层状金属有机框架材料用于水溶液中137Cs的高效去除

doi:10.15541/jim20190434

无机材料学报 ›› 2020, Vol. 35 ›› Issue (3): 367-372.DOI: 10.15541/jim20190434

所属专题： 2020年环境材料论文精选(一)放射性元素去除；【虚拟专辑】放射性污染物去除(2020~2021)

层状金属有机框架材料用于水溶液中¹³⁷Cs的高效去除

李国东¹,姬国勋¹(),孙新利¹,杜伟²,刘伟²(),王殳凹³

^1. 火箭军工程大学核工程学院, 西安 710025
^2. 烟台大学环境与材料工程学院, 烟台 264005
^3. 苏州大学放射医学及交叉学科研究院, 苏州 215123

收稿日期:2019-08-16 修回日期:2019-09-08 出版日期:2020-03-20 网络出版日期:2019-10-23
作者简介:李国东(1994-), 男, 硕士研究生. E-mail: guodong-l@163.com
基金资助:
国家自然科学基金(21825601)

Layered Metal Organic Framework for Effective Removal of ¹³⁷Cs from Aqueous Solution

LI Guodong¹,JI Guoxun¹(),SUN Xinli¹,DU Wei²,LIU Wei²(),WANG Shuao³

^1. Nuclear Engineering College, Rocket Force University of Engineering, Xi’an 710025, China
^2. School of Environment and Material Engineering, Yantai University, Yantai 264005, China
^3. School for Radiological and Interdisciplinary Sciences (RAD-X) Soochow University, Suzhou 215123, China

Received:2019-08-16 Revised:2019-09-08 Published:2020-03-20 Online:2019-10-23
About author:LI Guodong (1994-), male, Master candidate. E-mail: guodong_l@163.com
Supported by:
National Natural Science Foundation of China(21825601)

摘要/Abstract

摘要：

¹³⁷Cs主要来源于核武器试验和核电站产生的放射性废物, 具有高溶解度和高迁移率的特点, 因此从放射性废液中有效去除 ¹³⁷Cs是一项长期的挑战。本研究通过溶剂热法合成了一种二维层状阴离子骨架材料SZ-6, 并对其吸附性能进行了系统的研究。利用单晶衍射仪、X射线衍射仪和扫描电子显微镜等对SZ-6的结构、形貌和稳定性进行了表征与测试。采用批实验研究了水溶液中Cs ⁺的吸附行为。结果表明: 在浓度为10 mg/L的Cs ⁺溶液中, SZ-6的吸附动力学可在5 min内达到平衡, 是目前去除Cs ⁺最快的吸附剂材料之一; SZ-6在pH4~12范围内表现出良好的去除能力; 在过量Na ⁺、K ⁺、Ca ²⁺竞争阳离子存在的情况下仍具有较好的选择性。

关键词: 金属有机框架材料, 放射性核素, ¹³⁷Cs, 吸附, 动力学

Abstract:

¹³⁷Cs is one of the most intractable β-emitters which is commonly generated from nuclear weapons test and nuclear power station. Due to the nature of high solubility and mobility, the effective sequestration of ¹³⁷Cs ⁺ from radioactive waste solution is considered as a long-term challenge. In this work, a two-dimensional layered anion framework material (SZ-6) was synthesized through conventional solvothermal reaction and the Cs ⁺ removal properties were systematically investigated. Single Crystal X-ray Diffraction (SCXRD) analysis revealed that SZ-6 adopts layer packed structure with large tetramethylammonium cations loaded between the layers which is greatly beneficial to cation exchange process. Powder X-ray Diffraction (XRD) and Scanning Electron Microscope (SEM) confirmed the material with high purity and excellent hydrolytic stability. Batch experiments were used to investigate the adsorption behavior towards Cs ⁺ in aqueous solutions. The adsorption kinetics of SZ-6 could be achieved within 5 min, which is currently one of the fastest sorbents for the removal of Cs ⁺. Meanwhile, SZ-6 exhibits superior decontamination capability over a wide pH range from 4 to 12. Furthermore, it possesses marked selectivity in the presence of large excess of Na ⁺, K ⁺, Ca ²⁺ competing cations.

Key words: Metal Organic Frameworks, radionuclide, ¹³⁷Cs, adsorption, kinetics

中图分类号:

X591

李国东, 姬国勋, 孙新利, 杜伟, 刘伟, 王殳凹. 层状金属有机框架材料用于水溶液中¹³⁷Cs的高效去除[J]. 无机材料学报, 2020, 35(3): 367-372.

LI Guodong, JI Guoxun, SUN Xinli, DU Wei, LIU Wei, WANG Shuao. Layered Metal Organic Framework for Effective Removal of ¹³⁷Cs from Aqueous Solution[J]. Journal of Inorganic Materials, 2020, 35(3): 367-372.

图/表 10

图1 SZ-6的晶体结构图

Fig. 1 Crystal structure of SZ-6 (a) Coordination environment of In3+ center; (b) Asymmetric unit of SZ-6; (c ) Layer packed structure of SZ-6 along the a axis; (d) Rhombic channels viewed along the c axis Atom colors: In = cyan, C = anthracite, N = blue, O =red

图2 SZ-6的X射线粉末衍射图谱

Fig. 2 Powder XRD patterns of SZ-6

图3 SZ-6的SEM-EDS分析结果

Fig. 3 SEM-EDS analyses of SZ-6 (a) SEM image, (b) Distribution of In; (c) EDS pattern of SZ-6

图4 SZ-6的热重分析曲线

Fig. 4 Thermogravimetric analysis curve of SZ-6

图5 不同pH的Cs+溶液浸泡后样品的X射线粉末衍射图谱

Fig. 5 PXRD patterns of samples before and after immersed in Cs+ aqueous solutions with different pH

图6 Cs+的吸附动力学

Fig. 6 Uptake kinetics of Cs+ Inset: simulation curve of Pseudo-second-order model

图7 SZ-6对Cs+的等温吸附实验结果

Fig. 7 Sorption isotherm curves of Cs+ by SZ-6 (Solid curve: Langmuir equilibrium isotherm model; Dotted curve: Freundlich equilibrium isotherm model)

表1 Langmuir模型和Freundlich模型拟合参数

Table 1 Fitting parameters of Langmuir model and Freundlich model

Langmuir			Freundlich
q_m/(mg·g^-1)	K_L/(mg·g^-1)	R²	k_F/(mg·g^-1)	n	R²
140.005	0.024	0.997	20.368	3.295	0.844

图8 溶液pH对SZ-6吸附Cs+的影响

Fig. 8 Effect of pH of solution on the adsorption of Cs+ by SZ-6

表2 Na+, K+, Ca+对SZ-6吸附Cs+的影响

Table 2 Effect of Na+, K+, Ca2+ on the removal of Cs+ by SZ-6

Competing cation		Cs⁺/Na⁺	Cs⁺/K⁺	Cs⁺/Ca²⁺
Solid/Liquid /(g•L^-1)		2	2	5
Cs⁺ removal/%	MR=1 : 1	87.2	84.7	91.2
	MR=1 : 10	84.2	75.7	90.1
	MR=1 : 20	75.8	65.5	85
	MR=1 : 30	70.3	59	73.7
	MR=1 : 50	63.5	49.3	65.7

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层状金属有机框架材料用于水溶液中¹³⁷Cs的高效去除

Layered Metal Organic Framework for Effective Removal of ¹³⁷Cs from Aqueous Solution

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