Mechanism Study on Degradation of Tetracycline Hydrochloride by Ag/Ag2O/g-C3N4/BiVO4 Composite Photocatalytic System
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摘要: 为提高钒酸铋(BiVO4)对盐酸四环素(TC-HCl)在水溶液中的降解效率，以银基材料(Ag/Ag2O)和石墨相氮化碳(g-C3N4)共同改性BiVO4，通过水热法、煅烧法、湿浸渍法、沉淀和热分解法分步制备了Ag/Ag2O/g-C3N4/BiVO4四元复合材料；采用X-射线衍射(XRD)、扫描电子显微镜(SEM)、X-射线光电子能谱(XPS)及紫外-可见漫反射光谱法(UV-vis DRS)等方法对复合材料的形貌结构、元素分布及光学性质进行了表征. 结果表明：①沉积了Ag/Ag2O粒子后，复合材料对TC-HCl的吸附能力显著提高. ②纳米Ag粒子的表面等离子体共振效应(SPR)以及g-C3N4的协同作用拓宽了光响应范围，表现出更好的光催化性能. ③相较于BiVO4、g-C3N4及g-C3N4/BiVO4，该复合材料对TC-HCl的降解效果最佳，降解率可达89.19%，且经过4次循环使用后仍能保持74.8%的降解率. ④UV-vis及XPS分析证明，该复合材料的可见光响应拓展至548 nm，可吸收更多可见光. ⑤体系自由基捕获试验证明，·O2-和h+在光催化降解TC-HCl过程中发挥主要作用，且h+的作用大于·O2-. 研究显示，Ag/Ag2O/g-C3N4/BiVO4是一种高效稳定的复合光催化剂，其在处理TC-HCl抗生素废水方面具有潜在的应用前景.
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关键词:
- 光催化 /
- 石墨相氮化碳(g-C3N4) /
- 氧化银 /
- 钒酸铋(BiVO4)
Abstract: In order to improve the degradation efficiency of bismuth vanadate (BiVO4) on tetracycline hydrochloride (TC-HCl) in aqueous solution, silver-based material (Ag/Ag2O) and graphitic phase carbon nitride (g-C3N4) were used to co-modify BiVO4, and the Ag/Ag2O/g-C3N4/BiVO4 quaternary composites were constructed by hydrothermal, calcination, wet impregnation, precipitation and thermal decomposition methods in a stepwise manner. The composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Ultraviolet-visible diffuse reflectance spectrometry (UV-vis DRS) for their morphological structure, elemental distribution and optical properties. The experimental results showed that: (1) The deposition of Ag/Ag2O particles significantly increased the adsorption capacity of the material for TC-HCl. (2) The surface plasmon resonance effect (SPR) of Ag nanoparticles and the synergistic effect of g-C3N4 broadened the photoresponse range and improved the photocatalytic performance. (3) Compared with BiVO4, g-C3N4 and g-C3N4/BiVO4, the composite had the best degradation effect on TC-HCl, with the degradation rate up to 89.19%, and the degradation efficiency was still 74.8% after four cycles. (4) UV-vis and XPS analysis determined that the visible light response of the composite extended to 548 nm and could absorb more visible light. (5) The system radical trapping test demonstrated that ·O2- and h+ played a major role in the photocatalytic degradation of TC-HCl, and the role of h+ was greater than that of ·O2-. The above results show that Ag/Ag2O/g-C3N4/BiVO4 is an efficient and stable composite photocatalyst with potential application in the treatment of TC-HCl antibiotic wastewater. -
图 2 BiVO4、g-C3N4和Ag/Ag2O/g-C3N4/BiVO4复合材料的SEM图像
Figure 2. SEM images of BiVO4, g-C3N4, and Ag/Ag2O/g-C3N4/BiVO4 composites
图 3 Ag/Ag2O/g-C3N4/BiVO4的EDS扫描能谱分析的元素面分布
注：在图 2(c)所示尺度下拍摄的图谱.
Figure 3. Elemental surface distribution for EDS maps of Ag/Ag2O/g-C3N4/BiVO4
图 4 Ag/Ag2O/g-C3N4/BiVO4复合材料的EDS图谱
Figure 4. EDS images of Ag/Ag2O/g-C3N4/BiVO4 composites
图 5 Ag/Ag2O/g-C3N4/BiVO4复合材料XPS图谱
Figure 5. XPS spectra of Ag/Ag2O/g-C3N4/BiVO4 composite
图 6 BiVO4、g-C3N4、Ag/Ag2O/g-C3N4/BiVO4的UV-Vis光谱以及BiVO4和g-C3N4的禁带宽度
Figure 6. UV-Vis spectra of BiVO4, g-C3N4, Ag/Ag2O/g-C3N4/BiVO4 and forbidden band widths of BiVO4 and g-C3N4
图 7 不同光催化剂对TC-HCl降解效果的时间变化曲线
Figure 7. Degradation curves of TC-HCl by different photocatalysts
图 9 Ag/Ag2O/g-C3N4/BiVO4光催化降解TC-HCl的捕获试验
Figure 9. Capture experiments of Ag/Ag2O/g-C3N4/BiVO4 photocatalytic degradation of TC-HCl
图 10 Ag/Ag2O/g-C3N4/BiVO4复合材料的光催化机理示意
Figure 10. Schematic diagram of the possible photocatalytic mechanism of Ag/Ag2O/g-C3N4/BiVO4 composites
表 1 不同光催化材料对TC-HCl光催化降解的拟一级动力学参数
Table 1. Proposed primary kinetic parameters for the photocatalytic degradation of TC-HCl by different photocatalytic materials
光催化材料 拟一级动力学模型 反应动力学常数(kap)/min-1 相关系数(R2) g-C3N4 -ln(C0/Ct)=0.014 8t+0.014 8 0.014 8 0.982 0 BiVO4 -ln(C0/Ct)=0.032 0t+0.024 8 0.032 0 0.938 4 g-C3N4/BiVO4 -ln(C0/Ct)=0.030 3t+0.036 5 0.030 3 0.979 1 Ag/Ag2O/g-C3N4/BiVO4 -ln(C0/Ct)=0.070 3t+0.086 9 0.070 3 0.952 8 
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