质结，可以有效地拓宽材料的光响应范围，提高光催化性能。采用简单的两步水热法制备了BiO_2- _x /ZnWO₄复合材料，利用XRD、SEM和UV-vis漫反射光谱等表征研究了BiO_2- _x /ZnWO₄的结构、形貌和光学性能，并考察了其在可见光下对四环素的光催化降解性能和循环稳定性能。研究结果表明，BiO_2- _x /ZnWO₄复合材料借助BiO_2- _x 和ZnWO₄的协同作用，光生载流子可得到有效分离，光吸收能力显著增强；可见光照射90 min后，复合材料对四环素的光降解效率为86.04%，光响应范围和光催化活性均优于单体BiO_2- _x 和ZnWO₄，且该材料具有良好的稳定性。捕获实验和ESR证实，复合材料在光照下产生h⁺、O₂ ^·-和·OH，其中空穴h⁺和O₂ ^·-是光催化过程中的主要活性物质，而·OH是次要活性物种，其作用大小依次是h⁺>O₂ ^·->·OH；推断BiO_2- _x /ZnWO₄复合材料的电子转移机制为Z型异质结。

关键词: 光催化, 钨酸锌, 抗生素, Z型异质结

CLC Number:

TQ426
X703

Hongsen HUANG, Xinyu ZHENG, Zhenfeng LIN, Yongfu GUO. Photocatalytic properties of Z-scheme heterojunction BiO_2- _x /ZnWO₄ on antibiotics in water[J]. Industrial Water Treatment, 2024, 44(4): 138-146.

黄宏森, 郑欣钰, 林振锋, 郭永福. Z型异质结BiO_2- _x /ZnWO₄对水中抗生素的光催化研究[J]. 工业水处理, 2024, 44(4): 138-146.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2023-0256

https://www.iwt.cn/EN/Y2024/V44/I4/138

Figures/Tables 13

Fig.1 XRD of ZnWO₄，BiO_2- _x and BiO_2- _x /ZnWO₄

Fig.2 SEM of ZnWO₄， BiO_2- _x and BiO_2- _x /ZnWO₄

Fig.3 FT-IR of ZnWO₄， BiO_2- _x and BiO_2- _x /ZnWO₄

Fig.4 XPS of BiO_2- _x， ZnWO₄， BiO_2- _x /ZnWO₄， Bi 4f， Zn 2p， W 4f and O 1s

Fig.5 UV-vis diffuse reflection spectrum of materials （a） and Tauc （b），（c）

Fig.6 Photodegradation efficiency （a） and TOC removal property （b） of tetracycline

Fig.7 Kinetic fitting results of photodegradation of tetracycline

Fig.8 Cycling degradation efficiency for tetracycline degradation （a） and XRD patterns before and after reaction （b）

Fig.9 Experimental effect of free radical trapping

Fig.10 ESR of DMPO-O₂ ^·- （a） and DMPO-·OH （b）

Table 1 Intermediate products of degradation

编号	产物	m/z
TC	C₂₂H₂O₈N₂	445
T1	C₂₂H₂₂O₇N₂	427
T2	C₂₁H₂₁O₆N	384
T3	C₁₈H₁₇O₇N	360
T4	C₁₅H₁₈O₅	279
T5	C₉H₁₀O₂	149
T6	C₃H₄O₅	121

Fig.11 Possible degradation pathway

Fig.12 Photocatalytic mechanism of BiO_2- _x /ZnWO₄ under visible light

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Photocatalytic properties of Z-scheme heterojunction BiO_2- _x /ZnWO₄ on antibiotics in water

Z型异质结BiO_2- _x /ZnWO₄对水中抗生素的光催化研究

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