结构和价态调控的Ce-MOFs及其衍生物吸附水中氟离子的机理
DOI:
CSTR:
作者:
作者单位:

1.长安大学 建筑工程学院;2.长安大学建筑工程学院

作者简介:

通讯作者:

中图分类号:

TU991.21

基金项目:

中央高校高新技术研究培育项目(300102281201)、中国博士后科学基金(2021M692510)、陕西省基金项目(2020JM-264)、陕西省自然科学基础研究计划项目(2021JQ-222)、陕西省高校科协青年人才托举计划(20200413)。


Adsorption mechanism of fluorion removal from water by structure and valence-regulated Ce-MOFs and their derivatives
Author:
Affiliation:

1.School of Civil Engineering,Chang’an University,Xi’an;2.School of Civil Engineering, Chang’an University

Fund Project:

the High and New Technology Research and Cultivation Program of the Central Universities (No.: 300102281201), China Postdoctoral Science Foundation (No.: 2021M692510), Shaanxi Provincial Foundation (No.: 2020JM-264), Natural Science Basic Research Project of Shaanxi Province (No.2021JQ-222), Young Talent fund of University Association for Science and Technology in Shaanxi (20200413).

  • 摘要
  • |
  • 图/表
  • |
  • 访问统计
  • |
  • 参考文献
  • |
  • 相似文献
  • |
  • 引证文献
  • |
  • 资源附件
  • |
  • 文章评论
    摘要:

    严控饮水氟浓度,可以有效降低人体罹患氟骨症和氟牙症的风险。近年来,铈基吸附材料在解决氟污染问题中表现优异,而铈盐与有机酸反应生成的铈基金属有机框架材料(Ce-MOFs)或其衍生物,能有效去除水中的氟离子。硝酸铈铵(Ce(NH4)2(NO3)6)和均苯三甲酸(H3BTC)在不同反应时长下生成了Ce-MOFs CeT1及其衍生物CeT2,更换H3BTC为对苯二甲酸(H2BDC),反应生成两种Ce-MOFs,CeD1和CeD2。利用XRD、BET、SEM、XPS和FTIR对材料的结构、比表面积、元素含量和组成基团,进行系统的表征;通过控制吸附时间、溶质初始浓度、溶液pH值和竞争离子种类研究四种材料的吸附性能;对实验数据进行吸附动力学模型和吸附等温模型拟合,探究吸附机理。表征结果显示,CeT1为高度配位不饱和的Ce(Ⅳ)-MOFs,CeD1为比表面积最大(1003.10 m2/g)的Ce(Ⅳ)-MOFs,而CeT2和CeD2则同为Ce(Ⅲ)占比较高的吸附材料。吸附实验中,CeT1、CeT2、CeD1和CeD2的最大吸附容量分别为99.38 mg/g、142.45 mg/g、60.45 mg/g和124.55 mg/g,CeT1、CeT2和CeD2符合假二级动力学模型,CeD1符合假一级动力学模型。四种材料对氟离子的吸附机理主要为静电吸引、离子交换和沉淀。其中,CeT1的不饱和配位可提供吸附位点进行离子交换和静电吸引,CeD1的大比表面积增加了污染物与材料的碰撞几率,而CeT2和CeD2中含有的Ce(Ⅲ),可通过形成溶度积常数极小的CeF3(Ksp=8×10-16),以沉淀作用固定氟离子。实验探究了四种材料的特点与吸附性能之间的关系,为Ce-MOFs及其衍生物的制备与优选提供参考。

    Abstract:

    Strictly controlling the concentration of fluorion in drinking water can effectively reduce the risk of bone fluorosis and dental fluorosis. In recent years, cerium based adsorption materials have shown excellent performance in solving the problem of fluorion pollution, and cerium organic framework materials (Ce-MOFs) or their derivatives generated by the reaction of cerium salt with organic acids can effectively remove fluorion from water. Ce-MOFs CeT1 and its derivative CeT2 were produced by ammonium cerium nitrate (Ce(NH4)2(NO3)6) and homophenic acid (H3BTC) at different reaction times. When H3BTC was replaced by terephthalic acid (H2BDC), two Ce-MOFs, CeD1 and CeD2, were generated. XRD, BET, SEM, XPS and FTIR were used to systematically characterize the structure, specific surface area, element content and constituent groups of the materials. The adsorption properties of the four materials were studied by controlling the adsorption time, the initial concentration of solute, the pH value of solution and the types of competing ions. The adsorption kinetics model and adsorption isothermal model were fitted to the experimental data to explore the adsorption mechanism. The characterization results showed that CeT1 was Ce(Ⅳ)-MOFs with high coordination unsaturated, CeD1 was Ce(Ⅳ)-MOFs with the largest specific surface area (1003.10 m2/g), and both CeT2 and CeD2 were Ce(Ⅲ) adsorption materials. In the adsorption experiments, the maximum adsorption capacities of CeT1, CeT2, CeD1 and CeD2 are 99.38 mg/g, 142.45 mg/g, 60.45 mg/g and 124.55 mg/g, respectively. CeT1, CeT2 and CeD2 conform to the pseudo-second-order kinetic model. CeD1 conforms to the pseudo-first-order kinetic model. The adsorption mechanisms of fluorion in the four materials are mainly electrostatic attraction, ion exchange and precipitation. Among them, the unsaturated coordination of CeT1 can provide adsorption sites for ion exchange and electrostatic attraction, the large specific surface area of CeD1 increases the probability of collision between pollutants and materials, and the Ce(Ⅲ) contained in CeT2 and CeD2 can be fixed by precipitation by forming CeF3 (Ksp=8×10-16) with minimal solubility product constant. The characteristics and defluorination ability of the four materials were analyzed, and the defluorination mechanism was explored, so as to provide reference for the preparation and optimization of Ce-MOFs and its derivatives.

    参考文献
    相似文献
    引证文献
引用本文
分享
相关视频

文章指标
  • 点击次数:
  • 下载次数:
  • HTML阅读次数:
  • 引用次数:
历史
  • 收稿日期:2022-08-04
  • 最后修改日期:2023-09-13
  • 录用日期:2023-09-14
  • 在线发布日期:
  • 出版日期:
文章二维码