铋基光催化剂降解四环素的研究进展

doi:10.19965/j.cnki.iwt.2020-0728

摘要/Abstract

摘要：

四环素是一种常用的广谱抑菌剂。其在人体和动物体内代谢不完全，可释放到环境中。近年来，四环素在水环境及土壤中均有检出，其污染问题逐渐引起人们的关注。光催化法是高效去除抗生素的方法之一。而常用的TiO₂光催化剂具有光响应范围较窄，电子-空穴对易复合等缺陷。采用铋基光催化材料去除水体中的四环素，具有稳定性高、载流子密度低、平均自由程长等性能。总结了铋基光催化材料的种类、改进方法及降解四环素的关键操作参数(pH、四环素浓度、催化剂投加量、光强)，总结了反应机理和常见的光催化中间产物，并对铋基光催化剂未来的研究方向进行展望。

关键词: 铋基材料, 光催化, 四环素

Abstract:

Tetracycline(TC) is a widely used bacteriostatic agent. Its metabolism in human and animal body is not complete, can be released into the environment. In recent years, TC has been detected in water environment and soil, and its pollution has gradually attracted people's attention. Photocatalysis is one of the most effective methods to remove antibiotics. The commonly used TIO₂ has some defects, such as narrow photoresponse range and easy recombination of electron-hole pair. Bismuthal photocatalysts could be used in the TC degradation in water, which had the advantages of high stability, low carrier density, and long average free path. The types and improvements of bismuthal photocatalysts were summarized. The key parameters, such as pH, TC concentration, catalyst dosage, and light intensity on TC degradation were discussed. The reaction mechanisms and the common intermediate products of TC degradation were listed. Finally, the future research direction of bismuthal photocatalyst was proposed.

Key words: bismuthal materials, photocatalysis, tetracycline

中图分类号:

X703

邢超,陈悦,汪晟,史静. 铋基光催化剂降解四环素的研究进展[J]. 工业水处理, 2021, 41(8): 7-12, 46.

Chao Xing,Yue Chen,Sheng Wang,Jing Shi. Research progress in the tetracycline degradation by bismuthal photocatalysts[J]. Industrial Water Treatment, 2021, 41(8): 7-12, 46.

https://www.iwt.cn/CN/Y2021/V41/I8/7

图/表 4

参考文献 57

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反应体系	催化剂	光源	影响因素	最优条件	TC降解率/%
光催化	Bi₂O₇Sn₂-Bi₇O₉I₃	太阳光	pH: 2、6、11 催化剂: 0.5、1、1.5g/L TC 35、55 mg/L	pH为6、催化剂1 g/L、 TC35 mg/L	80^〔30〕
光催化	Bi₂Sn₂O₇-C₃N₄/沸石	400 W卤钨灯, 无滤光片	pH: 3、6、9 催化剂: 0.75、1、1.25 g/L TC: 10、20、30 mg/L	pH为6、催化剂1 g/L、 TC20 mg/L	80.4^〔31〕
光催化	Cu/Bi₂Ti₂O₇/氧化石墨烯	100 W氙灯, λ>420 nm	pH: 3~10 TC: 25、50、75、100、125 mg/L	pH为7、催化剂5 g/L、 TC25 mg/L	92^〔32〕
光催化	Ag₃PO₄/AgBr/g-C₃N₄	300 W氙灯, λ>420nm	pH: 3.0、5.4、7.0、9.0 TC: 10、20、30、40、50 mg/L	pH为9.0、催化剂0.5 g/L、 TC10 mg/L	90^〔26〕
光催化	Sr-Bi₂O₃	500 W氙灯, λ>420 nm	pH: 3、5、7、9、11 TC: 5、10、20、50 mg/L	pH为9、催化剂0.06 g/L、 TC5 mg/L	91.2^〔33〕
光催化	BiOBr	10 W LED灯, λ>420 nm	pH: 3.1、5.1、6.2、7.3、9.1、11.0 催化剂: 0.5、1.0、1.5 g/L	pH为9.1、催化剂1.5 g/L、 TC20 mg/L	94^〔34〕
光催化	AgBr/Bi₂	WO₆氙灯, λ>420 nm	pH: 2、4、6、8、10 TC: 20、30、40、50、60 mg/L	pH无波动、催化剂1 g/L、 TC20 mg/L	87.5^〔27〕
光催化	BiOI/Ag@AgI	300 W氙灯, λ>420 nm	催化剂: 0.10、0.30、0.50、1.00 g/L TC: 20、30、40、50、60 mg/L	催化剂0.30 g/L、 TC20 mg/L	86.4^〔35〕
光催化	Bi_mO_nBr_z	400 W卤钨灯, 无滤光片	pH: 2、6、11 催化剂: 0.5、1、1.5、2 g/L TC: 25、45 mg/L	pH为6、催化剂1 g/L、 TC25 mg/L	98.9^〔36〕
光催化	BiVO₄/Bi₂Ti₂O₇/Fe₃O₄	500 W氙灯, λ>365 nm	pH: 3.00、5.00、6.00、7.00、9.00 催化剂: 0.25、0.50、1.00、2.00、3.00 g/L TC: 10、20、30、40、50 mg/L	pH为6.00、催化剂1.00 g/L、 TC10 mg/L	97.22^〔37〕
光催化	Bi₂₄O₃₁Br₁₀	1 000 W氙灯, λ>420 nm	催化剂: 0.5、1.0、1.5、2.0、2.5 g/L TC: 20、40、60、80、100 mg/L	pH为4、催化剂1.5 g/L、 TC 20 mg/L	94^〔38〕

反应体系	催化剂	光源	影响因素	最优条件	TC降解率/%
光催化	Bi₂O₇Sn₂-Bi₇O₉I₃	太阳光	pH: 2、6、11 催化剂: 0.5、1、1.5g/L TC 35、55 mg/L	pH为6、催化剂1 g/L、 TC35 mg/L	80^〔30〕
光催化	Bi₂Sn₂O₇-C₃N₄/沸石	400 W卤钨灯, 无滤光片	pH: 3、6、9 催化剂: 0.75、1、1.25 g/L TC: 10、20、30 mg/L	pH为6、催化剂1 g/L、 TC20 mg/L	80.4^〔31〕
光催化	Cu/Bi₂Ti₂O₇/氧化石墨烯	100 W氙灯, λ>420 nm	pH: 3~10 TC: 25、50、75、100、125 mg/L	pH为7、催化剂5 g/L、 TC25 mg/L	92^〔32〕
光催化	Ag₃PO₄/AgBr/g-C₃N₄	300 W氙灯, λ>420nm	pH: 3.0、5.4、7.0、9.0 TC: 10、20、30、40、50 mg/L	pH为9.0、催化剂0.5 g/L、 TC10 mg/L	90^〔26〕
光催化	Sr-Bi₂O₃	500 W氙灯, λ>420 nm	pH: 3、5、7、9、11 TC: 5、10、20、50 mg/L	pH为9、催化剂0.06 g/L、 TC5 mg/L	91.2^〔33〕
光催化	BiOBr	10 W LED灯, λ>420 nm	pH: 3.1、5.1、6.2、7.3、9.1、11.0 催化剂: 0.5、1.0、1.5 g/L	pH为9.1、催化剂1.5 g/L、 TC20 mg/L	94^〔34〕
光催化	AgBr/Bi₂	WO₆氙灯, λ>420 nm	pH: 2、4、6、8、10 TC: 20、30、40、50、60 mg/L	pH无波动、催化剂1 g/L、 TC20 mg/L	87.5^〔27〕
光催化	BiOI/Ag@AgI	300 W氙灯, λ>420 nm	催化剂: 0.10、0.30、0.50、1.00 g/L TC: 20、30、40、50、60 mg/L	催化剂0.30 g/L、 TC20 mg/L	86.4^〔35〕
光催化	Bi_mO_nBr_z	400 W卤钨灯, 无滤光片	pH: 2、6、11 催化剂: 0.5、1、1.5、2 g/L TC: 25、45 mg/L	pH为6、催化剂1 g/L、 TC25 mg/L	98.9^〔36〕
光催化	BiVO₄/Bi₂Ti₂O₇/Fe₃O₄	500 W氙灯, λ>365 nm	pH: 3.00、5.00、6.00、7.00、9.00 催化剂: 0.25、0.50、1.00、2.00、3.00 g/L TC: 10、20、30、40、50 mg/L	pH为6.00、催化剂1.00 g/L、 TC10 mg/L	97.22^〔37〕
光催化	Bi₂₄O₃₁Br₁₀	1 000 W氙灯, λ>420 nm	催化剂: 0.5、1.0、1.5、2.0、2.5 g/L TC: 20、40、60、80、100 mg/L	pH为4、催化剂1.5 g/L、 TC 20 mg/L	94^〔38〕

m/z	编号	催化剂	结构式
461	A1	AgBr/Bi₂WO₆^〔27〕 CdS/Bi₃O₄Cl^〔49〕 Cu/Bi₂Ti₂O₇/氧化石墨烯^〔32〕 BiVO₄/Bi₂Ti₂O₇^〔50〕碳掺杂氮化/Bi₁₂O₁₇C_l2^〔51〕 BiOI/Ag@AgI^〔35〕 Bi₂WO6^〔52〕
	A2	BiOBr/Bi₂SiO₅^〔53〕
	A2	AgI/Bi₂Sn₂O₇^〔54〕
417	B1	AgI/Bi₂Sn₂O₇^〔54〕 Bi₂WO₆^〔52〕 Sr-Bi₂O₃^〔33〕 BiOBr/Bi₂SiO₅^〔53〕 BiOI/Ag@AgI^〔35〕 Ag₃PO₄/多壁碳纳米管/Bi2WO6^〔55〕
417	B2	Bi₂MoO₆^〔56〕
431	C	AgBr/Bi₂WO₆^〔27〕 Ag₃PO₄/多壁碳纳米管/Bi₂WO₆^〔55〕 BiOI/Ag@AgI^〔35〕
402	D1	Cu/Bi₂Ti₂O₇/氧化石墨烯^〔32〕 Bi₅FeTi₃O₁₅^〔57〕 BiVO₄/Bi₂Ti₂O₇^〔50〕
402	D2	AgI/Bi₂Sn₂O₇^〔54〕

m/z	编号	催化剂	结构式
461	A1	AgBr/Bi₂WO₆^〔27〕 CdS/Bi₃O₄Cl^〔49〕 Cu/Bi₂Ti₂O₇/氧化石墨烯^〔32〕 BiVO₄/Bi₂Ti₂O₇^〔50〕碳掺杂氮化/Bi₁₂O₁₇C_l2^〔51〕 BiOI/Ag@AgI^〔35〕 Bi₂WO6^〔52〕
	A2	BiOBr/Bi₂SiO₅^〔53〕
	A2	AgI/Bi₂Sn₂O₇^〔54〕
417	B1	AgI/Bi₂Sn₂O₇^〔54〕 Bi₂WO₆^〔52〕 Sr-Bi₂O₃^〔33〕 BiOBr/Bi₂SiO₅^〔53〕 BiOI/Ag@AgI^〔35〕 Ag₃PO₄/多壁碳纳米管/Bi2WO6^〔55〕
417	B2	Bi₂MoO₆^〔56〕
431	C	AgBr/Bi₂WO₆^〔27〕 Ag₃PO₄/多壁碳纳米管/Bi₂WO₆^〔55〕 BiOI/Ag@AgI^〔35〕
402	D1	Cu/Bi₂Ti₂O₇/氧化石墨烯^〔32〕 Bi₅FeTi₃O₁₅^〔57〕 BiVO₄/Bi₂Ti₂O₇^〔50〕
402	D2	AgI/Bi₂Sn₂O₇^〔54〕

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