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金属学报  2019, Vol. 55 Issue (7): 821-830    DOI: 10.11900/0412.1961.2019.00079
  本期目录 | 过刊浏览 |
Fe-BTC表面氨基化及对染料和重金属离子的吸附性能研究
曹梦薇,蔡桃,张霞()
东北大学理学院 沈阳 110819
Study on Amination Modification of Fe-BTC and Their Adsorption for Dyes and Heavy Metal Ions
Mengwei CAO,Tao CAI,Xia ZHANG()
College of Sciences, Northeastern University, Shenyang 110819, China
全文: PDF(8080 KB)   HTML
摘要: 

利用二乙烯三胺(DETA)对Fe-BTC结构进行改性,并系统研究了其对刚果红(CR)和重金属离子Pb(II)的吸附性能。应用SEM、XRD、Fourier变换红外光谱仪(FT-IR)、N2吸附-解吸实验、Zeta电位测定等方法对改性前后的Fe-BTC材料进行结构和表面性质表征。结果表明,在保持Fe-BTC晶体结构的前提下,DETA的掺杂可有效增加Fe-BTC表面—NH2并改变其表面的电性。在对CR和Pb(II)的吸附实验中,DETA-Fe-BTC对CR和Pb(Ⅱ)的吸附量明显提高,对比实验证明了DETA-Fe-BTC对于CR和Pb(II)的吸附选择性。对吸附条件进行了优化并对于吸附的热力学和动力学数据进行了拟合。在循环吸附脱附实验中,DETA-Fe-BTC表现出对于CR和Pb(II)优秀的吸附性能稳定性。

关键词 固相吸附金属有机骨架材料表面功能化有机染料重金属离子    
Abstract

The efficient removal of synthetic organics and metal ions from wastewater is an urgent target in the environment remedy. Metal-organic frameworks (MOFs) have received extensive attention owing to their large surface area, tunable pore size and versatile composition of metal and organic ligand, which have presented potential applications in the adsorption/separation of gas, metal ions and also organic dyes. Furthermore, the surface functionalization with some special groups has been proved to be effective in improving the adsorption activity and selectivity. In this work, the diethylenetriamine (DETA) was used to modify the Fe-BTC, and then their adsorption properties toward Congo red (CR) and Pb(II) were studied systematically. SEM, XRD, Fourier transform infrared spectroscopy (FT-IR), N2 adsorption-desorption experiments and Zeta potential measurements were employed to characterize the structure and surface properties of these modified Fe-BTC materials. The results showed that the incorporation of DETA maintained the crystal structure of Fe-BTC as while as effectively increased the surface—NH2 group and also changed the surface charge properties. In the adsorption experiments of CR and Pb(II), the adsorption capacity on the DETA-Fe-BTC was significantly increased compared to that on original Fe-BTC, the adsorption conditions were optimized and the adsorption thermodynamics were analyzed. The adsorption selectivity of DETA-BTC for CR and Pb(II) was also determined through the contrast experiments. In the cyclic adsorption experiments, the DETA-Fe-BTC also exhibited the excellent adsorption stability for CR and Pb(II).

Key wordssolid adsorption    metal-organic framework    surface functionalization    organic dye    heavy metal ion
收稿日期: 2019-03-25     
ZTFLH:  TQ13  
基金资助:中央高校基本科研业务专项资金项目(No.182410001);国家级大学生创新创业训练计划项目(No.201910145028)
通讯作者: 张霞     E-mail: xzhang@mail.neu.edu.cn
Corresponding author: Xia ZHANG     E-mail: xzhang@mail.neu.edu.cn
作者简介: 曹梦薇,女,1998年生,本科生

引用本文:

曹梦薇,蔡桃,张霞. Fe-BTC表面氨基化及对染料和重金属离子的吸附性能研究[J]. 金属学报, 2019, 55(7): 821-830.
Mengwei CAO, Tao CAI, Xia ZHANG. Study on Amination Modification of Fe-BTC and Their Adsorption for Dyes and Heavy Metal Ions. Acta Metall Sin, 2019, 55(7): 821-830.

链接本文:

https://www.ams.org.cn/CN/10.11900/0412.1961.2019.00079      或      https://www.ams.org.cn/CN/Y2019/V55/I7/821

图1  Fe-BTC和DETA-Fe-BTC的XRD谱以及Fourier变换红外光谱
图2  Fe-BTC和DETA-Fe-BTC表面Zeta电位随pH值变化曲线以及N2吸附-脱附曲线
图3  原始Fe-BTC和DETA-Fe-BTC的SEM像
图4  不同条件下,Fe-BTC和DETA-Fe-BTC对于CR和Pb(II)的平衡吸附量和吸附动力学曲线
图5  CR和 Pb(II)的吸附动力学拟合曲线

Adsorbate[border:border-top:solid;border-right:solid;]

c0

mg·L-1

qt(max)

mg·g-1

Pseudo-first orderPseudo-second order

qe

mg·g-1

kl

min-1

R2

qe

mg·g-1

k2

g·mg-1·min-1

R2

CR

Pb(Ⅱ)

1500

100

2569.72

134.83

659.14

8.44

1.85×10-2

4.29×10-3

0.79551

0.78881

2696.43

135.32

4.48×10-5

1.18×10-2

0.99779

0.99998

表1  分别应用准一级和准二级动力学方程对于CR和Pb(II)的吸附动力学进行拟合的参数
图6  Fe-BTC 和DETA-Fe-BTC对于CR和Pb(II)的吸附等温线(25 ℃)
图7  分别应用Freundlich模型和Langmuir模型对DETA-Fe-BTC的吸附等温数据进行拟合的曲线
AdsorbateLangmuir modelFreundlich model
qmKLR2KFnR2
mg·g-1L·mg-1mg1-1/n·L1/n·g-1
CR3033.920.06230.97427529.803.07330.88471
Pb(Ⅱ)334.450.13970.9892457.702.12040.92303
表2  应用Freundlich模型和Langmuir模型对DETA-Fe-BTC表面CR和Pb(II)吸附等温线进行拟合的参数
图8  DETA-Fe-BTC对于不同金属离子和染料的吸附量对比
Solid adsorbentAdsorptionRef.
capacity
mg·g-1
DETA-Fe-BTC3033.92This work
Ni-MOFs2046[29]
MIL-68 (In) microrods318[30]
[Zn(BDC)(TIB)]·3H2O60[31]
UiO-671237[32]
PEI-Cu-BTC2578[28]
GO/ZIF82489[33]
[Co(L1)(tp)]n928.4[34]
Ce(III)-doped UiO-66826[35]
MIL-68(In) nanorods1204[30]
表3  不同MOFs对CR的吸附容量对比[28,29,30,31,32,33,34,35]
Solid adsorbentAdsorptionRef.
capacity
mg·g-1
DETA-Fe-BTC334.45This work
MIL-10115.8[23]
ED-MIL-101(2 mmol)25.6[23]
ED-MIL-101(5 mmol)81.1[23]
UiO-668.4[36]
UiO-66-NH231.2[36]
Zr-MOFs72.1[37]
Melamine-Zr-MOFs122[37]
表4  不同MOFs对Pb(II)的吸附容量对比[23,36,37]
图9  DETA-Fe-BTC去除CR和Pb(II)的循环性能测试
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