金属有机框架材料吸附分离水中铀的应用

doi:10.16085/j.issn.1000-6613.2018-1919

摘要/Abstract

摘要：

金属有机框架材料（metal-organic frameworks，MOFs）具有极高的比表面积和孔隙率，结构可设计调控，但在水相吸附分离方面存在水稳定和选择吸附性较差、分离困难、合成与再生成本偏高等问题。针对MOFs的缺陷，可以通过有目的的功能化改性从而提升其对目标污染物的吸附性能。本文介绍了MOFs的结构优势，分析了水稳定性的影响因素和判断手段，简述了具有代表性的高水稳定性MOFs材料的特性；根据MOFs改性方法的分类回顾了MOFs及改性MOFs在去除水相中放射性铀的应用；基于不同分析技术探讨了MOFs与铀酰离子的吸附机理；提出推动MOFs在吸附铀方面规模化应用发展的核心是合成高稳定性MOFs，通过改性提高MOFs的选择吸附性能和再生性以及深入研究吸附机理。

关键词: 金属有机框架材料, 吸附, 水溶液, 铀, 稳定性, 模拟

Abstract:

Metal-organic frameworks (MOFs) have extremely high surface area and porosity, and their structures can be designed and regulated. However, there are some problems in its adsorption and separation in aqueous phase, such as poor water stability, poor adsorption selectivity, difficult separation from water, high cost of synthesis and regeneration. In light of this, MOFs can be functionalized purposefully to improve the adsorption performance on target pollutants. This review introduces the structural advantages of MOFs, analyzes the influencing factors and judgment methods of MOFs water stability, and briefly describes the characteristics of representative highly water stable MOFs materials. Special emphasis is put on the applications of different MOFs and modified MOFs in the removal of radioactive uranium from aqueous phase. Based on different analytical techniques, the adsorption mechanism of uranyl ions on MOFs was discussed. Finally, it is proposed that the key to promote the large-scale application of MOFs in uranium adsorption is to synthesize highly stable MOFs, improve the adsorption selectivity and regenerability through modification, and to study the adsorption mechanism in-depth.

Key words: metal-organic frameworks, adsorption, aqueous solution, uranium, stability, simulation

中图分类号:

TB383
X591

彭莹, 张晓文, 李密, 张宇, 吴晓燕. 金属有机框架材料吸附分离水中铀的应用[J]. 化工进展, 2019, 38(07): 3227-3242.

Ying PENG, Xiaowen ZHANG, Mi LI, Yu ZHANG, Xiaoyan WU. Application of metal-organic frameworks in adsorption and separation of uranium from water[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3227-3242.

图/表 10

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吸附剂	比表面积 /m²·g^-1	最佳pH		固液比 /g·L^-1		q _max /mg·g^-1		符合的动力学模型	符合的热力学方程	吸附机理	参考文献
UiO-68-DPPU	1350	2.5		1		217		—	Langmuir	DFT计算得出DPPU与UO₂ ²⁺的吸附原理符合2:1的结合模式	[15]
MOF-76	—	3.0		0.4		298		—	Langmuir	—	[77]
HKUST-1		6		0.6		787.4		准二级	Langmuir	通过热力学参数ΔG、ΔH、ΔS推测吸附过程是自发吸热的过程	[45]
MIL-101(Cr)-ED	517	4.5		0.5		200(exp, c ₀=100mg·L^-1)		—	—	X射线吸收光谱(XANES+EXAFS)研究了铀与氨基的结合模式和ED嫁接量的影响	[62]
MIL-101	3065	5		0.4		20(exp)		准二级	Langmuir	FTIR和EXAFS联合分析得出MIL-101-NH₂上的NH₂由于苯环的空间位阻作用而影响了U-N的结合	[65]
MIL-101-NH₂	1645					90(exp)
MIL-101-DETA	1074					350(exp)
MIL-101-ED	753					200(exp)
Zn(HBTC)(L)·(H₂O)₂	—	2		—		0.53^①		准二级	Langmuir	IR光谱分析推测吸附作用主要是由于MOF材料1D通道上独立的羧基与UO₂ ²⁺的U-O键合作用	[66]
MIL-101-COOH	890.5	7		—		314		准二级	Langmuir	MDS(分子动力学模拟)和DFT（密度泛函理论计算）联合从分子水平分析了MOFs与U的结合	[52]
Coumarin-modified Zn-MOF-74	—	4		1		360（exp, c ₀=400mg·L^-1）		准二级	—	—	[63]
UiO-66	1382					109.9		准二级	Langmuir	简单推测NH₂并没有提高UiO-66吸附能力的原因是苯环上氨基的低活性、比表面积的降低和NH₂之间氢键的形成	[58]
UiO-66-NH₂	1050	5.5		0.4		114.9
HKUST-1@H₃PW₁₂O₄₀	467	6	0.2		14.58		准二级		Langmuir	通过热力学参数ΔG，ΔH，ΔS推测吸附过程是自发吸热的过程	[88]
UiO-66-AO	711	—	—		2.68^②		准二级		—	EXAFS分析得出偕胺肟能够与U(Ⅵ)进行螯合，形成六角形双锥体配位几何体	[25]
MIL-53(Al)-AO	—	5.5	0.4		454.54		准二级		Freundlich	—	[27]
CMPO@MIL-101(Cr)	1014	—	—		—		—		—	该篇文献主要是研究材料很好的选择性和可重复利用性，批实验和机理分析少	[52]
MIL-101-Ship	2365	4	1		27.99		准二级		Langmuir	—	[67]
Fe₃O₄@ZIF-8	1137	3	—		523.5(exp)		准二级		Langmuir	—	[68]
Fe₃O₄@AMCA-MIL53(Al)	197.8	5.5	0.8		227.3		准二级		Langmuir	通过热力学参数ΔG、ΔH、ΔS推测吸附过程是自发吸热的过程	[69]
GO–COOH/UiO-66	767.12	8	0.5		998(exp, c ₀=502.2mg·L^-1)		准二级		Langmuir	FTIR光谱法、X射线光电子能谱（XPS）和XRD联合分析得出COOH和铀主要是螯合作用，还有一点离子交换作用	[71]
Co-SLUG-35	—	9	—		1.03^③		准二级		Langmuir	FTIR、SEM、XPS分析得出MOFs对铀的吸附机理是阴离子交换	[85]
MIL-100(Al)	—	5	—		110(exp, c _e=10000mg·L^-1)		准二级		Freundlich	—	[46]
SZ-1	10.2	—	—		—		—		—	XAS(XANES+EXAFS)、XPS光谱和MDS模拟表明，UO₂ ^{2 +}和SZ-2之间的强静电相互作用有效地将UO₂ ²⁺驱动到SZ-2的骨架中，而更紧密的氢键网络的形成导致UO₂ ²⁺被充分捕获	[51]
SZ-2	225	4.5	—		58.18		—		Langmuir
SZ-3	594	4.5			58.18		—		Langmuir

吸附剂	比表面积 /m²·g^-1	最佳pH		固液比 /g·L^-1		q _max /mg·g^-1		符合的动力学模型	符合的热力学方程	吸附机理	参考文献
UiO-68-DPPU	1350	2.5		1		217		—	Langmuir	DFT计算得出DPPU与UO₂ ²⁺的吸附原理符合2:1的结合模式	[15]
MOF-76	—	3.0		0.4		298		—	Langmuir	—	[77]
HKUST-1		6		0.6		787.4		准二级	Langmuir	通过热力学参数ΔG、ΔH、ΔS推测吸附过程是自发吸热的过程	[45]
MIL-101(Cr)-ED	517	4.5		0.5		200(exp, c ₀=100mg·L^-1)		—	—	X射线吸收光谱(XANES+EXAFS)研究了铀与氨基的结合模式和ED嫁接量的影响	[62]
MIL-101	3065	5		0.4		20(exp)		准二级	Langmuir	FTIR和EXAFS联合分析得出MIL-101-NH₂上的NH₂由于苯环的空间位阻作用而影响了U-N的结合	[65]
MIL-101-NH₂	1645					90(exp)
MIL-101-DETA	1074					350(exp)
MIL-101-ED	753					200(exp)
Zn(HBTC)(L)·(H₂O)₂	—	2		—		0.53^①		准二级	Langmuir	IR光谱分析推测吸附作用主要是由于MOF材料1D通道上独立的羧基与UO₂ ²⁺的U-O键合作用	[66]
MIL-101-COOH	890.5	7		—		314		准二级	Langmuir	MDS(分子动力学模拟)和DFT（密度泛函理论计算）联合从分子水平分析了MOFs与U的结合	[52]
Coumarin-modified Zn-MOF-74	—	4		1		360（exp, c ₀=400mg·L^-1）		准二级	—	—	[63]
UiO-66	1382					109.9		准二级	Langmuir	简单推测NH₂并没有提高UiO-66吸附能力的原因是苯环上氨基的低活性、比表面积的降低和NH₂之间氢键的形成	[58]
UiO-66-NH₂	1050	5.5		0.4		114.9
HKUST-1@H₃PW₁₂O₄₀	467	6	0.2		14.58		准二级		Langmuir	通过热力学参数ΔG，ΔH，ΔS推测吸附过程是自发吸热的过程	[88]
UiO-66-AO	711	—	—		2.68^②		准二级		—	EXAFS分析得出偕胺肟能够与U(Ⅵ)进行螯合，形成六角形双锥体配位几何体	[25]
MIL-53(Al)-AO	—	5.5	0.4		454.54		准二级		Freundlich	—	[27]
CMPO@MIL-101(Cr)	1014	—	—		—		—		—	该篇文献主要是研究材料很好的选择性和可重复利用性，批实验和机理分析少	[52]
MIL-101-Ship	2365	4	1		27.99		准二级		Langmuir	—	[67]
Fe₃O₄@ZIF-8	1137	3	—		523.5(exp)		准二级		Langmuir	—	[68]
Fe₃O₄@AMCA-MIL53(Al)	197.8	5.5	0.8		227.3		准二级		Langmuir	通过热力学参数ΔG、ΔH、ΔS推测吸附过程是自发吸热的过程	[69]
GO–COOH/UiO-66	767.12	8	0.5		998(exp, c ₀=502.2mg·L^-1)		准二级		Langmuir	FTIR光谱法、X射线光电子能谱（XPS）和XRD联合分析得出COOH和铀主要是螯合作用，还有一点离子交换作用	[71]
Co-SLUG-35	—	9	—		1.03^③		准二级		Langmuir	FTIR、SEM、XPS分析得出MOFs对铀的吸附机理是阴离子交换	[85]
MIL-100(Al)	—	5	—		110(exp, c _e=10000mg·L^-1)		准二级		Freundlich	—	[46]
SZ-1	10.2	—	—		—		—		—	XAS(XANES+EXAFS)、XPS光谱和MDS模拟表明，UO₂ ^{2 +}和SZ-2之间的强静电相互作用有效地将UO₂ ²⁺驱动到SZ-2的骨架中，而更紧密的氢键网络的形成导致UO₂ ²⁺被充分捕获	[51]
SZ-2	225	4.5	—		58.18		—		Langmuir
SZ-3	594	4.5			58.18		—		Langmuir

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