共价有机框架材料在环境修复领域中吸附有机污染物的研究进展

doi:10.16085/j.issn.1000-6613.2024-0795

摘要/Abstract

摘要：

共价有机框架（COFs）是一类由轻质元素通过共价键连接的具有周期有序的新兴多孔晶体材料，具有比表面积大、孔隙可调、热稳定性高、结构易修饰等特点，是环境修复领域中吸附去除有机污染物的理想材料。本文主要综述了近年来氮基键、离子型、接枝官能团、手性、复合功能化五种不同类型COFs材料吸附去除药物、农药、染料、工业副产物等有机污染物的研究进展。首先，从COFs拓扑结构和孔壁化学环境两个角度揭示了COFs材料捕获有机污染物有效路径，分类讨论了其吸附机理机制；接着，分析了五种不同类型COFs材料的具体合成路径及其吸附应用效果，并简要归纳了相应性能指标参数；最后，针对目前 COFs材料在环境修复领域中工业化大规模生产面临的实际问题提供了一些建议，总结了“自下而上”、“后合成”两种策略调控COFs高效吸附与特异性选择相匹配面临的挑战，并指出基于构效结合思维获得性能良好的COFs材料仍任重道远。

关键词: 共价有机框架材料, 有机污染物, 吸附, 作用机理

Abstract:

Covalent organic frameworks (COFs) are a class of newly developed porous crystal materials with periodic order composed of light elements via strong covalent bonds. It has broad application prospect as a promising material for the elimination of various organic pollutants due to their large specific surface area, adjustable pores, abundant active functional groups, high thermal stability and recyclability. Hence, this review highlighted the recent progress and advances of the adsorption and removal of organic pollutants such as drugs, pesticides, dyes and industrial by-product by five different types of COFs (nitrogen bond, ionic type, grafting functional group, chiral and complex functionalization). Firstly, the effective path of COFs to capture pollutants was revealed from the perspectives of COFs topological structure and pore wall chemical environment, and the adsorption mechanism was discussed. Then, the specific synthetic paths and adsorption effects of different types of COFs were analyzed, and the corresponding performance parameters were briefly summarized. Finally, some suggestions were provided for industrial mass production of COFs in the field of environmental remediation, and the challenges of “bottom-up” and “post-synthesis” strategies in regulating the efficient adsorption and specific selection of COFs were summarized. It was also pointed out that it was still a long way to obtain good performance COFs based on structure-activity combination thinking.

Key words: covalent organic frameworks, organic pollutants, adsorption, action mechanism

中图分类号:

TQ05

候林丽, 张梦玲, 郎锋祥, 郑希怡, 刘利民. 共价有机框架材料在环境修复领域中吸附有机污染物的研究进展[J]. 化工进展, 2024, 43(10): 5837-5856.

HOU Linli, ZHANG Mengling, LANG Fengxiang, ZHENG Xiyi, LIU Limin. A review on the adsorption of organic pollutants by covalent organic frameworks (COFs) from environmental remediation[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5837-5856.

图/表 19

参考文献 75

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COFs	比表面积/m²·g^-1	目标污染物	最佳 pH	最大吸附容量/mg·g^-1	平衡时间/min	循环利用次数/次	参考文献
氮基键COFs
TFPPy-CB	284.5	木樨草素槲皮素芦丁		66.32 67.85 10.69	5 5 5	5 5 5	[20] [20] [20]
TFPPy-ODH	667.6	木樨草素槲皮素芦丁		73.20 70.83 9.76	5 5 5	5 5 5	[20] [20] [20]
TpPa-1 TpTph TpBD	1179 715 592	磺胺嘧啶磺胺嘧啶磺胺嘧啶	4~7 4~7 4~7	82.9 150 188	240 240 240	5 5 5	[11] [11] [11]
TpBch	652.7	盐酸阿霉素	7.4~8.5	137.4	90	4	[50]
离子型COFs
TFP-Dg_Cl	12.70	双氯芬酸钠	5	1100.08	60		[24]
TPA-TG_Cl	26.8	双氯芬酸钠酮洛芬	5.7 4.3	724.64 240.96	180 180	5 5	[12] [12]
TpPa-SO₃H	102	磺胺嘧啶	7	174	120	4	[51]
接枝官能团COFs
COF-NH₂	282	酮洛芬布洛芬萘普生		33 18 16	180 180 180		[32] [32] [32]
COF-NO₂	679	酮洛芬布洛芬萘普生		70 94 80	120 120 120		[32] [32] [32]
TzDa-PBA	274.3	木犀草素槲皮素黄芩素杨梅素	8 8 8 8	219.3 213.0 189.0 134.0	20 20 20 20	5 5 5 5	[18] [18] [18] [18]
HP-COFs	743	磺胺嘧啶	6	168	240	5	[52]
COF-3-NH₂	114	双氯芬酸钠	5	410.0	30	4	[31]
复合功能化COFs
COF@MXene	131.26	左氧氟沙星洛美沙星环丙沙星加替沙星莫西沙星	7~8 7~8 7~8 7~8 7~8	84.20 54.63 71.89 57.04 147.91	90 90 90 90 90	6 6 6 6 6	[15] [15] [15] [15] [15]
Tb@TpPa-SO₃H	236	诺氟沙星环丙沙星恩诺沙星	8 8 8	989 956 998	2 2 2	5 5 5	[43] [43] [43]
Fe₃O₄@COF-TpDBd	265.24	环丙沙星诺氟沙星	7 7	219.25 225.31	30 30	5 5	[46] [46]
PAN@v-TTT		氧氟沙星		236			[44]
OH-MCOF	89.80	双氯芬酸钠	5	203.4	30	5	[53]
MCC/COF/PANI	69.86	吲哚美辛双氯芬酸钠		149.1 112.5	60 60	5 5	[49] [49]

COFs	比表面积/m²·g^-1	目标污染物	最佳 pH	最大吸附容量/mg·g^-1	平衡时间/min	循环利用次数/次	参考文献
氮基键COFs
TFPPy-CB	284.5	木樨草素槲皮素芦丁		66.32 67.85 10.69	5 5 5	5 5 5	[20] [20] [20]
TFPPy-ODH	667.6	木樨草素槲皮素芦丁		73.20 70.83 9.76	5 5 5	5 5 5	[20] [20] [20]
TpPa-1 TpTph TpBD	1179 715 592	磺胺嘧啶磺胺嘧啶磺胺嘧啶	4~7 4~7 4~7	82.9 150 188	240 240 240	5 5 5	[11] [11] [11]
TpBch	652.7	盐酸阿霉素	7.4~8.5	137.4	90	4	[50]
离子型COFs
TFP-Dg_Cl	12.70	双氯芬酸钠	5	1100.08	60		[24]
TPA-TG_Cl	26.8	双氯芬酸钠酮洛芬	5.7 4.3	724.64 240.96	180 180	5 5	[12] [12]
TpPa-SO₃H	102	磺胺嘧啶	7	174	120	4	[51]
接枝官能团COFs
COF-NH₂	282	酮洛芬布洛芬萘普生		33 18 16	180 180 180		[32] [32] [32]
COF-NO₂	679	酮洛芬布洛芬萘普生		70 94 80	120 120 120		[32] [32] [32]
TzDa-PBA	274.3	木犀草素槲皮素黄芩素杨梅素	8 8 8 8	219.3 213.0 189.0 134.0	20 20 20 20	5 5 5 5	[18] [18] [18] [18]
HP-COFs	743	磺胺嘧啶	6	168	240	5	[52]
COF-3-NH₂	114	双氯芬酸钠	5	410.0	30	4	[31]
复合功能化COFs
COF@MXene	131.26	左氧氟沙星洛美沙星环丙沙星加替沙星莫西沙星	7~8 7~8 7~8 7~8 7~8	84.20 54.63 71.89 57.04 147.91	90 90 90 90 90	6 6 6 6 6	[15] [15] [15] [15] [15]
Tb@TpPa-SO₃H	236	诺氟沙星环丙沙星恩诺沙星	8 8 8	989 956 998	2 2 2	5 5 5	[43] [43] [43]
Fe₃O₄@COF-TpDBd	265.24	环丙沙星诺氟沙星	7 7	219.25 225.31	30 30	5 5	[46] [46]
PAN@v-TTT		氧氟沙星		236			[44]
OH-MCOF	89.80	双氯芬酸钠	5	203.4	30	5	[53]
MCC/COF/PANI	69.86	吲哚美辛双氯芬酸钠		149.1 112.5	60 60	5 5	[49] [49]

COFs	比表面积/m²·g^-1	目标污染物	最佳 pH	最大吸附容量/mg·g^-1	平衡时间/min	循环利用次数/次	参考文献
接枝官能团COFs
COF-Bu COF-F COF-F_0.5	1516 354 1573	氟虫腈氟虫腈氟虫腈		122.4 149.8 194.7			[25] [25] [25]
COF-(CF₃)₂	1533	氟虫灵氟虫腈		151 171			[17] [17]
mTpBD-Me₂		亲脂性毒死蜱阿特拉津		270 54	120 120	5 5	[54] [54]
COF-F1N5	190.2	全氟己磺酸盐全氟辛烷磺酸	6 6	300.2μmol/g 879.8μmol/g	1440 1440	5 5	[26] [26]
COF-300-乙烷		全氟辛酸	2	250	1080		[30]
复合功能化COFs
磁性COF	1543	哒嗪硫磷辛硫磷嘧硫磷甲拌磷		163.9 172.4 175.4 178.6	30 30 30 30	10 10 10 10	[45] [45] [45] [45]

COFs	比表面积/m²·g^-1	目标污染物	最佳 pH	最大吸附容量/mg·g^-1	平衡时间/min	循环利用次数/次	参考文献
接枝官能团COFs
COF-Bu COF-F COF-F_0.5	1516 354 1573	氟虫腈氟虫腈氟虫腈		122.4 149.8 194.7			[25] [25] [25]
COF-(CF₃)₂	1533	氟虫灵氟虫腈		151 171			[17] [17]
mTpBD-Me₂		亲脂性毒死蜱阿特拉津		270 54	120 120	5 5	[54] [54]
COF-F1N5	190.2	全氟己磺酸盐全氟辛烷磺酸	6 6	300.2μmol/g 879.8μmol/g	1440 1440	5 5	[26] [26]
COF-300-乙烷		全氟辛酸	2	250	1080		[30]
复合功能化COFs
磁性COF	1543	哒嗪硫磷辛硫磷嘧硫磷甲拌磷		163.9 172.4 175.4 178.6	30 30 30 30	10 10 10 10	[45] [45] [45] [45]

COFs	比表面积/m²·g^-1	目标污染物	最佳pH	最大吸附容量/mg·g^-1	平衡时间/min	循环利用次数/次	参考文献
氮基键 COFs
BFTB-PyTA BFTB-BFTB BFTB-BCTA	1133 1040 834	罗丹明B 罗丹明B 罗丹明B		2127 1854 1605	5 5 5	5 5 5	[19] [19] [19]
TzDBd	162.3	龙胆紫亮绿	6 6	307.7 276.1	2 2		[55] [55]
COF-Z1	512.52	罗丹明B 亚甲基蓝龙胆紫刚果红	7 7 7 7	344 510 564 425	120 120 120 120	4 4 4 4	[56] [56] [56] [56]
COF-Z2	549.44	罗丹明B 亚甲基蓝龙胆紫刚果红	7 7 7 7	430 315 395 483	120 120 120 120	4 4 4 4	[56] [56] [56] [56]
PI-based COFs		亚甲基蓝	10	315.6	250		[57]
TzTPT-COF		亚甲基蓝		572.484	20		[22]
苯并咪唑-COF	240	甲基橙亚甲基蓝	3 11	256 185	160 160	5 5	[58] [58]
离子型COFs
TpBd(SO₃H)₂-COF	32.4	亚甲基蓝	6~7	166 ± 13			[59]
TFPB-Pa-SO₃H COF	105.4	结晶紫亚甲基蓝罗丹明B	9 9 9	1559 1174 1062	80 120 240	5 5 5	[23] [23] [23]
TFPB-BDSA COF	127.8	结晶紫亚甲基蓝罗丹明B	9 9 9	1288 1166 1054	100 150 350	5 5 5	[23] [23] [23]
TpStb-SO₃Na	15.4	亚甲基蓝结晶紫孔雀石绿黄花绿B		1078 1861 5857 1339	10 10 10 10	5 5 5 5	[13] [13] [13] [13]
接枝官能团COFs
COF-TPDD-COOH		亚甲基蓝结晶紫孔雀石绿	10 10 10	102.89 88.02 128.64	60 60 60		[28] [28] [28]
COF-OH	252.74	铬黑T 铬蓝黑刚果红		229.12 90.71 158.39	20 20 20	3 3 3	[27] [27] [27]
复合功能化COFs
MOF-5/COF	7.025	金胺O 罗丹明B	9.5 9.5	17.95 16.18	8 8	6 6	[41] [41]
Fe₃O₄@MOF(Fe)@COF Fe₃O₄@MOF(Zr)@COF	808.35 347.62	刚果红刚果红	5 5	1250.02 625.13	120 120	7 7	[48] [48]
Fe₃O₄@MOF(Ti)@COF	63.50	黄果苷	5	294.12	120	7	[48]
BiPy-MCOF	192.87	甲基橙	3.1	440.990 μmol/g	180	4	[47]