共价有机框架材料的合成策略及其在重金属离子吸附中的研究进展

doi:10.16085/j.issn.1000-6613.2024-1408

摘要/Abstract

摘要：

在众多重金属离子废水处理技术中，吸附被认定是最出色的技术之一。共价有机框架（COFs）作为一类新兴的有机多孔聚合物，具有高结晶度、大比表面积、高吸附容量等特性。与传统吸附剂相比，这些特性使COFs在吸附去除水体中重金属离子方面具有巨大潜力。本文首先综述了COFs的结构设计和主要的合成策略，而后介绍了本征COFs、官能化COFs和COFs复合材料在去除水体中重金属离子方面的研究进展。重点介绍了N、O、S官能化COFs的吸附性能，并结合空间结构特性阐述了COFs的影响机制。此外，还分析了COFs与重金属离子之间的各种相互作用机理。最后，讨论了目前COFs在去除重金属离子方面存在的问题，提出了官能化和复合材料是COFs吸附剂的未来发展方向，以期为COFs的设计和应用提供参考。

关键词: 共价有机框架, 吸附, 重金属离子, 机理

Abstract:

Among the diverse technologies for treating heavy metal ions in wastewater, adsorption has emerged as one of the most effective and promising methods. Covalent organic frameworks (COFs), an emerging class of organic porous polymers, are characterized by their high crystallinity, large specific surface area and high adsorption capacity. These properties give COFs a distinct advantage over traditional adsorbents and highlight their enormous potential for heavy metal ions removal from wastewater. This paper firstly reviewed the design of COFs structure and the main synthesis strategies, and then introduced the research progress regarding heavy metal ions removal from water by pristine COFs, functionalized COFs and COFs composites. The adsorption performance of COFs with functional groups containing N, O and S activities was emphasized, and the influence mechanisms of COFs were elaborated in conjunction with their spatial structure properties. In addition, various interaction mechanisms between COFs and heavy metal ions were analyzed. Finally, the current problems of COFs in removing heavy metal ions were analyzed, and functionalization and composite materials were proposed as future development directions of COFs adsorbents, aiming to offer references for the design and adsorption applications of COFs.

Key words: covalent organic frameworks, adsorption, heavy metal ions, mechanism

中图分类号:

TQ424.3

何边燕, 王玉冰, 李珊珊, 延卫. 共价有机框架材料的合成策略及其在重金属离子吸附中的研究进展[J]. 化工进展, 2025, 44(10): 5956-5974.

HE Bianyan, WANG Yubing, LI Shanshan, YAN Wei. Recent progress on synthesis strategies of covalent organic framework materials and their adsorption application for heavy metal ions[J]. Chemical Industry and Engineering Progress, 2025, 44(10): 5956-5974.

图/表 14

图1 不同类型吸附剂的吸附容量比较

图2 COFs的结构设计

表1 不同制备方法合成的COFs的比较

制备方法	优势	劣势
溶剂热法合成	结晶度、孔隙率和形貌控制良好	反应时间长，反应速度慢
离子热法合成	热稳定性高	反应温度高，结晶度差，特殊反应溶剂
机械化学合成	操作方便，生产成本低，生态友好	结晶度和孔隙率有限，重现性差
微波辅助合成	反应时间短，产率高	密封容器
声化学合成	产率高，操作方便	结构多样，纯度低
界面合成	二维薄膜产物	结晶度差

表2 本征COFs去除重金属

目标污染物	反应类型	吸附剂	C∶N∶O∶S（摩尔比）	比表面积/ m²·g^-1	吸附容量/ mg·g^-1	参考文献
Hg(Ⅱ)	Schiff 碱	C $̿$ C@COF	1∶0.07∶0∶0	282.2	<40	[65]
Hg(Ⅱ)	Schiff 碱	COF-1	1∶0.17∶0.17∶0	417.4	53.1	[30]
Hg(Ⅱ)	Schiff 碱	COF-V	1∶0.07∶0∶0	1152	147	[63]
Pb(Ⅱ)	Schiff 碱	C $̿$ C@COF	1∶0.07∶0∶0	282.2	<40	[65]
Pb(Ⅱ)	Schiff 碱	TAVA	1∶0.15∶0∶0	1046.59	105	[68]
Pb(Ⅱ)	S_NAr	JUC-500	1∶0.1∶0.2∶0	189.824	133.92	[67]
Cd(Ⅱ)	离子热三聚反应	CTF-1	1∶0.25∶0∶0	490	29.2	[64]
Cd(Ⅱ)	Schiff 碱	TpBD COF	1∶0.11∶0.11∶0	885	29.6	[66, 71]
Cu(Ⅱ)	Schiff 碱	TFBODH	1∶0.5∶0.25∶0	94	23	[70]
Cu(Ⅱ)	Schiff 碱	TpTc	1∶0.43∶0.29∶0.14	63.5	73.5	[69]

表2 本征COFs去除重金属

目标污染物	反应类型	吸附剂	C∶N∶O∶S（摩尔比）	比表面积/ m²·g^-1	吸附容量/ mg·g^-1	参考文献
Hg(Ⅱ)	Schiff 碱	C $̿$ C@COF	1∶0.07∶0∶0	282.2	<40	[65]
Hg(Ⅱ)	Schiff 碱	COF-1	1∶0.17∶0.17∶0	417.4	53.1	[30]
Hg(Ⅱ)	Schiff 碱	COF-V	1∶0.07∶0∶0	1152	147	[63]
Pb(Ⅱ)	Schiff 碱	C $̿$ C@COF	1∶0.07∶0∶0	282.2	<40	[65]
Pb(Ⅱ)	Schiff 碱	TAVA	1∶0.15∶0∶0	1046.59	105	[68]
Pb(Ⅱ)	S_NAr	JUC-500	1∶0.1∶0.2∶0	189.824	133.92	[67]
Cd(Ⅱ)	离子热三聚反应	CTF-1	1∶0.25∶0∶0	490	29.2	[64]
Cd(Ⅱ)	Schiff 碱	TpBD COF	1∶0.11∶0.11∶0	885	29.6	[66, 71]
Cu(Ⅱ)	Schiff 碱	TFBODH	1∶0.5∶0.25∶0	94	23	[70]
Cu(Ⅱ)	Schiff 碱	TpTc	1∶0.43∶0.29∶0.14	63.5	73.5	[69]

图3 硫醚官能化卟啉基聚合物（TPP1和TPP2）的合成表征和吸附性能[76]

图4 COFs吸附剂的官能化改性标准

表3 官能化COFs去除重金属

目标污染物	官能化原子	反应类型	吸附剂	BET比表面积/m²·g^-1	吸附容量/mg·g^-1	等温线	参考文献
Hg(Ⅱ)	N	Knoevenagel	Bpy-sp²c-COF	567	718.48	Langmuir	[79]
Hg(Ⅱ)	N	Schiff base	Pyridine-COF	348.5	719.4	Langmuir	[77]
Hg(Ⅱ)	N	Schiff base	Tpy-COF-2	1220	295	Langmuir	[94]
Hg(Ⅱ)	N	Schiff base	Tpy-COF-1	137	420	Langmuir	[94]
Hg(Ⅱ)	S	Schiff base	TABB-BMTTPA-COF	1934	734	Langmuir	[85]
Hg(Ⅱ)	N	Friedel-Crafts	TPA-TPC (3/1)	148	270	Langmuir	[90]
Hg(Ⅱ)	N	Friedel-Crafts	TPA-TPC-8MA	656	781	Freundlich	[90]
Hg(Ⅱ)	S	Schiff base	JNU-3	420	959	Langmuir	[73]
Hg(Ⅱ)		Schiff base	COF-1	417.4	53.1	Langmuir	[30]
Hg(Ⅱ)	S	Schiff base	COF-SH	235.0	1282.6	Langmuir	[30]
Hg(Ⅱ)		Schiff base	COF-V	1152	147	Langmuir	[63]
Hg(Ⅱ)	S	Schiff base	COF-S-SH	546	1350	Langmuir	[63]
Hg(Ⅱ)	N	Schiff base	TBN-1	1270.10	1630	Langmuir	[78]
Hg(Ⅱ)	N、O	Schiff base	TpODH	835	1692	Langmuir	[70]
Hg(Ⅱ)	N、S	Schiff base	TPB-DMTP-COF-SH	291	4395	Langmuir	[75]
Pb(Ⅱ)		Schiff base	PDA-TFPT-COF	533.19	77.7	Langmuir	[95]
Pb(Ⅱ)	O	Schiff base	DDA-TFPT-COF	948.04	128	Langmuir	[95]
Pb(Ⅱ)	N、O	Schotten-Baumann	COF-TP	11.4	140.0	Freundlich	[72]
Pb(Ⅱ)	N、O	Schotten-Baumann	COF-TE	3.5	185.7	Freundlich	[72]
Pb(Ⅱ)	N	Schiff base	Tpy-COF-1	137	167	Langmuir	[94]
Pb(Ⅱ)	N	Schiff base	Tpy-COF-2	1220	200	Langmuir	[94]
Pb(Ⅱ)		Schiff base	COF-V	167.3	38.24	Freundlich	[87]
Pb(Ⅱ)	S	Schiff base	COF-SH	40.4	239	Freundlich	[87]
Pb(Ⅱ)		Schiff base	TAVA	1046.59	105	Langmuir	[68]
Pb(Ⅱ)	S	Schiff base	TAVA-S-Et-SH	145.70	303	Langmuir	[68]
Pb(Ⅱ)		SNAr	JUC-500	189.824	133.92	Langmuir	[67]
Pb(Ⅱ)	N、O	SNAr	COF-NHOH	37.665	368.68	Langmuir	[67]
Pb(Ⅱ)	O	SNAr	JUC-505-COOH	380	559	Langmuir	[32]
Pb(Ⅱ)	N	Schiff base	TBN-1	1270.10	730	Langmuir	[78]
Cd(Ⅱ)	O	Schiff base	COF-ETTA-2,3-DHA	1476.5	116	—	[96]
Cd(Ⅱ)		Schiff base	TpBD COF	885	29.6	Langmuir	[66, 71]
Cd(Ⅱ)	O	Schiff base	TpBD-COOH COF	339	150	Langmuir	[66]
Cd(Ⅱ)	N	Schiff base	N-riched COF	1935	396.76	Langmuir	[80]
Cd(Ⅱ)	O	SNAr	JUC-505-COOH	380	504	Langmuir	[32]
Cu(Ⅱ)		Schiff base	TFBODH	94	23	Langmuir	[70]
Cu(Ⅱ)	O	Schiff base	TpODH	835	324	Langmuir	[70]
Cr(Ⅵ)		Schiff base	COF-BTA-BZ	1048	64	—	[82, 83]
Cr(Ⅵ)	O	Schiff base	COF-BTA-DHBZ	816	384	—	[82]
Cr(Ⅵ)	O	Schiff base	COF-1	28.79	462.96	Langmuir	[97]
Cr(Ⅵ)	O	Schiff base	COF-2	26.40	649.35	Langmuir	[97]
Au(Ⅲ)	S	Schiff base	TTB-COF	36	560	—	[88]
Au(Ⅲ)	O	Scholl	COP-TPC8	7.0144	943.4	Langmuir	[84]
Au(Ⅲ)	O	Scholl	COP-TPC6	11.9693	1157	Langmuir	[84]
Au(Ⅲ)	N	Schiff base	Ionic-COF-Cl	452.9	1270.8	Langmuir	[91]

表3 官能化COFs去除重金属

目标污染物	官能化原子	反应类型	吸附剂	BET比表面积/m²·g^-1	吸附容量/mg·g^-1	等温线	参考文献
Hg(Ⅱ)	N	Knoevenagel	Bpy-sp²c-COF	567	718.48	Langmuir	[79]
Hg(Ⅱ)	N	Schiff base	Pyridine-COF	348.5	719.4	Langmuir	[77]
Hg(Ⅱ)	N	Schiff base	Tpy-COF-2	1220	295	Langmuir	[94]
Hg(Ⅱ)	N	Schiff base	Tpy-COF-1	137	420	Langmuir	[94]
Hg(Ⅱ)	S	Schiff base	TABB-BMTTPA-COF	1934	734	Langmuir	[85]
Hg(Ⅱ)	N	Friedel-Crafts	TPA-TPC (3/1)	148	270	Langmuir	[90]
Hg(Ⅱ)	N	Friedel-Crafts	TPA-TPC-8MA	656	781	Freundlich	[90]
Hg(Ⅱ)	S	Schiff base	JNU-3	420	959	Langmuir	[73]
Hg(Ⅱ)		Schiff base	COF-1	417.4	53.1	Langmuir	[30]
Hg(Ⅱ)	S	Schiff base	COF-SH	235.0	1282.6	Langmuir	[30]
Hg(Ⅱ)		Schiff base	COF-V	1152	147	Langmuir	[63]
Hg(Ⅱ)	S	Schiff base	COF-S-SH	546	1350	Langmuir	[63]
Hg(Ⅱ)	N	Schiff base	TBN-1	1270.10	1630	Langmuir	[78]
Hg(Ⅱ)	N、O	Schiff base	TpODH	835	1692	Langmuir	[70]
Hg(Ⅱ)	N、S	Schiff base	TPB-DMTP-COF-SH	291	4395	Langmuir	[75]
Pb(Ⅱ)		Schiff base	PDA-TFPT-COF	533.19	77.7	Langmuir	[95]
Pb(Ⅱ)	O	Schiff base	DDA-TFPT-COF	948.04	128	Langmuir	[95]
Pb(Ⅱ)	N、O	Schotten-Baumann	COF-TP	11.4	140.0	Freundlich	[72]
Pb(Ⅱ)	N、O	Schotten-Baumann	COF-TE	3.5	185.7	Freundlich	[72]
Pb(Ⅱ)	N	Schiff base	Tpy-COF-1	137	167	Langmuir	[94]
Pb(Ⅱ)	N	Schiff base	Tpy-COF-2	1220	200	Langmuir	[94]
Pb(Ⅱ)		Schiff base	COF-V	167.3	38.24	Freundlich	[87]
Pb(Ⅱ)	S	Schiff base	COF-SH	40.4	239	Freundlich	[87]
Pb(Ⅱ)		Schiff base	TAVA	1046.59	105	Langmuir	[68]
Pb(Ⅱ)	S	Schiff base	TAVA-S-Et-SH	145.70	303	Langmuir	[68]
Pb(Ⅱ)		SNAr	JUC-500	189.824	133.92	Langmuir	[67]
Pb(Ⅱ)	N、O	SNAr	COF-NHOH	37.665	368.68	Langmuir	[67]
Pb(Ⅱ)	O	SNAr	JUC-505-COOH	380	559	Langmuir	[32]
Pb(Ⅱ)	N	Schiff base	TBN-1	1270.10	730	Langmuir	[78]
Cd(Ⅱ)	O	Schiff base	COF-ETTA-2,3-DHA	1476.5	116	—	[96]
Cd(Ⅱ)		Schiff base	TpBD COF	885	29.6	Langmuir	[66, 71]
Cd(Ⅱ)	O	Schiff base	TpBD-COOH COF	339	150	Langmuir	[66]
Cd(Ⅱ)	N	Schiff base	N-riched COF	1935	396.76	Langmuir	[80]
Cd(Ⅱ)	O	SNAr	JUC-505-COOH	380	504	Langmuir	[32]
Cu(Ⅱ)		Schiff base	TFBODH	94	23	Langmuir	[70]
Cu(Ⅱ)	O	Schiff base	TpODH	835	324	Langmuir	[70]
Cr(Ⅵ)		Schiff base	COF-BTA-BZ	1048	64	—	[82, 83]
Cr(Ⅵ)	O	Schiff base	COF-BTA-DHBZ	816	384	—	[82]
Cr(Ⅵ)	O	Schiff base	COF-1	28.79	462.96	Langmuir	[97]
Cr(Ⅵ)	O	Schiff base	COF-2	26.40	649.35	Langmuir	[97]
Au(Ⅲ)	S	Schiff base	TTB-COF	36	560	—	[88]
Au(Ⅲ)	O	Scholl	COP-TPC8	7.0144	943.4	Langmuir	[84]
Au(Ⅲ)	O	Scholl	COP-TPC6	11.9693	1157	Langmuir	[84]
Au(Ⅲ)	N	Schiff base	Ionic-COF-Cl	452.9	1270.8	Langmuir	[91]

图5 COFs复合材料的功能化吸附应用

图6 COFs复合材料的载体化吸附应用

图7 静电相互作用机理

图8 离子交换机理作用机理

图9 o-FCMP与PdCl42-结合和TBN-1与Hg(Ⅱ)的结合

图10 Pyridine-COF@Hg的分子结构示意（a）和ELF示意图（b）[77]

图12 氢键机理示意图

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