基于钛基金属有机框架的孔径调控策略及其在海水提铀中的应用★

doi:10.6023/A25050193

化学学报 ›› 2025, Vol. 83 ›› Issue (9): 987-992.DOI: 10.6023/A25050193 上一篇下一篇

研究通讯

基于钛基金属有机框架的孔径调控策略及其在海水提铀中的应用^★

江惠星, 郑丽彬, 陈小丰, 张珍珍^*(), 陈秋水^*(), 杨黄浩^*()

福州大学化学学院新基石科学实验室食品安全与生物分析教育部重点实验室福州 350108

投稿日期:2025-05-28 发布日期:2025-07-23
作者简介:
^★ “中国青年化学家”专辑.
基金资助:
国家自然科学基金(U2441224); 国家自然科学基金(62134003); 国家自然科学基金(22305040); 福建省自然科学基金(2023J01384)

Pore Size Regulation in Titanium-based Metal-Organic Frameworks for Uranium Extraction from Seawater^★

Huixing Jiang, Libin Zheng, Xiaofeng Chen, Zhenzhen Zhang^*(), Qiushui Chen^*(), Huanghao Yang^*()

New Cornerstone Science Laboratory & MOE Key Laboratory for Analytical Science of Food Safety and Biology & College of Chemistry, Fuzhou University, Fuzhou 350108, China

Received:2025-05-28 Published:2025-07-23
Contact: * E-mail: zhenzhenzhang@fzu.edu.cn;qchen@fzu.edu.cn;hhyang@fzu.edu.cn
About author:
^★ For the VSI “Rising Stars in Chemistry”.
Supported by:
National Natural Science Foundation of China(U2441224); National Natural Science Foundation of China(62134003); National Natural Science Foundation of China(22305040); Natural Science Foundation of Fujian Province(2023J01384)

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1. Supporting Information-A25050193.pdf(1898KB)

摘要/Abstract

铀(U)是核反应堆的主要燃料, 海水提铀是实现核能可持续发展的一种极具潜力的方法. 然而, 由于海水中铀含量极低、易形成碳酸盐配合物以及存在高浓度竞争性离子, 开发满足实际应用的吸附剂仍是当前一大挑战. 本研究发展了一种钛基金属有机框架(Ti-MOFs)孔径调节策略, 成功实现了高效率的铀酰提取. 相较于大孔径的MOF-902, 小孔径的MOF-901展现出更优异的吸附性能, 最大吸附容量可达468.5 mg•g⁻¹. X射线光电子能谱分析表明, MOF-901孔道中的N位点是其与铀酰配位的主要活性位点. 孔径与晶体结构分析进一步揭示, 孔径效应和空间位阻效应与Ti-MOFs的铀酰吸附容量紧密相关. 此外, MOF-901在模拟海水(浓度为10 mg•L⁻¹)的吸附实验中表现出超过99%的铀酰提取率, 证明了Ti-MOFs材料在海水提铀领域的应用潜力.

关键词: 钛基金属有机框架, 孔径调控, 海水提铀, 吸附位点, 多孔材料

Uranium (U) is the dominant fuel for nuclear reactors, and uranium extraction from seawater is a promising method to ensure the sustainable development of nuclear energy. However, the development of adsorbents for practical applications remains a challenge due to the extremely low concentration (≈3.3 μg•L⁻¹) and its propensity to form carbonate complexes of uranium, as well as the presence of high concentrations of competing ions. The adsorption performance of adsorbents is affected by the pore size and the distribution of adsorption active sites. Excessively narrow pores will restrict the access of target ions and thus reduce the adsorption rate. Increasing pore sizes is effective to promote the adsorption kinetics but may undermine coordination stability. How to balance the relationship between adsorption capacity and adsorption kinetics is a very important issue in the process of pore size regulation. In this study, titanium-based metal-organic frameworks (Ti-MOFs) were synthesized by solvothermal method and pore size regulation strategy was utilized to improve the extraction efficiency of uranium. The materials were systematically characterized by powder X-ray diffraction (PXRD), Brunauer- Emmett-Teller (BET), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA), demonstrating successive synthesis of Ti-MOFs. Compared to MOF-902 with larger pores, MOF-901 adsorbents with smaller pores exhibit a higher extraction efficiency for uranium, with an adsorption capacity of up to 468.5 mg•g⁻¹. The adsorption mechanism was investigated by X-ray photoelectron spectroscopy (XPS), pore size distribution and crystal structure analysis, and it was proved that MOF-901 is mainly coordinated with U through the N sites in the pore architecture and steric hindrance effect as well as pore size effect are closely related to the uranium adsorption capacity of Ti-MOFs. Adsorption experiments in simulated seawater (initial concentration of 10 mg•L⁻¹) were also carried out, and the adsorption efficiency of uranium by MOF-901 was more than 99%, demonstrating the potential application of Ti-MOFs in the field of uranium extraction from seawater.

Key words: titanium-based metal-organic framework, pore size regulation, uranium extraction from seawater, adsorption site, porous material

引用此文

江惠星, 郑丽彬, 陈小丰, 张珍珍, 陈秋水, 杨黄浩. 基于钛基金属有机框架的孔径调控策略及其在海水提铀中的应用^★[J]. 化学学报, 2025, 83(9): 987-992.

Huixing Jiang, Libin Zheng, Xiaofeng Chen, Zhenzhen Zhang, Qiushui Chen, Huanghao Yang. Pore Size Regulation in Titanium-based Metal-Organic Frameworks for Uranium Extraction from Seawater^★[J]. Acta Chimica Sinica, 2025, 83(9): 987-992.

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图/表 3

图1. (a) MOF-901和MOF-902的合成示意图; (b) MOF-901和MOF-902的模拟与实验PXRD图; (c) FTIR图; (d) N2吸附/脱附等温线; (e) MOF-901的SEM图; (f) MOF-902的SEM图; (g) TGA曲线

Figure 1. (a) Synthesis schematic of MOF-901 and MOF-902; (b) Simulated and experimental PXRD patterns of MOF-901 and MOF-902; (c) FT-IR; (d) Nitrogen adsorption/desorption isotherms; (e) SEM image of MOF-901; (f) SEM image of MOF-902; (g) TGA curve

图2. (a)不同pH值下Ti-MOFs的铀提取率; (b)吸附动力学(pH=6.0, 初始浓度为100 mg•L−1); (c)吸附等温线(pH=6.0); (d) MOF-901对不同离子的提取率(pH=6.0); (e) MOF-901的可重复使用性(初始浓度为20 mg•L−1); (f) Ti-MOFs在加标海水(浓度为10 mg•L−1)中的铀吸附比

Figure 2. (a) Uranium extraction rate of Ti-MOFs at different pH; (b) Adsorption kinetics (pH=6.0, initial concentration of 100 mg•L−1); (c) Adsorption isotherm (pH=6.0); (d) Extraction rate of MOF-901 for different ions (pH=6.0); (e) Reusability of MOF-901 (initial concentration of 20 mg•L−1); (f) Uranium adsorption ratio of Ti-MOFs in spiked seawater (concentration of 10 mg•L−1)

图3. (a) MOF-901吸附$\text{UO}_{2}^{2+}$前后的XPS谱图; (b) MOF-901和MOF-902的孔径分布图; (c) MOF-901的N1s高分辨XPS谱图; (d) Ti-MOFs的孔径对铀吸附的影响示意图

Figure 3. (a) XPS spectra of MOF-901 before and after adsorption of $\text{UO}_{2}^{2+}$; (b) Pore size distribution of MOF-901 and MOF-902; (c) High resolution XPS of N1s from MOF-901; (d) Schematic representation of the effect of pore aperture on uranium extraction for Ti-MOFs

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基于钛基金属有机框架的孔径调控策略及其在海水提铀中的应用^★

Pore Size Regulation in Titanium-based Metal-Organic Frameworks for Uranium Extraction from Seawater^★

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基于钛基金属有机框架的孔径调控策略及其在海水提铀中的应用★

Pore Size Regulation in Titanium-based Metal-Organic Frameworks for Uranium Extraction from Seawater★

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基于钛基金属有机框架的孔径调控策略及其在海水提铀中的应用^★

Pore Size Regulation in Titanium-based Metal-Organic Frameworks for Uranium Extraction from Seawater^★