碳量子点修饰半导体复合光催化剂降解水中有机污染物

doi:10.16085/j.issn.1000-6613.2022-2044

摘要/Abstract

摘要：

可见光有效利用率低、光生载流子复合快是导致传统光催化剂在应用于降解水中有机污染物中效率不高、应用受限的主要原因。碳量子点（carbon quantum dots，CQDs）作为新兴的纳米零维材料，用其修饰半导体光催化剂能够抑制光生载流子复合、加速载流子的分离与转移、改善光谱响应范围、增强吸附性能、促进间接氧化过程中过渡金属还原，有效增强光催化剂催化降解水中有机污染物。本文主要介绍了CQDs修饰半导体复合光催化剂材料在降解水中各类有机污染物中的应用，重点阐述了CQDs及其修饰半导体复合光催化剂材料的合成以及CQDs在多相光催化体系中的增强作用；简要说明了光降解实验参数、CQDs改性对光催化反应活性的影响；最后对CQDs修饰半导体复合光催化剂发展过程中尚待解决的问题进行了总结并对未来发展方向进行了展望。

关键词: 碳量子点, 半导体, 光催化剂, 复合材料, 降解, 有机污染物

Abstract:

The primary causes of the low efficiency and limited use of conventional photocatalysts in the degradation of organic pollutants in water are the low effective utilisation of visible light and the fast recombination rate of photogenerated charge carrier. Carbon quantum dots (CQDs), a novel nano-zero-dimensional material that modifies semiconductor photocatalysts, can inhibit the recombination of photogenerated carriers, speed up the separation and transfer of carriers, improve the spectral response range, improve the performance of adsorption, promote the reduction of transition metals in the indirect oxidation process and effectively enhance the photocatalytic degradation of organic pollutants in water. This paper reviewed the application of CQDs modified semiconductor composite photocatalyst materials in the degradation of various organic pollutants in water. It focused on the synthesis strategy of CQDs and its modified semiconductor composite photocatalyst materials as well as the enhancement of CQDs in multiphase photocatalytic systems. Furthermore, a brief description was given of the effects of the photocatalytic experimental parameters and the modification of CQDs on the photocatalytic reaction activity. Finally, this paper summarized the unresolved issues during the development of CQDs modified semiconductor composite photocatalysts and gave an outlook on the future development direction.

Key words: carbon quantum dots (CQDs), semiconductor, photocatalyst, composites, degradation, organic pollutants

中图分类号:

O643.3

章萍萍, 丁书海, 高晶晶, 赵敏, 俞海祥, 刘玥宏, 谷麟. 碳量子点修饰半导体复合光催化剂降解水中有机污染物[J]. 化工进展, 2023, 42(10): 5487-5500.

ZHANG Pingping, DING Shuhai, GAO Jingjing, ZHAO Min, YU Haixiang, LIU Yuehong, GU Lin. Carbon quantum dots modified semiconductor composite photocatalysts for degradation of organic pollutants in water[J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5487-5500.

图/表 8

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合成方法	优点	缺点	文献
自上而下
电化学法	制备的CQDs的均匀性较好；碳源利用率高	步骤烦琐耗时；量子产率较低	[11]
激光销蚀法	—	使用仪器昂贵；量子产率较低；制备的CQDs杂质多	[17-18]
超声剥离	操作过程简单方便；反应条件温和	量子产率较低；反应时间较长	[9]
化学氧化法	碳源较易获得；产物有利于进一步修饰	反应时间较长；后处理复杂，产物不易收集；存在环境问题；制备的CQDs粒径不够均一	[12, 19]
自下而上
微波辅助法	操作简便快捷	制备的CQDs粒径不均匀	[13]
热解法	操作简便；碳源成本低；适宜大规模制备	反应时间较长；能源消耗大	[14-15]
水热/溶剂热法	操作简便；成本较低；制备的CQDs粒径均匀；量子产率较高	反应时间较长；能源消耗大	[16, 20]
模板法	量子产率较高，粒径分布均匀；水溶性好；生物毒性低	步骤相对复杂	[18]

合成方法	优点	缺点	文献
自上而下
电化学法	制备的CQDs的均匀性较好；碳源利用率高	步骤烦琐耗时；量子产率较低	[11]
激光销蚀法	—	使用仪器昂贵；量子产率较低；制备的CQDs杂质多	[17-18]
超声剥离	操作过程简单方便；反应条件温和	量子产率较低；反应时间较长	[9]
化学氧化法	碳源较易获得；产物有利于进一步修饰	反应时间较长；后处理复杂，产物不易收集；存在环境问题；制备的CQDs粒径不够均一	[12, 19]
自下而上
微波辅助法	操作简便快捷	制备的CQDs粒径不均匀	[13]
热解法	操作简便；碳源成本低；适宜大规模制备	反应时间较长；能源消耗大	[14-15]
水热/溶剂热法	操作简便；成本较低；制备的CQDs粒径均匀；量子产率较高	反应时间较长；能源消耗大	[16, 20]
模板法	量子产率较高，粒径分布均匀；水溶性好；生物毒性低	步骤相对复杂	[18]

CQDs的作用	光催化材料	污染物	带隙宽度/eV		吸收边/nm		文献
CQDs的作用	光催化材料	污染物	CQDs引入前	CQDs引入后	CQDs引入前	CQDs引入后	文献
光谱转换器	NCQDs/BiO_1-_x Br	氧氟沙星	BiOBr：3.24	NCQDs/BiO_1-xBr：2.96	BiOBr：425	红移	[42]
	CQDs/g-C₃N₄	双酚A	g-C₃N₄：2.70	CQDs/g-C₃N₄：2.57	g-C₃N₄：450	红移	[46]
	CQDs/CeO₂/BiOCl	罗丹明B	CeO₂：2.90 BiOCl：3.40	CQDs/CeO₂/BiOCl：2.23	—	红移	[47]
光敏剂	CQDs/ZnO	苯酚	ZnO：3.26	CQDs/ZnO：2.96	—	红移	[45]
	CQDs/TiO₂	苯酚	TiO₂：3.2	CQDs/TiO₂：2.9	TiO₂：390	CQDs/TiO₂：425	[48]
	TiO₂/WO₃/CQDs	头孢氨苄	TiO₂：3.18 TiO₂/WO₃：2.76	TiO₂/WO₃/CQDs：2.61	TiO₂：390	TiO₂/CQDs：475 TiO₂/WO₃/CQDs：红移	[25]
	CQDs/g-C₃N₄/Bi₂MoO₆	环丙沙星	g-C₃N₄：2.70 Bi₂MoO₆/g-C₃N₄：2.64	CQDs/Bi₂MoO₆/g-C₃N₄：2.07	g-C₃N₄：443 Bi₂MoO₆ /g-C₃N₄：520	CQDs/Bi₂MoO₆ /g-C₃N₄：599	[21]

CQDs的作用	光催化材料	污染物	带隙宽度/eV		吸收边/nm		文献
CQDs的作用	光催化材料	污染物	CQDs引入前	CQDs引入后	CQDs引入前	CQDs引入后	文献
光谱转换器	NCQDs/BiO_1-_x Br	氧氟沙星	BiOBr：3.24	NCQDs/BiO_1-xBr：2.96	BiOBr：425	红移	[42]
	CQDs/g-C₃N₄	双酚A	g-C₃N₄：2.70	CQDs/g-C₃N₄：2.57	g-C₃N₄：450	红移	[46]
	CQDs/CeO₂/BiOCl	罗丹明B	CeO₂：2.90 BiOCl：3.40	CQDs/CeO₂/BiOCl：2.23	—	红移	[47]
光敏剂	CQDs/ZnO	苯酚	ZnO：3.26	CQDs/ZnO：2.96	—	红移	[45]
	CQDs/TiO₂	苯酚	TiO₂：3.2	CQDs/TiO₂：2.9	TiO₂：390	CQDs/TiO₂：425	[48]
	TiO₂/WO₃/CQDs	头孢氨苄	TiO₂：3.18 TiO₂/WO₃：2.76	TiO₂/WO₃/CQDs：2.61	TiO₂：390	TiO₂/CQDs：475 TiO₂/WO₃/CQDs：红移	[25]
	CQDs/g-C₃N₄/Bi₂MoO₆	环丙沙星	g-C₃N₄：2.70 Bi₂MoO₆/g-C₃N₄：2.64	CQDs/Bi₂MoO₆/g-C₃N₄：2.07	g-C₃N₄：443 Bi₂MoO₆ /g-C₃N₄：520	CQDs/Bi₂MoO₆ /g-C₃N₄：599	[21]

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