磁性纳米CeO2/Fe3O4非均相Fenton反应催化降解氧氟沙星

doi:10.15541/jim20150542

摘要/Abstract

摘要：

为了提高Fe₃O₄的催化活性, 制备了磁性CeO₂/Fe₃O₄复合纳米粒子, 构成非均相Fenton反应体系, 催化降解水环境中的氧氟沙星抗生素。研究了CeO₂含量、H₂O₂浓度、pH等因素对CeO₂/Fe₃O₄非均相催化活性的影响, 并通过溶出铁离子测定、动力学拟合等方式对反应机理进行探究。结果表明, CeO₂/Fe₃O₄较Fe₃O₄具有更强的催化活性, 氧氟沙星的降解率随CeO₂含量、H₂O₂浓度和溶液酸度的增加而提高, 当H₂O₂浓度为100 mmol/L 以及pH为3时, CeO₂/Fe₃O₄(摩尔比=0.780)-H₂O₂体系催化降解氧氟沙星的效果最佳。CeO₂/Fe₃O₄体系催化降解氧氟沙星反应遵循一级反应动力学方程, 反应机理主要为催化剂表面的催化反应, 同时CeO₂产生氧空位的电子转移对Fe₃O₄的催化反应起到协同强化的作用。

关键词: Fe3O4, CeO2, 降解, 氧氟沙星

Abstract:

CeO₂/Fe₃O₄ magnetic nanoparticles were prepared for promoting the catalytic activity of Fe₃O₄, which is applied as the catalyst of heterogeneous Fenton reaction system for the degradation of ofloxacin. Several factors that affected the degradation efficiency of the system such as CeO₂ content, H₂O₂concentration and pH were investigated. The mechanism of catalytic degradation was also explored via the measurement of iron ion and kinetics fitting. The results show that the catalytic activity of CeO₂/Fe₃O₄ is better than that of Fe₃O₄. The degradation efficiency of ofloxacin increases with the addition of CeO₂ content, H₂O₂concentration or solution acidity increase. The degradation effect of ofloxacin is the best for CeO₂/Fe₃O₄(molar roction=0.780)-H₂O₂ catalytic system when H₂O₂concentration is 100 mmol/L and pH is 3, which accords first order kinetics model. The catalytic ability of CeO₂/Fe₃O₄is strengthened through surface catalytic reaction and electronic transfer of oxygen vacancies of CeO₂during catalytic reaction.

Key words: ferriferrous oxide, cerium oxide, degradation, ofloxacin

中图分类号:

胡晓丹, 周志伟, 张伟, 张晓红, 张海黔. 磁性纳米CeO₂/Fe₃O₄非均相Fenton反应催化降解氧氟沙星[J]. 无机材料学报, 2016, 31(6): 613-620.

HU Xiao-Dan, ZHOU Zhi-Wei, ZHANG Wei, ZHANG Xiao-Hong, ZHANG Hai-Qian. Heterogeneous Fenton Reaction for Degradation of Ofloxacin with Magnetic CeO₂/Fe₃O₄[J]. Journal of Inorganic Materials, 2016, 31(6): 613-620.

图/表 14

表1 CeO2/Fe3O4样品中元素的质量百分比

Table 1 Element weight percent of CeO2/Fe3O4 samples

	FC1	FC2	FC3	FC4
Fe(wt%)	80.52	57.73	50.53	43.16
Ce(wt%)	4.44	7.81	27.29	28.10
CeO₂: Fe₃O₄ (mol:mol)	0.066	0.162	0.647	0.780

图1 CeO2/Fe3O4样品的XRD图谱

Fig. 1 XRD pattern of CeO2/Fe3O4 sample

图2 CeO2/Fe3O4样品的透射电镜照片及其电子衍射照片

Fig. 2 TEM (HRTEM) and SAED images of CeO2/Fe3O4 sample

图3 CeO2/Fe3O4样品的的XPS图谱

Fig. 3 XPS spectra of CeO2/Fe3O4 sample. (a) wide-scan, (b) Fe2p, (c) O1s, and (d) Ce3d

图4 Fe3O4与CeO2/Fe3O4样品的(a)磁化曲线和(b)局部放大图

Fig. 4 Magnetic hystersis loop (a) and partial enlarged drawing of Fe3O4 and CeO2/Fe3O4 samples (b)

图5 不同样品的催化效果

Fig. 5 Catalytic effects of different samples

图6 CeO2含量对降解氧氟沙星的影响

Fig. 6 Effect of the amount of CeO2 on the degradation of ofloxacin

图7 H2O2浓度对降解氧氟沙星的影响

Fig. 7 Effect of H2O2 dosage on the degradation of ofloxacin

图8 pH对降解氧氟沙星的影响

Fig. 8 Effect of pH on the degradation of ofloxacin

图9 溶液中铁含量的变化

Fig. 9 Changes of iron concentration in the solution

图10 铁离子对降解氧氟沙星的影响

Fig. 10 Effect of iron ion on the degradation of ofloxacin

图11 (a)零级、(b)一级和(c)二级反应动力学拟合

Fig. 11 Kinetic fitting of zero- (a), first- (b) and second- (c) order reaction

表2 零级、一级、二级动力学拟合相关系数

Table 2 Correlation coefficent of zero, first and second-order kinetic fitting

R²	Fe₃O₄	FC1	FC2	FC3	FC4
Zero	0.938825	0.916653	0.890551	0.845094	0.727916
First	0.982795	0.958715	0.977587	0.992056	0.991458
Second	0.927562	0.96293	0.873888	0.739858	0.616759

图12 非均相Fenton反应的机理图

Fig. 12 Mechanism of heterogeneous Fenton reaction

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磁性纳米CeO₂/Fe₃O₄非均相Fenton反应催化降解氧氟沙星

Heterogeneous Fenton Reaction for Degradation of Ofloxacin with Magnetic CeO₂/Fe₃O₄

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