Zn2SiO4-ZnO-生物炭复合物的制备及其可见光催化H2O2降解甲硝唑

doi:10.15541/jim20190530

摘要/Abstract

摘要：

以松木碱解液代替NaOH溶液作为锌盐沉淀剂, 采用水热法制备了Zn₂SiO₄-ZnO-生物炭三元复合材料(SOB-x-y, x代表松木粉的用量, y代表NaOH浓度), 通过不同手段对样品进行表征, 研究了光催化H₂O₂降解甲硝唑的性能。结果表明, 制备的催化剂由枣核状硅锌矿型Zn₂SiO₄介晶、多边形六方晶相ZnO和松木生物炭构成; 与纯六方晶相ZnO相比, 它具有更大的比表面积与孔容、更小的带隙能和更弱的荧光发射, 因而具有更好的光催化活性。Zn₂SiO₄-ZnO-生物炭对甲硝唑的光催化H₂O₂降解过程符合准一级动力学方程, 其催化活性随NaOH浓度的增大而提高, 随松木粉用量的增加先增加后减小, 以SOB-3-4的性能最优。SOB-3-4的速率常数(k)和降解率(η)随pH的降低而增大, 随H₂O₂浓度的升高而增大, 随催化剂用量的增加先增大后减小; 甲硝唑的降解率随其初始浓度的升高逐渐越低。当初始pH为3、催化剂用量为0.4 g/L、H₂O₂投加浓度为80 mmol/L及甲硝唑初始浓度为300 mg/L时, k为2.68×10 ^-2 min ^-1, 反应3 h后η达到99.70%。本研究结果对处理难降解制药废水提供了重要的实验依据。

关键词: Zn₂SiO₄-ZnO-生物炭复合材料, 松木碱解液, 水热合成, 光催化, 甲硝唑

Abstract:

Using pine alkali hydrolysate to replace NaOH solution as zinc salt precipitator, the Zn₂SiO₄-ZnO-biochar (SOB-x-y, x is the dosage of pine powder, while y is the concentration of NaOH) ternary composites were prepared by hydrothermal method. The photocatalysts were characterized by different methods. The degradation of metronidazole over the H₂O₂ photocatalysis was studied. Results showed that the as-prepared photocatalysts were composed of jujube-type willemite Zn₂SiO₄ mesocrystals, hexagonal ZnO and pine biochar. Compared with pure hexagonal ZnO, the SOB-x-y photocatalysts has better H₂O₂ photocatalytic activity due to the higher surface area and pore volume, lower band gap energy, lower PL emission peak intensity. Metronidazole degradation using the H₂O₂ photocatalysis was well-fitted to a pseudo-first-order kinetic model by SOB-x-y. Its catalytic activity increased with the increase of NaOH concentration, and increased at first and then decreased with the increase of pine flour content. The SOB-3-4 has best photocatalytic acitivity. Meanwhile, rate constant (k) and degradation rate (η) of SOB-3-4 increase with the decrease of pH, increase with the increase of H₂O₂ concentration, increase firstly and then decrease with the increase of catalyst dosage. Degradation rate of metronidazole gradually decreases with the increase of its initial concentration. Under the optimal condition (pH=3, catalyst dosage of 0.4 g/L, H₂O₂ dosage of 80 mmol/L, initial metronidazole concentration of 300 mg/L), k value was 2.68×10 ^-2 min ^-1 and η reached 99.70% after reaction for 3 h. This study provides an important experimental basis for the treatment of pharmaceutical wastewater.

Key words: Zn₂SiO₄-ZnO-biochar composites, pine alkali hydrolysate, hydrothermal syntheticsis, photocatalysis, metronidazole

中图分类号:

张东硕,蔡昊,高凯茵,马子川. Zn₂SiO₄-ZnO-生物炭复合物的制备及其可见光催化H₂O₂降解甲硝唑[J]. 无机材料学报, 2020, 35(8): 923-930.

ZHANG Dongshuo,CAI Hao,GAO Kaiyin,MA Zichuan. Preparation and Visible-light Photocatalytic Degradation on Metronidazole of Zn₂SiO₄-ZnO-biochar Composites[J]. Journal of Inorganic Materials, 2020, 35(8): 923-930.

图/表 13

图1 催化剂对甲硝唑的吸附动力学曲线

Fig. 1 Adsorption kinetic curves of metronidazole on the catalysts

图2 光催化H2O2降解甲硝唑的动力学分析

Fig. 2 Degradation kinetics of metronidazole by H2O2 photocatalysis (a) Effect of NaOH concentration; (b) Effect of pine wood flour dosage

图3 不同反应体系降解甲硝唑效果比较

Fig. 3 Comparison of metronidazole degradation in different reaction systems

图4 SOB-3-4和ZnO的XRD图谱

Fig. 4 XRD patterns of SOB-3-4 and ZnO

图5 (a)ZnO的SEM照片, SOB-3-4的(b)SEM照片和(c)EDS谱图

Fig. 5 (a) SEM image of ZnO, (b) SEM image and (c) EDS results of SOB-3-4

图6 ZnO和SOB-3-4的红外光谱图

Fig. 6 FT-IR spectra of ZnO and SOB-3-4

表1 不同催化剂的比表面积、孔容及孔径

Table 1 Specific surface area, pore volume and pore size of catalysts

Catalyst	Specific surface area/(m²?g^-1)	Pore volume/ (cm³?g^-1)	Pore size/nm
SOB-3-4	31.29	0.32	20.40
ZnO	24.39	0.24	19.74

图7 SOB-3-4和ZnO的紫外-可见漫反射光谱(a)及其对应的(αhν)2与光子能量关系图(b)

Fig. 7 UV-Vis diffuse reflectance spectra of SOB-3-4 and ZnO (a), and corresponding relationship between (αhv)2 and photonic energy(b)

图8 SOB-3-4和ZnO的光致发光光谱图

Fig. 8 PL spectra of SOB-3-4 and ZnO

图9 SOB-3-4在不同pH条件下对甲硝唑的降解率

Fig. 9 Effect of pH on metronidazole degradation over SOB-3-4

图10 H2O2浓度对SOB-3-4的甲硝唑降解性能的影响

Fig. 10 Effect of H2O2 concentration on the degradation efficiency of metronidazole over SOB-3-4

图11 SOB-3-4的用量对甲硝唑的降解效能的影响

Fig. 11 Effect of SOB-3-4 amount on the degradation efficiency of metronidazole

图12 甲硝唑浓度对其光芬顿降解效果的影响

Fig. 12 Effect of initial concentration of metronidazole on the degradation over SOB-3-4

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Zn₂SiO₄-ZnO-生物炭复合物的制备及其可见光催化H₂O₂降解甲硝唑

Preparation and Visible-light Photocatalytic Degradation on Metronidazole of Zn₂SiO₄-ZnO-biochar Composites

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