Two New Three-Dimensional Lanthanide Metal-organic Frameworks for the Highly Efficient Removal of Cs+ Ions※

doi:10.6023/A21120614

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (5): 640-646.DOI: 10.6023/A21120614 Previous Articles Next Articles

Special Issue: 中国科学院青年创新促进会合辑

Article

两例新的镧系金属-有机框架化合物高效去除Cs⁺离子研究^※

吕天天^a^,^b, 马文^b, 詹冬笋^b, 邹燕敏^b, 李继龙^b, 冯美玲^b^,^*(), 黄小荥^b

a 中北大学材料科学与工程学院太原 030051
b 中国科学院福建物质结构研究所结构化学国家重点实验室福州 350002

投稿日期:2021-12-31 发布日期:2022-05-31
通讯作者: 冯美玲
作者简介:
^※庆祝中国科学院青年创新促进会十年华诞.
基金资助:
国家自然科学基金(U21A20296); 国家自然科学基金(22076185); 国家自然科学基金(21771183); 福建省自然科学基金(2020J06033)

Two New Three-Dimensional Lanthanide Metal-organic Frameworks for the Highly Efficient Removal of Cs⁺ Ions^※

Tiantian Lü^a^,^b, Wen Ma^b, Dongsun Zhan^b, Yanmin Zou^b, Jilong Li^b, Meiling Feng^b(), Xiaoying Huang^b

a College of Material Science and Engineering, North University of China, Taiyuan 030051
b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002

Received:2021-12-31 Published:2022-05-31
Contact: Meiling Feng
About author:
^※Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
National Natural Science Foundation of China(U21A20296); National Natural Science Foundation of China(22076185); National Natural Science Foundation of China(21771183); Natural Science Foundation of Fujian Province(2020J06033)

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Abstract

¹³⁷Cs has the strong radioactivity and long half-life. In the event of leaking, it will pose a great danger to human health and the environment. The effective removal of ¹³⁷Cs⁺ from complex radioactive waste streams remains a challenge due to its high solubility, easy migration and the influence of interfering ions in the waste streams. In this study, two new three-dimensional microporous lanthanide metal-organic framework compounds (Me₂NH₂)_0.5(H₃O)_0.25Na_0.25Ln(OH)(stp)• 0.25H₂O (FJSM-LnMOF; Ln=Eu, Tb; H₃stp=2-sulfonic acid terephthalic acid) are synthesized by the solvothermal method, which have the good water stability and acid-base resistance. The adsorption performance of FJSM-LnMOFs for Cs⁺ are tested with solid-liquid ratio of 1∶1 under stirring at room temperature for 8 h. The adsorption kinetics of FJSM-EuMOF for Cs⁺ are tested with low-concentration Cs⁺ solution. FJSM-LnMOFs show fast kinetics and high adsorption capacities of Cs⁺ ions (the maximum adsorption capacities q_m^Cs of FJSM-EuMOF and FJSM-TbMOF are 229.25 and 211.28 mg/g, respectively). They have good selectivity for Cs⁺ ions (K_d^Cs value up to 2.18×10³ mL/g). Even in the presence of interfering Na⁺, K⁺, Mg²⁺, Ca²⁺ ions, they still show selective adsorption performance for Cs⁺ ions. Impressively, we successfully obtain the single crystal structure of Cs⁺-absorbed product by soaking FJSM-EuMOF crystals in 20,000 mg/L Cs⁺ solution, which confirms that the adsorption mechanism of Cs⁺ ions is ion exchange by the means of single crystal structure analysis combined with various characterization methods including X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (IR), energy dispersion spectrum (EDS), elemental analysis (EA). The results indicate that the highly efficient Cs⁺ adsorption of FJSM-LnMOF mainly originates from the strong interactions between COO^– and $\text{SO}_{3}^{}$ functional groups from organic ligands and Cs⁺ ions, and the presence of easily exchangeable [Me₂NH₂]⁺ cations and [H₃O]⁺ located in the channels. This work indicates the potential application of lanthanide metal-organic frameworks in the remediation of radioactive cesium.

Key words: lanthanide-organic framework, crystal structure, removal of cesium, adsorption mechanism, ion exchange, kinetics, adsorption capacity, selectivity

Cite this article

Tiantian Lü, Wen Ma, Dongsun Zhan, Yanmin Zou, Jilong Li, Meiling Feng, Xiaoying Huang. Two New Three-Dimensional Lanthanide Metal-organic Frameworks for the Highly Efficient Removal of Cs⁺ Ions^※[J]. Acta Chimica Sinica, 2022, 80(5): 640-646.

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Figure 1. (a) Photographs of FJSM-EuMOF and FJSM-EuMOF-Cs powders and crystals. (b) Simulated and experimental PXRD patterns of FJSM-EuMOF and FJSM-EuMOF-Cs. (c) Three-dimensional structure of FJSM-EuMOF along the c-axis direction. (d) Three-dimensional structure of FJSM-EuMOF-Cs along the c-axis direction. (e) The [Eu4] unit in FJSM-EuMOF. (f) A one-dimensional chain along the c axis formed by interlinking [Eu4] units via stp3– ligands

Figure 2. (a) Kinetics of FJSM-EuMOF for Cs+ absorption plotted as CtCs (mg/L) (black line) and RCs (%) (blue line) vs. the time t (min). (b) The fitting results with pseudo-second-order kinetic model for the Cs+ absorption kinetics of FJSM-EuMOF. Adsorption isotherms of FJSM-EuMOF (c) and FJSM-TbMOF (d) for Cs+ fitted by Langmuir (blue line), Langmuir-Freundlich (red line) and Freundlich models (black line)

Figure 3. (a) KdCs (column) and RCs (line chart) values of FJSM-EuMOF at various initial pH values. (b) KdCs and KdNa of FJSM-EuMOF under the different molar ratios of Na/Cs. (c) Kd of FJSM-EuMOF for various metal ions in the solution 1 and solution 2. (d) R values of metal ion adsorbed by FJSM-EuMOF in tap water spiked with Cs+

Figure 4. (a) The elemental distribution mappings of FJSM-EuMOF-Cs. (b) XPS spectra of FJSM-EuMOF before and after Cs+ adsorption. (c) XPS of cesium for FJSM-EuMOF-Cs

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两例新的镧系金属-有机框架化合物高效去除Cs⁺离子研究^※

Two New Three-Dimensional Lanthanide Metal-organic Frameworks for the Highly Efficient Removal of Cs⁺ Ions^※

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两例新的镧系金属-有机框架化合物高效去除Cs+离子研究※

Two New Three-Dimensional Lanthanide Metal-organic Frameworks for the Highly Efficient Removal of Cs+ Ions※

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Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 4

References 45

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两例新的镧系金属-有机框架化合物高效去除Cs⁺离子研究^※

Two New Three-Dimensional Lanthanide Metal-organic Frameworks for the Highly Efficient Removal of Cs⁺ Ions^※