介孔金属有机框架材料吸附水中重金属离子研究进展

doi:10.16085/j.issn.1000-6613.2021-1614

摘要/Abstract

摘要：

介孔金属有机框架材料（介孔MOFs）相较于传统吸附剂具有孔径大、孔隙率可调、比表面积大、官能团丰富，便于功能化改性修饰等优点，可高效地吸附水体中重金属污染物。本文介绍介孔MOFs的特性、合成策略及四种合成介孔MOFs的方法，重点分析四种方法的介孔形成机理及其所面临的问题，并将四种合成方法的优劣进行了比较。详述介孔MOFs吸附去除水中重金属离子、类重金属阴离子以及放射性金属离子的研究进展；介绍了介孔MOFs在吸附去除重金属离子方面的可重复利用性；阐述介孔MOFs吸附去除水中重金属污染物的作用机理。对介孔MOFs成本高昂、合成条件苛刻、回收利用难等问题提出了优化方向，指出提高介孔MOFs的水稳定性、易回收利用、简便绿色合成技术以及痕量去除将是未来的研究方向。

关键词: 介孔金属有机框架材料, 合成策略, 吸附, 重金属离子, 重复利用性

Abstract:

Compared with traditional adsorbents, mesoporous metal organic frameworks (MOFs) have many advantages, such as large pore size, adjustable porosity, large specific surface area, rich functional groups, convenient for functional modification and so on, which can efficiently adsorb heavy metal pollutants in water. The characteristics, synthesis strategies and four synthesis methods of mesoporous MOFs are introduced in this paper. The formation mechanism of mesoporous MOFs and the problems that those four methods faced are analyzed, the advantages and disadvantages of four synthesis methods are compared. The research progress of adsorption and removal of heavy metal ions, heavy metal like anions and radioactive metal ions by mesoporous MOFs and the reusability of mesoporous MOFs in adsorption and removal of heavy metal ions is reviewed. The adsorption mechanism of mesoporous MOFs for the removal of heavy metal pollutants in water is described. The optimization direction is put forward for those problems such as high cost, harsh synthesis conditions and difficult recycling. It is pointed out that improving the water stability of mesoporous MOFs, easy recycling, simple green synthesis technology and trace removal will be the research direction in the future.

Key words: mesoporous metal organic frameworks, synthesis strategy, adsorption, heavy metals ion, reusability

中图分类号:

X703.1

唐朝春, 王顺藤, 黄从新, 冯文涛, 阮以宣, 史纯菁. 介孔金属有机框架材料吸附水中重金属离子研究进展[J]. 化工进展, 2022, 41(6): 3263-3278.

TANG Chaochun, WANG Shunteng, HUANG Congxin, FENG Wentao, RUAN Yixuan, SHI Chunjing. Research progress on adsorption of heavy metal ions in water by mesoporous metal organic framework materials[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3263-3278.

图/表 16

图1 介孔MOFs图示、合成方法以及重金属污染物吸附应用

图2 配体延伸法制备介孔MOFs示意图

图3 混合配体法合成介孔MOFs示意图

图4 UMCM-1、DUT-6结构示意图及微孔/介孔HKUST-1合成示意图

图5 软模板法合成介孔MOFs示意图[26]

图6 硬模板法合成介孔MOFs示意图

表1 几种介孔MOFs的制备方法比较

制备方法	制备要素	介孔形成机理	缺点
配体延伸法	需要有一定结构强度的长配体	延长配体长度以扩大孔径范围	配体相互渗透影响材料结构；受配体柔性结构的影响，结构易坍塌
混合配体法	将两种或多种结构长度不同有机配体混合	长配体构建MOFs介孔道，短配体稳定框架结构	易形成单体共聚的混合物，不易检测其配位模式及骨架结构
软模板法	以表面活性剂或者嵌段共聚物，超临界CO₂为结构导向剂	利用SDAs在反应体系中构建介孔架构进而形成介孔孔道	有机溶剂的大量使用增加成本同时污染环境
硬模板法	以纳米粒子或不稳定的组装体为牺牲模板	移除被引入的纳米粒子进而形成介孔孔道	硬模板剂不易去除

图7 PCN-221、JUC-62、MOF-808及MOF-808/AO对不同重金属的吸附性能图

图8 MOFs、melamine-MOFs、MOF-MA及AMCA-MIL-53(Al)对重金属Pb2+吸附性能图

图9 BUT-39、FJI-C11和MIL-101对Cr2O72-吸附动力学

图10 MIL-100(Fe)对AsO43-的吸附等温线及去除率随时间变化曲线

图11 CoFe2O4@MIL-100(Fe)对初始浓度为10mg/L的AsO43-和AsO33-吸附动力学图谱

表2 各种介孔MOFs吸附重金属污染物效能对比

金属离子	MOFs	介孔大小/nm	吸附量/mg·g^-1	主要吸附机理	文献来源
Hg²⁺	PCN-221	—	277	卟啉簇中吡咯功能位点同Hg(Ⅱ)之间的配位作用	［59］
Hg²⁺	JUC-62	5.0833	836.7	静电作用以及配位作用	［60］
Hg²⁺	MOF-808	13.6~17.1	343.6	锆金属簇同Cr₂O $7 2 -$ 配位作用	［61］
Hg²⁺	MOF-808(AO)	3.5	383.8	配位作用及MOF-808(AO)中AO基团与Hg(Ⅱ)成键作用	［61］
Pb²⁺	melamine-MOFs	2.0	205	—NH₂与Pb(Ⅱ)之间的配位作用	［65］
Pb²⁺	MOF-MA	5.7	510	巯基配体和Pb(Ⅱ)之间的强亲和力	［66］
Cr₂O $7 2 -$	BUT-39	2.0	215	BUT-39中的锆金属簇同Cr₂O $7 2 -$ 之间的静电作用以及形成了不可逆的配位结构	［72］
Cr₂O $7 2 -$	FJI-C11	2.4~3.1	551	Cr₂O $7 2 -$ 同Cl^-之间的离子交换作用	［74］
AsO $4 3 -$	MIL-100(Fe)	2.5~2.9	110	通过末端羟基的取代形成Fe—O—As配合物	［76］
AsO $4 3 -$	CoFe₂O₄@MIL-100(Fe)	20.6	115	通过末端羟基的取代形成Fe—O—As配合物	［77］
AsO $3 3 -$	CoFe₂O₄@MIL-100(Fe)	20.6	144	通过末端羟基的取代形成Fe—O—As配合物	［77］
U⁶⁺	MIL-100(Al)	2.5	110	配位作用	［80］

表2 各种介孔MOFs吸附重金属污染物效能对比

金属离子	MOFs	介孔大小/nm	吸附量/mg·g^-1	主要吸附机理	文献来源
Hg²⁺	PCN-221	—	277	卟啉簇中吡咯功能位点同Hg(Ⅱ)之间的配位作用	［59］
Hg²⁺	JUC-62	5.0833	836.7	静电作用以及配位作用	［60］
Hg²⁺	MOF-808	13.6~17.1	343.6	锆金属簇同Cr₂O $7 2 -$ 配位作用	［61］
Hg²⁺	MOF-808(AO)	3.5	383.8	配位作用及MOF-808(AO)中AO基团与Hg(Ⅱ)成键作用	［61］
Pb²⁺	melamine-MOFs	2.0	205	—NH₂与Pb(Ⅱ)之间的配位作用	［65］
Pb²⁺	MOF-MA	5.7	510	巯基配体和Pb(Ⅱ)之间的强亲和力	［66］
Cr₂O $7 2 -$	BUT-39	2.0	215	BUT-39中的锆金属簇同Cr₂O $7 2 -$ 之间的静电作用以及形成了不可逆的配位结构	［72］
Cr₂O $7 2 -$	FJI-C11	2.4~3.1	551	Cr₂O $7 2 -$ 同Cl^-之间的离子交换作用	［74］
AsO $4 3 -$	MIL-100(Fe)	2.5~2.9	110	通过末端羟基的取代形成Fe—O—As配合物	［76］
AsO $4 3 -$	CoFe₂O₄@MIL-100(Fe)	20.6	115	通过末端羟基的取代形成Fe—O—As配合物	［77］
AsO $3 3 -$	CoFe₂O₄@MIL-100(Fe)	20.6	144	通过末端羟基的取代形成Fe—O—As配合物	［77］
U⁶⁺	MIL-100(Al)	2.5	110	配位作用	［80］

表3 各种介孔MOFs可重复利用性对比

污染物	吸附剂	解吸剂	再生性能	文献来源
Hg²⁺	PCN-221	0.01mol/L硝酸溶液	75%（3次）	［59］
Hg²⁺	NENU-401	乙腈和硫代乙二醇	90%（4次）	［82］
Pb²⁺	AMCA-MIL-53(Al)	0.1mol/L盐酸溶液、硫酸溶液、硝酸溶液	79.5%（1次）	［67］
Cr₂O $7 2 -$	FJI-C11	0.1mol/L盐酸溶液	93%（3次）	［74］
AsO $4 3 -$ ，AsO $3 3 -$	MIL-100(Fe)	0.1mol/L盐酸溶液	86%（3次）	［76］

表3 各种介孔MOFs可重复利用性对比

污染物	吸附剂	解吸剂	再生性能	文献来源
Hg²⁺	PCN-221	0.01mol/L硝酸溶液	75%（3次）	［59］
Hg²⁺	NENU-401	乙腈和硫代乙二醇	90%（4次）	［82］
Pb²⁺	AMCA-MIL-53(Al)	0.1mol/L盐酸溶液、硫酸溶液、硝酸溶液	79.5%（1次）	［67］
Cr₂O $7 2 -$	FJI-C11	0.1mol/L盐酸溶液	93%（3次）	［74］
AsO $4 3 -$ ，AsO $3 3 -$	MIL-100(Fe)	0.1mol/L盐酸溶液	86%（3次）	［76］

图12 介孔MOFs吸附去除重金属离子的可能机理

图13 MOFs吸附二价金属离子过程中静电相互作用的示意图[84]pHlow—pH小于等电点；pHhigh—pH大于等电点

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