多孔碳BVO/Zn@ZPC的制备及其光降解性能

doi:10.12422/j.issn.1006-396X.2023.06.004

摘要/Abstract

摘要：

降解四环素（TC）是防治水污染的难点。以ZIF?8为前驱体，采用直接焙烧法制备了多孔碳材料Zn@ZPC；采用水热法制备了BiVO₄（BVO），然后以Zn@ZPC和BVO为原料经原位热处理方法制备了BVO/Zn@ZPC复合材料；讨论了合成过程中BVO添加量（质量）和焙烧温度对催化剂物性及光催化性能的影响；分别采用XRD、SEM、TEM、N₂吸附?脱附、XPS、UV?vis DSR和ESR等技术，对光催化剂的形貌结构、金属物种的状态、孔结构等进行了分析。结果表明，在ZnO和BVO间形成了Z型异质结；在焙烧温度为600 ℃、BVO添加量为40 mg的条件下制得的BVO?40/Zn@ZPC?600复合材料具有最佳的光催化降解TC的性能；在可见光照射下，5 mg催化剂在60 min内可将100 mL的TC（50 mg/L）完全降解。

关键词: ZIF?8, 多孔碳, BiVO₄, 光催化, 四环素

Abstract:

Degradation of tetracycline(TC) is a challenge in the process of water pollution.A porous carbon material Zn@ZPC was obtained via direct roasting of ZIF?8 precursor and BiVO₄ （BVO）was prepared by a hydrothermal method. Subsequently,a hybrid BVO/Zn@ZPCcomposites were prepared by in?situ heat treatment of Zn@ZPC and BVO.Meanwhile,the effects of the addition amount of BVO and roasting temperature on catalyst properties and photocatalytic performance were discussed in the process.The morphology and structure of the photocatalysts,the state of the metal species, and the pore structure were analysed by XRD,SEM,TEM,XPS,N₂ adsorption?desorption,UV?vis DSR,and ESR techniques,respectively.The results showed that a Z?type heterojunction was formed between ZnO and BVO.In the experiments of photodegradation of tetracycline, BVO?40/Zn@ZPC?600 with a roasting temperature of 600 ℃and a BVO additive amount of 40 mg had the best photocatalytic degradation performance: under the irradiation of visible light,5 mg of the catalyst was able to completely degrade 100 mL TC(50 mg/L) within 60 min.

Key words: ZIF?8, Porous carbon, BiVO₄, Photocatalysis, Tetracycline

中图分类号:

TQ032.41

宁尧, 刘满, 刘素燕. 多孔碳BVO/Zn@ZPC的制备及其光降解性能[J]. 石油化工高等学校学报, 2023, 36(6): 36-47.

Yao NING, Man LIU, Suyan LIU. Preparation and Photodegradation Performances of Porous Carbon BVO/Zn@ZPC[J]. Journal of Petrochemical Universities, 2023, 36(6): 36-47.

图/表 15

图1 样品的XRD和LRS谱图

Fig.1 XRD and LRS spectra of the samples

图2 样品的SEM和EDX图像

Fig.2 SEM image and EDX images of the samples

图3 样品的TEM和HRTEM图像

Fig.3 TEM image and HRTEM image of the samples

图4 样品的N2吸附?脱附等温线和NL?DFT孔径分布曲线

Fig.4 N2 adsorption?desorption isotherm and NL?DFT pore size distribution curve of the samples

表1 样品的比表面积和孔体积

Table 1 Specific surface area and pore volume of the samples

样品	S_BET/（m² $⋅$ g^-1）	S_mic/（m² $⋅$ g^-1）	S_ext/（m² $⋅$ g^-1）	V_total/（cm³ $⋅$ g^-1）
Zn@ZPC⁃600	220.1	52.2	167.9	0.511
BVO⁃40/Zn@ZPC⁃600	25.3	9.3	16.0	0.109
BVO	8.4	3.6	4.8	0.043

表1 样品的比表面积和孔体积

Table 1 Specific surface area and pore volume of the samples

样品	S_BET/（m² $⋅$ g^-1）	S_mic/（m² $⋅$ g^-1）	S_ext/（m² $⋅$ g^-1）	V_total/（cm³ $⋅$ g^-1）
Zn@ZPC⁃600	220.1	52.2	167.9	0.511
BVO⁃40/Zn@ZPC⁃600	25.3	9.3	16.0	0.109
BVO	8.4	3.6	4.8	0.043

图5 样品的XPS谱图

Fig.5 XPS spectra of the samples

图6 样品的紫外漫反射谱图

Fig.6 UV diffuse reflectance spectra of the samples

图7 样品的光学带隙图

Fig.7 Optical bandgap spectra of the samples

图8 样品的荧光谱图

Fig.8 Fluorescence spectra of the samples

图9 样品的光降解性能评价

Fig.9 Photodegradation performance evaluation chart

图10 BVO、Zn@ZPC?600和BVO?40/Zn@ZPC?600的动力学曲线

Fig.10 Kinetic curves of BVO, Zn@ZPC?600 and BVO?40/Zn@ZPC?600

图11 样品的莫特肖特基图和VB?XPS图

Fig.11 Mott?Schottky diagram,VB?XPS diagram of the samples

图12 样品的自由基捕获图（a） DMPO-· O2- （b） DMPO-· OH

Fig.12 Free radical capture diagram of the samples

图13 样品的瞬时光电流响应图和阻抗谱图

Fig.13 Instantaneous current response plot and impedance spectrum of the samples

图14 BVO?40/Zn@ZPC?600在可见光条件下降解TC的机理示意图

Fig.14 Diagram of the mechanism of degradation of TC by BVO?40/Zn@ZPC?600 under visible light conditions

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