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磁性金属有机骨架材料(MOF) Fe3O4-COOH@MIL-101(Cr)的制备及其吸附/催化协同作用去除新型污染物尼泊金甲酯

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蒋琦, 章涵, 王俊二, 杨旎妮, 沈昊宇, 胡美琴, 成瑾瑾. 磁性金属有机骨架材料(MOF) Fe3O4-COOH@MIL-101(Cr)的制备及其吸附/催化协同作用去除新型污染物尼泊金甲酯[J]. 环境化学, 2020, (10): 2937-2946. doi: 10.7524/j.issn.0254-6108.2019070705
引用本文: 蒋琦, 章涵, 王俊二, 杨旎妮, 沈昊宇, 胡美琴, 成瑾瑾. 磁性金属有机骨架材料(MOF) Fe3O4-COOH@MIL-101(Cr)的制备及其吸附/催化协同作用去除新型污染物尼泊金甲酯[J]. 环境化学, 2020, (10): 2937-2946. doi: 10.7524/j.issn.0254-6108.2019070705
shu
JIANG Qi, ZHANG Han, WANG Juner, YANG Nini, SHEN Haoyu, HU Meiqin, CHENG Jinjin. Preparation of magnetic metal-organic organic frameworks (MOF) Fe3O4-COOH@MIL-101(Cr) and its adsorption/catalytic joint-removal of the emerging contaminants-methylparaben[J]. Environmental Chemistry, 2020, (10): 2937-2946. doi: 10.7524/j.issn.0254-6108.2019070705
Citation: JIANG Qi, ZHANG Han, WANG Juner, YANG Nini, SHEN Haoyu, HU Meiqin, CHENG Jinjin. Preparation of magnetic metal-organic organic frameworks (MOF) Fe3O4-COOH@MIL-101(Cr) and its adsorption/catalytic joint-removal of the emerging contaminants-methylparaben[J]. Environmental Chemistry, 2020, (10): 2937-2946. doi: 10.7524/j.issn.0254-6108.2019070705
shu

磁性金属有机骨架材料(MOF) Fe3O4-COOH@MIL-101(Cr)的制备及其吸附/催化协同作用去除新型污染物尼泊金甲酯

  • 浙大宁波理工学院, 生物与化学工程学院, 宁波, 315100

    • 通讯作者: 沈昊宇, E-mail: hyshen@nit.zju.edu.cn ; 
  • 基金项目:

    国家自然科学基金（51608479），宁波市自然科学基金（2018A610206），浙江省公益基金（LGC20B070001），国家级大学生创新创业训练计划项目（201813022009）和浙江省新苗计划项目（2018R401181）资助.

Preparation of magnetic metal-organic organic frameworks (MOF) Fe3O4-COOH@MIL-101(Cr) and its adsorption/catalytic joint-removal of the emerging contaminants-methylparaben

  • NingboTech. University, Ningbo, 315100, China

    • Corresponding author: SHEN Haoyu, hyshen@nit.zju.edu.cn ; 
  • Fund Project: Supported by the National Natural Science Foundation(51608479), National Natural Science Foundation of Ningbo(2018A610206), Natural Science Foundation of Zhejiang (LGC20B070001), National College Students' Innovation and Entrepreneurship Training Program(201813022009) and Xinmiao Students' Innovation Training Program of Zhejiang Province(2018R401181).

  • 摘要: 采用溶剂热法合成了羧基功能化Fe3O4磁性微球Fe3O4-COOH，进一步与金属有机骨架材料MIL-101（Cr）复合，得到磁性MOF复合材料Fe3O4-COOH@MIL-101（Cr）.通过X-射线衍射（XRD）、傅里叶变换红外光谱（FTIR）、洛伦兹透射电镜（TEM）、扫描电镜（SEM）、振动样品磁强计（VSM）等手段对其进行了组成、结构、形貌、磁性等表征，并研究了其吸附和富集新型污染物尼泊金甲酯（MPB）的性能，进一步以H2O2为氧化剂，考察了MPB在该材料上富集后的催化氧化降解性能.通过考察溶液pH值、MPB初始浓度、吸附温度、吸附时间、体系中H2O2浓度等影响因素，初步研讨了吸附/降解机理.结果表明，Fe3O4-COOH@MIL-101（Cr）平均粒径约为100 nm，饱和磁化强度为10.1 emu·g-1.对MPB的等温吸附线符合Langmuir模型，吸附热力学研究表明，吸附过程为自发进行的吸热熵增的过程.吸附动力学研究表明，吸附过程符合准二级动力学模型，吸附活化能Ea为46.48 kJ·mol-1；将吸附后的材料加入氧化剂H2O2，采用类Fenton反应可以实现MPB在可见光下降解.在pH 3.0—8.0，45 min内可以实现MPB近100%降解，较普通Fenton反应体系有更宽的pH适用范围.且材料可循环使用，是有优异潜力的水中MPB绿色吸附与降解材料.
    Abstract: Carboxyl-functionalized magnetic material Fe3O4-COOH was firstly synthesized by mysolvothermal method, followed by grafted on metal-organic frameworks (MOF) material, MIL-101(Cr), to obtain magnetic MOF composite Fe3O4-COOH@MIL-101(Cr). The Fe3O4-COOH@MIL-101(Cr) was characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectrometer (FTIR), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). Its application for adsorption and degradation of methylparaben (MPB) was investigated. The results showed that the Fe3O4-COOH@MIL-101(Cr) had an average size of about 100 nm, with the saturation magnetization intensity of 10.1 emu·g-1. The adsorption capacities were investigated by adsorbing the MPB from aqueous solutions. Thermodynamic studies suggested that the adsorption processes fit the Langmuir isotherms well. The adsorption process was a spontaneous process of endothermic entropy favorable. The adsorption kinetic studies showed that the kinetic data were well fitted to the pseudo-second-order model with the adsorption activation energy Ea of 46.48 kJ·mol-1. By adding H2O2 to the post-adsorbed material, catalytic degradation of MPB via Fenton-like reaction under visible light could be realized. The results indicated that at pH 3.0—8.0, the degradation of MPB could be reached to almost 100% within 45 min. The present magnetic MOF composite Fe3O4-COOH@MIL-101(Cr) was a potential effective and reusable material for adsorption and degradation of MPB.
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  • 收稿日期:  2019-07-07
蒋琦, 章涵, 王俊二, 杨旎妮, 沈昊宇, 胡美琴, 成瑾瑾. 磁性金属有机骨架材料(MOF) Fe3O4-COOH@MIL-101(Cr)的制备及其吸附/催化协同作用去除新型污染物尼泊金甲酯[J]. 环境化学, 2020, (10): 2937-2946. doi: 10.7524/j.issn.0254-6108.2019070705
引用本文: 蒋琦, 章涵, 王俊二, 杨旎妮, 沈昊宇, 胡美琴, 成瑾瑾. 磁性金属有机骨架材料(MOF) Fe3O4-COOH@MIL-101(Cr)的制备及其吸附/催化协同作用去除新型污染物尼泊金甲酯[J]. 环境化学, 2020, (10): 2937-2946. doi: 10.7524/j.issn.0254-6108.2019070705
shu
JIANG Qi, ZHANG Han, WANG Juner, YANG Nini, SHEN Haoyu, HU Meiqin, CHENG Jinjin. Preparation of magnetic metal-organic organic frameworks (MOF) Fe3O4-COOH@MIL-101(Cr) and its adsorption/catalytic joint-removal of the emerging contaminants-methylparaben[J]. Environmental Chemistry, 2020, (10): 2937-2946. doi: 10.7524/j.issn.0254-6108.2019070705
Citation: JIANG Qi, ZHANG Han, WANG Juner, YANG Nini, SHEN Haoyu, HU Meiqin, CHENG Jinjin. Preparation of magnetic metal-organic organic frameworks (MOF) Fe3O4-COOH@MIL-101(Cr) and its adsorption/catalytic joint-removal of the emerging contaminants-methylparaben[J]. Environmental Chemistry, 2020, (10): 2937-2946. doi: 10.7524/j.issn.0254-6108.2019070705
shu

磁性金属有机骨架材料(MOF) Fe3O4-COOH@MIL-101(Cr)的制备及其吸附/催化协同作用去除新型污染物尼泊金甲酯

    通讯作者: 沈昊宇, E-mail: hyshen@nit.zju.edu.cn ; 
  • 浙大宁波理工学院, 生物与化学工程学院, 宁波, 315100
  • 收稿日期:  2019-07-07
基金项目:

国家自然科学基金（51608479），宁波市自然科学基金（2018A610206），浙江省公益基金（LGC20B070001），国家级大学生创新创业训练计划项目（201813022009）和浙江省新苗计划项目（2018R401181）资助.

摘要: 采用溶剂热法合成了羧基功能化Fe3O4磁性微球Fe3O4-COOH，进一步与金属有机骨架材料MIL-101（Cr）复合，得到磁性MOF复合材料Fe3O4-COOH@MIL-101（Cr）.通过X-射线衍射（XRD）、傅里叶变换红外光谱（FTIR）、洛伦兹透射电镜（TEM）、扫描电镜（SEM）、振动样品磁强计（VSM）等手段对其进行了组成、结构、形貌、磁性等表征，并研究了其吸附和富集新型污染物尼泊金甲酯（MPB）的性能，进一步以H2O2为氧化剂，考察了MPB在该材料上富集后的催化氧化降解性能.通过考察溶液pH值、MPB初始浓度、吸附温度、吸附时间、体系中H2O2浓度等影响因素，初步研讨了吸附/降解机理.结果表明，Fe3O4-COOH@MIL-101（Cr）平均粒径约为100 nm，饱和磁化强度为10.1 emu·g-1.对MPB的等温吸附线符合Langmuir模型，吸附热力学研究表明，吸附过程为自发进行的吸热熵增的过程.吸附动力学研究表明，吸附过程符合准二级动力学模型，吸附活化能Ea为46.48 kJ·mol-1；将吸附后的材料加入氧化剂H2O2，采用类Fenton反应可以实现MPB在可见光下降解.在pH 3.0—8.0，45 min内可以实现MPB近100%降解，较普通Fenton反应体系有更宽的pH适用范围.且材料可循环使用，是有优异潜力的水中MPB绿色吸附与降解材料.

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