Modulation strategies of metal-organic framework materials and its adsorption performance on typical heavy metal ions

doi:10.16085/j.issn.1000-6613.2023-0130

Abstract

Abstract:

Metal-organic framework materials have the advantages of larger specific surface area, tunable pore and topological structures, and abundant active functional groups compared with traditional adsorbent materials, which can be used as high-performance adsorbents for the removal of heavy metal pollutants from water. In this paper, the structural characteristics of MOFs as adsorbents for water treatment were introduced. The regulatory strategies of MOFs based on metal node doping, side group functionalization and post-synthetic modification, such as porosity, surface activity, framework flexibility, water stability, scalability, biotoxicity and recyclability, were emphatically analyzed. Then, the research progress of MOFs in the removal of heavy metal ions was introduced, mainly on cationic heavy metal ions such as Pb(Ⅱ) and Hg(‍Ⅱ), and anionic oxyanions such as Cr(Ⅵ) and As(Ⅲ)/As(Ⅴ) in water, and the mechanism of the action of MOFs in the removal of heavy metal ions in water was elaborated. Finally, the research directions of improving the water stability and adsorption performance of MOFs, balancing the relationship between the structural characteristics of MOFs, studying the migration and enrichment of MOFs in nature, and the controllable preparation of MOFs with low cost and high benefit were put forward for improving the reference of MOFs in the field of high-performance adsorption.

Key words: metal-organic framework materials, adsorption, heavy metal ions, nanostructure, stability

摘要：

金属-有机框架材料（MOFs）相较于传统吸附材料具有较大的比表面积、可调的孔隙和拓扑结构、丰富的活性官能团等优点，可作为高性能吸附剂去除水体中的重金属污染物。本文介绍了MOFs作为水处理吸附的结构特性，重点分析了基于金属节点掺杂、侧基功能化和合成后修饰的多孔性、表面活性、框架柔性、水稳定性、可扩展性、生物毒性和循环使用性MOFs的调控策略，而后介绍了MOFs在去除重金属离子方面的研究进展，详细介绍了MOFs对水中Pb(Ⅱ)、Hg(Ⅱ)等阳离子型重金属离子和Cr(Ⅵ)、As(Ⅲ)/As(Ⅴ)等阴离子型含氧离子的吸附性能，并阐述MOFs去除水中重金属离子的作用机理。最后，提出了提升MOFs的水稳定性与吸附性能、平衡MOFs结构特性的关系、研究MOFs在自然界的迁移与富集以及MOFs的低成本高效益的可控性制备等研究方向，以期对MOFs在高性能吸附领域提供参考。

关键词: 金属-有机框架材料, 吸附, 重金属离子, 纳米结构, 稳定性

CLC Number:

TQ424

XU Chunshu, YAO Qingda, LIANG Yongxian, ZHOU Hualong. Modulation strategies of metal-organic framework materials and its adsorption performance on typical heavy metal ions[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6518-6534.

许春树, 姚庆达, 梁永贤, 周华龙. 金属-有机框架材料的调控策略及其对典型重金属离子的吸附性能[J]. 化工进展, 2023, 42(12): 6518-6534.

Figures/Tables 11

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毒性等级	体外	体内	参考文献
‒	MOF-74(Mg)、MOF-74(Co)、UiO-66、UiO-67	MOF-74(Mg)	[67-68]
+	MIL-100(Fe)	MOF-74(Co)、UiO-66、UiO-67	[67-68]
++	MIL-101(Fe)、ZIF-7、ZIF-8、MIL-88A、MIL-88B	MIL-100(Fe)、ZIF-7	[53,67,70]
+++	ZIF-67、NOTT-100、Hf-TPCC、MIL-125(Fe)	ZIF-8、MIL-101(Fe)、MIL-88A、MIL-88B、Hf-TPCC、MIL-125(Fe)	[66,69-70]
++++	HKUST-1、Cu-TPCC	HKUST-1、NOTT-100、Cu-TPCC、ZIF-67	[69,71]

毒性等级	体外	体内	参考文献
‒	MOF-74(Mg)、MOF-74(Co)、UiO-66、UiO-67	MOF-74(Mg)	[67-68]
+	MIL-100(Fe)	MOF-74(Co)、UiO-66、UiO-67	[67-68]
++	MIL-101(Fe)、ZIF-7、ZIF-8、MIL-88A、MIL-88B	MIL-100(Fe)、ZIF-7	[53,67,70]
+++	ZIF-67、NOTT-100、Hf-TPCC、MIL-125(Fe)	ZIF-8、MIL-101(Fe)、MIL-88A、MIL-88B、Hf-TPCC、MIL-125(Fe)	[66,69-70]
++++	HKUST-1、Cu-TPCC	HKUST-1、NOTT-100、Cu-TPCC、ZIF-67	[69,71]

MOFs	比表面积/m²·g^-1	重金属离子类型	吸附pH	循环次数	吸附量/mg·g^-1	参考文献
MIL-101(Fe)-NH₂	454.6	Pb(Ⅱ)	5	6	227.9	[20]
Zr-SA-SH	296	Pb(Ⅱ)	4	4	510	[25]
Zr-SA-SH	296	Hg(Ⅱ)	4	4	1080	[25]
UiO-66-SH	721	Hg(Ⅱ)	7	5	822	[32]
MOF-808-COOH	126.9	Pb(Ⅱ)	5.8	—	390.2	[35]
MIL-101(Fe)-(COOH)₂	184	Pb(Ⅱ)	5	5	467.63	[51]
ZIF-8/PSF	968	Pb(Ⅱ)	5.5	5	220.04	[73]
UiO-66-(COOH)₂	443	Pb(Ⅱ)	6	4	357.0	[74]
UiO-66-COOH	422.64	Pb(Ⅱ)	5.5	5	186.14	[75]
MOF-808-COOH	1411	Pb(Ⅱ)	5.2	6	192.68	[76]
UiO-66-NH₂	1144	Pb(Ⅱ)	5.5	5	227.80	[77]
Zr-TCPP	—	Hg(Ⅱ)	7.1	3	233.65	[79]
MIL-101(Fe/Co)	—	Hg(Ⅱ)	6	4	312.97	[80]
TMU-59	—	Hg(Ⅱ)	4.5	—	约1500	[81]
MOF-808-SH	636	Hg(Ⅱ)	5	6	977.5	[82]
UiO-66-NH₂	—	Hg(Ⅱ)	6.5	—	223.8	[83]
Zn-MOF	—	Hg(Ⅱ)	5	—	476	[84]
Zn-MOF	—	Pb(Ⅱ)	5	—	909	[84]
Cd-MOF	48.07	Pb(Ⅱ)	7	3	536.3	[87]

MOFs	比表面积/m²·g^-1	重金属离子类型	吸附pH	循环次数	吸附量/mg·g^-1	参考文献
MIL-101(Fe)-NH₂	454.6	Pb(Ⅱ)	5	6	227.9	[20]
Zr-SA-SH	296	Pb(Ⅱ)	4	4	510	[25]
Zr-SA-SH	296	Hg(Ⅱ)	4	4	1080	[25]
UiO-66-SH	721	Hg(Ⅱ)	7	5	822	[32]
MOF-808-COOH	126.9	Pb(Ⅱ)	5.8	—	390.2	[35]
MIL-101(Fe)-(COOH)₂	184	Pb(Ⅱ)	5	5	467.63	[51]
ZIF-8/PSF	968	Pb(Ⅱ)	5.5	5	220.04	[73]
UiO-66-(COOH)₂	443	Pb(Ⅱ)	6	4	357.0	[74]
UiO-66-COOH	422.64	Pb(Ⅱ)	5.5	5	186.14	[75]
MOF-808-COOH	1411	Pb(Ⅱ)	5.2	6	192.68	[76]
UiO-66-NH₂	1144	Pb(Ⅱ)	5.5	5	227.80	[77]
Zr-TCPP	—	Hg(Ⅱ)	7.1	3	233.65	[79]
MIL-101(Fe/Co)	—	Hg(Ⅱ)	6	4	312.97	[80]
TMU-59	—	Hg(Ⅱ)	4.5	—	约1500	[81]
MOF-808-SH	636	Hg(Ⅱ)	5	6	977.5	[82]
UiO-66-NH₂	—	Hg(Ⅱ)	6.5	—	223.8	[83]
Zn-MOF	—	Hg(Ⅱ)	5	—	476	[84]
Zn-MOF	—	Pb(Ⅱ)	5	—	909	[84]
Cd-MOF	48.07	Pb(Ⅱ)	7	3	536.3	[87]

MOFs	比表面积/m²·g^-1	含氧阴离子类型	吸附pH	循环次数	吸附量/mg·g^-1	参考文献
GUT-3	—	As(Ⅴ)	3	2	33.91	[15]
Zr-SA-SH	513	Cr(Ⅵ)	3	—	202.0	[24]
UiO-66	800	Cr(Ⅵ)	3	—	85.45	[85]
ZIF-8	1050	Cr(Ⅵ)	3	—	150.85	[85]
Ce-UiO-66	1101	Cr(Ⅵ)	—	—	30.03	[86]
Cd-MOF	48.07	Cr(Ⅵ)	6	3	703.0	[87]
UiO-66-NH₂	919	Cr(Ⅵ)	2	5	338.98	[88]
UiO-66@UiO-67	314.95	Cr(Ⅵ)	2	5	932.1	[89]
MIL-101(Cr)-NH₂	≈2000	Cr(Ⅵ)	4	—	45	[90]
UiO-66-CH₃	316.26	Cr(Ⅵ)	—	3	194.55	[91]
Ce-MOF-808	335.12	As(Ⅲ)	11	—	402.10	[92]
MOF-74(Zn)	604	As(Ⅲ)	12	3	204.92	[93]
MIL-101(Fe/Al)-NH₂	402	As(Ⅴ)	6.5	—	146.8	[95]
UiO-66(Fe/Zr)	498.33	As(Ⅲ)	7	5	121.81	[96]
UiO-66(Fe/Zr)	498.33	As(Ⅴ)	9	5	227.3	[96]
Eu-MOF-COOH	1069	As(Ⅴ)	8	—	23.68	[97]
Yb-MOF	—	As(Ⅴ)	5	—	81.169	[98]