磁性ZnFe2O4/埃洛石复合材料的结构及吸附性能研究

doi:10.15541/jim20170244

无机材料学报 ›› 2018, Vol. 33 ›› Issue (4): 390-396.DOI: 10.15541/jim20170244

磁性ZnFe₂O₄/埃洛石复合材料的结构及吸附性能研究

孙青^1,2, 祁琪¹, 张俭^1,2, 潘方珍³, 盛嘉伟^1,2

1. 浙江工业大学材料科学与工程学院, 杭州 310014;
2. 浙江工业大学温州科学技术研究院, 温州 325011;
3. 浙江省地质矿产研究所, 杭州 310008

收稿日期:2017-05-16 修回日期:2017-08-14 出版日期:2018-04-30 网络出版日期:2018-03-27
作者简介:孙青(1987-), 男, 讲师. E-mail: qingsun@zjut.edu.cn
基金资助:
国家自然科学基金(51604242);浙江省教育厅科研项目(Y201534915);浙江省非金属矿工程技术研究中心开放课题基金(ZD2015k06);温州市重大科技专项(ZG2017029)

Structure and Adsorption Property of Magnetic ZnFe₂O₄-halloysite Composite Material

SUN Qing^1,2, QI Qi¹, ZHANG Jian¹, PAN Fang-Zhen³, SHENG Jia-Wei^1,2

1. College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou 310014, China;
2. Wenzhou Institute of Science and Technology, Zhejiang University of Technology, Wenzhou 325011, China;
3. Zhejiang Institute of Geology and Mineral Resource, Hangzhou 310008, China

Received:2017-05-16 Revised:2017-08-14 Published:2018-04-30 Online:2018-03-27
About author:SUN Qing. E-mail: qingsun@zjut.edu.cn
Supported by:
National Natural Science Foundation of China (51604242);Research Project of Zhejiang Provincial Education Department (Y201534915;Open Project Program of Zhejiang Non-metallic Minerals Engineering and Technology Research Center (ZD2015k06);Major Science and Technology Project of Wenzhou (ZG2017029)

摘要/Abstract

摘要：

采用溶胶-凝胶法制备磁性ZnFe₂O₄/埃洛石复合材料(MHNTs), 并对其吸附亚甲基蓝(MB)的性能进行研究。利用X射线衍射仪(XRD)、透射电子显微电镜(TEM)、傅里叶变换红外光谱仪(FT-IR)和振动样品磁强计(VSM)等对MHNTs的结构、形貌和磁性能进行表征, 采用静态批量平衡法对MB在MHNTs上的吸附行为和机理进行探究, 并考察了初始浓度、吸附时间和温度等因素的影响。结果表明: 复合材料中ZnFe₂O₄以10~30 nm尖晶石型纳米粒子沉积到埃洛石纳米管表面, 通过谢乐公式计算纳米ZnFe₂O₄的晶粒尺寸为19.1 nm; MHNTs具有良好的顺磁性和磁回收性。MHNTs对MB的吸附行为符合准二级动力学方程, 其吸附热力学过程符合Langmuir吸附等温线; 温度对MB在MHNTs上的吸附影响较大, 且升高温度有利于MHNTs对MB的吸附。此外, MHNTs可通过磁外场有效回收, 经过5次重复使用后MHNTs对10 mg/L MB溶液的吸附性能基本没有下降。

关键词: ZnFe₂O₄, 埃洛石纳米管, MB, 吸附, 动力学, 热力学

Abstract:

Magnetic ZnFe₂O₄/halloysite composite (MHNTs) was synthesized by Sol-Gel process and its sorption behavior towards methylene blue (MB) was studied. Structure, morphology and magnetic property of MHNTs were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), fourier transfer infrared (FT-IR), and vibrating sample magnetometer (VSM). Static batch equilibrium method was used to investigate the adsorption behavior and mechanism of MB on MHNTs. The results show that ZnFe₂O₄ composites with 10~30 nm spinel type nanoparticles are well loaded on the surface of HNTs. The average grain size of nano-ZnFe₂O₄ is 19.1 nm calculated by Scherrer equation．MHNTs exhibit good paramagnetic and magnetic recovery properties. MB sorption of MHNTs follows pseudo-second order kinetic model and Langmuir thermodynamics model. MB sorption process is strongly affected by temperature, and higher temperature is beneficial for the adsorption of MB by MHNTs. Furthermore, MHNTs can be recovered effectively by magnetic field and the adsorption properties of MHNTs on 10 mg/L MB solutions hardly decreased after 5 times of repeated use.

Key words: ZnFe₂O₄, halloysite nanotubes, MB, adsorption, dynamics, thermodynamics

中图分类号:

TB332

孙青, 祁琪, 张俭, 潘方珍, 盛嘉伟. 磁性ZnFe₂O₄/埃洛石复合材料的结构及吸附性能研究[J]. 无机材料学报, 2018, 33(4): 390-396.

SUN Qing, QI Qi, ZHANG Jian, PAN Fang-Zhen, SHENG Jia-Wei. Structure and Adsorption Property of Magnetic ZnFe₂O₄-halloysite Composite Material[J]. Journal of Inorganic Materials, 2018, 33(4): 390-396.

图/表 11

图1 MHNTs(a)、ZnFe2O4(b)和HNTs(c)的XRD图谱

Fig. 1 XRD patterns of MHNTs (a), ZnFe2O4 (b) and HNTs(c)

图2 MHNTs的低倍(a)和高倍(b)TEM照片

Fig. 2 Low magnification (a) and high magnification (b) TEM images of MHNTs

图3 MHNTs的磁滞回线图

Fig. 3 VSM curve of MHNTs

图4 MHNTs的外磁场吸附图

Fig. 4 Adsorption of MHNTs by external magnetic field

图5 HNTs和MHNTs的红外光谱图

Fig. 5 FT-IR spectra of HNTs and MHNTs

图6 MHNTs用量对MB吸附效果的影响

Fig. 6 Effect of MHNTs dosage on adsorption towards MB

图7 吸附时间对MB吸附的影响及准二级动力学拟合

Fig. 7 Effect of contact time on the adsorption towards MB on MHNTs and the pseudo-second order rate equation fit of MB

图8 MHNTs对MB在不同温度下的吸附等温线

Fig. 8 Adsorption isotherms of MHNTs towards MB at different temperatures

图9 不同温度下MB在MHNTs上的Langmuir(a)和 Freundlich(b)吸附模型拟合曲线

Fig. 9 Langmuir (a) and Freundlich (b) isotherms of MB adsorption on MHNTs at different temperatures

表1 不同温度下MB在MHNTs上的Langmuir和Freundlich模拟的拟合参数

Table 1 Parameters for Langmuir and Freundlich isotherms of MB adsorption on MHNTs at different temperatures

T/℃	Langmuir			Freubdlich
T/℃	Q_m	K_L	R²	K_F	n	R²
20	23.47	0.73	0.992	3.43	13.47	0.963
35	23.19	1.29	0.987	3.71	34.43	0.961
50	28.40	0.19	0.985	3.47	11.05	0.948

图10 重复使用次数对MHNTs吸附MB的影响

Fig. 10 Influence of reuse times on the adsorption of MB by MHNTs

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磁性ZnFe₂O₄/埃洛石复合材料的结构及吸附性能研究

Structure and Adsorption Property of Magnetic ZnFe₂O₄-halloysite Composite Material

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