金属-有机框架材料结构设计及其对合成染料的吸附性能

doi:10.16085/j.issn.1000-6613.2022-2089

化工进展 ›› 2023, Vol. 42 ›› Issue (10): 5322-5338.DOI: 10.16085/j.issn.1000-6613.2022-2089

金属-有机框架材料结构设计及其对合成染料的吸附性能

许春树¹^,²(), 姚庆达²^,³, 梁永贤², 周华龙²^,⁴()

^1.晋江市质量计量检测所，福建泉州 362200
^2.四川大学(石狮)先进高分子材料研究中心，福建泉州 362700
^3.兴业皮革科技股份有限公司，福建泉州 362200
^4.四川大学制革清洁技术国家工程实验室，四川成都 610000

收稿日期:2022-11-09 修回日期:2022-12-21 出版日期:2023-10-15 发布日期:2023-11-11
通讯作者: 周华龙
作者简介:许春树（1981—），男，高级工程师，研究方向为鞋用材料的功能设计及检测分析。E-mail：echose@126.com。
基金资助:
省部级科学基金(FJQI2012060)

Structural design of metal-organic framework materials and its adsorption performance on synthetic dyes

XU Chunshu¹^,²(), YAO Qingda²^,³, LIANG Yongxian², ZHOU Hualong²^,⁴()

^1.Jinjiang Testing Institute of Quality and Metrology, Quanzhou 362200, Fujian, China
^2.Advanced Polymer Materials Research Center of Sichuan University (Shishi), Quanzhou 362700, Fujian, China
^3.Xingye Leather Technology Co. , Ltd. , Quanzhou 362200, Fujian, China
^4.National Engineering Laboratory for Clean Technology of Leather Manufacture, Sichuan University, Chengdu 610000, Sichuan, China

Received:2022-11-09 Revised:2022-12-21 Online:2023-10-15 Published:2023-11-11
Contact: ZHOU Hualong

摘要/Abstract

摘要：

金属-有机框架材料（MOFs）由于其巨大的比表面积、高孔隙率、有序的孔隙结构及优异的稳定性等特点，在诸多领域得到了广泛研究，其中在吸附/分离领域，特别是吸附水体中的合成染料方面展现出良好的应用前景。本文介绍了常见的MOFs作为多孔吸附材料的结构设计方法，重点分析了金属离子和配体的交换、有机配体的功能化修饰对MOFs的晶体结构、比表面积、孔容的影响，探讨了MOFs的结构设计与其吸附性能的关系，并探究MOFs对阳离子染料和阴离子染料的吸附机理，以此为基础，分析了MOFs对亚甲基蓝、罗丹明B等阳离子染料和刚果红、铬黑T等阴离子染料的吸附性能，最后总结了MOFs多孔吸附材料的技术优势及目前存在的问题，展望未来发展方向，以期对MOFs在合成染料高性能吸附领域的发展提高参考。

关键词: 金属-有机框架材料, 纳米结构, 吸附, 合成染料, 纳米材料

Abstract:

Metal-organic framework materials (MOFs) have been extensively studied in many fields due to their huge specific surface area, high porosity, ordered pore structure and excellent stability, among which they show good application prospects in the field of adsorption/separation, especially in the adsorption of synthetic dyes in aqueous humor. The structural design methods of common MOFs as porous adsorbent materials are introduced. The effects of exchange of metal ions and ligands, functionalized modification of organic ligands on the crystal structure, specific surface area and pore capacity of MOFs are analyzed with emphasis, and the relationship between the structural design of MOFs and their adsorption performance is investigated. And then, the adsorption mechanism of MOFs on cationic dyes and anionic dyes is investigated. Plus, the adsorption properties of MOFs on cationic dyes such as Methylene blue and Rhodamine B, and anionic dyes such as Congo red and Chromium black T are analyzed on this base. Finally, the technical advantages and current problems of MOFs porous adsorption materials are summarized, and the future development direction is prospected in order to improve the reference of MOFs for the development in the field of high-performance adsorption.

Key words: metal-organic framework materials, nanostructure, adsorption, synthetic dyes, nanomaterials

中图分类号:

TQ424

许春树, 姚庆达, 梁永贤, 周华龙. 金属-有机框架材料结构设计及其对合成染料的吸附性能[J]. 化工进展, 2023, 42(10): 5322-5338.

XU Chunshu, YAO Qingda, LIANG Yongxian, ZHOU Hualong. Structural design of metal-organic framework materials and its adsorption performance on synthetic dyes[J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5322-5338.

图/表 8

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MOFs	比表面积/m²·g^-1	染料类型	吸附pH	循环次数	吸附量/mg·g^-1	参考文献
Fe-Al-BDC	285	RhB	—	3	168.7	[21]
Fe-Ni-BDC	480	RhB	4	—	1091	[22]
Zn-N-MOFs	25.189	MB	7	—	458.24	[52]
UiO-66-NH₂	953.7	MB	9	6	571.5	[53]
ZIF-8	1802	RhB	7	4	9.88	[54]
Zr-BTB-H₄TBAPy	518	RhB	7	—	238	[55]
Cr-BDC-SO₃H	1411.89	MB	11	3	374	[56]
Fe-BDC-NH₂	16.329	MB	10	2	312.5	[57]
Fe-Al-BDC	—	RhB	5	7	114.94	[58]
Fe-ZIF-67	1245	RhB	10	4	135.14	[59]
ZIF-8@ZIF-67	1154	RhB	10	4	143.26	[60]
Cu-BTC	1418.3	MB	11	4	197.9	[61]
Ti-UiO-66	929	RhB	7	3	260	[62]
Fe-Zn-BDC-OH	860	MB	7	5	337	[63]
Cu-Metet	—	MB	11	—	171	[64]
Zr-BDC-NH₂	765	MB	9	—	90.48	[65]
Fe-Co-BDC	—	MB	4	6	23.92	[66]
Cr-BDC	1150	MB	—	—	314.5	[67]
Zn-MOFs	—	MB	8	5	46.23	[68]
Zr-BDC-COOH	505	MB	7	3	169	[69]
Er-BTC	775	MB	10	10	192.3	[70]
Ce-UiO-67	1408.6	MB	3	3	199.45	[71]
Cu-MOFs	341	MB	—	5	149.45	[72]
UiO-66-OH	941.74	MB	3	5	380.87	[73]
MIL-125	845	RhB	—	—	59.92	[74]
Cu-BDC-NH₂	900	RhB	6	3	156	[75]
Ti-BDC-NH₂	—	RhB	7	4	164	[76]
Fe-BTC	1068	RhB	4	5	194.17	[78]
Zr-BTC	1894	RhB	8.5	4	166.7	[79]

MOFs	比表面积/m²·g^-1	染料类型	吸附pH	循环次数	吸附量/mg·g^-1	参考文献
Fe-Al-BDC	285	RhB	—	3	168.7	[21]
Fe-Ni-BDC	480	RhB	4	—	1091	[22]
Zn-N-MOFs	25.189	MB	7	—	458.24	[52]
UiO-66-NH₂	953.7	MB	9	6	571.5	[53]
ZIF-8	1802	RhB	7	4	9.88	[54]
Zr-BTB-H₄TBAPy	518	RhB	7	—	238	[55]
Cr-BDC-SO₃H	1411.89	MB	11	3	374	[56]
Fe-BDC-NH₂	16.329	MB	10	2	312.5	[57]
Fe-Al-BDC	—	RhB	5	7	114.94	[58]
Fe-ZIF-67	1245	RhB	10	4	135.14	[59]
ZIF-8@ZIF-67	1154	RhB	10	4	143.26	[60]
Cu-BTC	1418.3	MB	11	4	197.9	[61]
Ti-UiO-66	929	RhB	7	3	260	[62]
Fe-Zn-BDC-OH	860	MB	7	5	337	[63]
Cu-Metet	—	MB	11	—	171	[64]
Zr-BDC-NH₂	765	MB	9	—	90.48	[65]
Fe-Co-BDC	—	MB	4	6	23.92	[66]
Cr-BDC	1150	MB	—	—	314.5	[67]
Zn-MOFs	—	MB	8	5	46.23	[68]
Zr-BDC-COOH	505	MB	7	3	169	[69]
Er-BTC	775	MB	10	10	192.3	[70]
Ce-UiO-67	1408.6	MB	3	3	199.45	[71]
Cu-MOFs	341	MB	—	5	149.45	[72]
UiO-66-OH	941.74	MB	3	5	380.87	[73]
MIL-125	845	RhB	—	—	59.92	[74]
Cu-BDC-NH₂	900	RhB	6	3	156	[75]
Ti-BDC-NH₂	—	RhB	7	4	164	[76]
Fe-BTC	1068	RhB	4	5	194.17	[78]
Zr-BTC	1894	RhB	8.5	4	166.7	[79]

MOFs	比表面积 /m²·g^-1	染料类型	吸附pH	循环次数	吸附量 /mg·g^-1	参考文献
Al-BDC	—	EBT	2	—	82.5	[80]
Al-BDC	630	AB	3	4	86.96	[81]
Fe-BTC	1906.5	CR	7	3	1166.2	[82]
Zn-MOFs	—	CR	—	—	233.38	[83]
Cd-aip-bpy	—	CR	7	3	211.86	[84]
Cd-hip-bpy	—	CR	7	3	267.37	[84]
Co-DPE	—	MO	7	—	95.23	[85]
ZIF-67	1208.67	CR	7	5	1044.58	[86]
Cr-BDC	2440	DR	7	—	526.31	[87]
Cu-MOFs	—	CR	—	—	656	[88]
ZIF-8-APTM	1055.5	CR	6	5	653.59	[89]
ZIF-67	1388	CR	6	3	714.3	[90]
Co-Fe-BDC	10.57	CR	8	—	1935.68	[91]
MIL-88A	29.8	CR	6	3	539.1	[92]
MIL-88A-NH₂	—	CR	—	4	769.23	[93]
Al-BDC	1160.7	EBT	—	4	296.3	[94]
ZIF-67-OAc	—	EBT	7	—	136.9	[94]
TMU-16	66.95	EBT	5	5	326.42	[96]
TMU-16-NH₂	155	EBT	5	5	588.23	[96]
Zn-dimb	—	EBT	—	5	180.1	[98]

MOFs	比表面积 /m²·g^-1	染料类型	吸附pH	循环次数	吸附量 /mg·g^-1	参考文献
Al-BDC	—	EBT	2	—	82.5	[80]
Al-BDC	630	AB	3	4	86.96	[81]
Fe-BTC	1906.5	CR	7	3	1166.2	[82]
Zn-MOFs	—	CR	—	—	233.38	[83]
Cd-aip-bpy	—	CR	7	3	211.86	[84]
Cd-hip-bpy	—	CR	7	3	267.37	[84]
Co-DPE	—	MO	7	—	95.23	[85]
ZIF-67	1208.67	CR	7	5	1044.58	[86]
Cr-BDC	2440	DR	7	—	526.31	[87]
Cu-MOFs	—	CR	—	—	656	[88]
ZIF-8-APTM	1055.5	CR	6	5	653.59	[89]
ZIF-67	1388	CR	6	3	714.3	[90]
Co-Fe-BDC	10.57	CR	8	—	1935.68	[91]
MIL-88A	29.8	CR	6	3	539.1	[92]
MIL-88A-NH₂	—	CR	—	4	769.23	[93]
Al-BDC	1160.7	EBT	—	4	296.3	[94]
ZIF-67-OAc	—	EBT	7	—	136.9	[94]
TMU-16	66.95	EBT	5	5	326.42	[96]
TMU-16-NH₂	155	EBT	5	5	588.23	[96]
Zn-dimb	—	EBT	—	5	180.1	[98]

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金属-有机框架材料结构设计及其对合成染料的吸附性能

Structural design of metal-organic framework materials and its adsorption performance on synthetic dyes

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