共价有机框架吸附放射性气态碘的研究进展

doi:10.16085/j.issn.1000-6613.2024-0895

摘要/Abstract

摘要：

核裂变产物中的放射性气态碘是污染环境的主要核素。核电厂采用固体吸附的方法捕集废气中的放射性碘。浸渍活性炭作为工业用碘吸附材料，具有吸附效率高、制造成本低的优点，但存在吸附容量低、易老化、高温易分解等问题。共价有机框架（covalent organic frameworks，COFs）作为一类共价键连接的新型晶态多孔材料，具有比表面积高、孔道结构有序、结构可设计性以及物理化学稳定性强等特点，展现出优异的碘吸附性能。本文探讨了不同种类碘化合物在COFs内的吸附机理，概述了不同种类COFs的碘吸附性能，系统总结了影响COFs碘吸附性能的多种因素，提出了高碘吸附性能COFs材料的设计策略。最后，总结了COFs实现工业应用的主要挑战及发展前景，指出需开发具有普适性的低成本COFs制备方法并加强其在实际工况条件下吸附性能的研究。

关键词: 共价有机框架, 放射性碘, 吸附, 吸附机理, 多孔材料

Abstract:

The radioactive gaseous iodine is the main nuclide harmful to the environment in nuclear fission products. Solid adsorption is used in nuclear power plants to capture radioactive iodine in exhausted gas. As an industrial iodine adsorption material, the impregnated activated carbon has the advantages of high adsorption efficiency and low manufacturing cost, but there are some problems such as low adsorption capacity, easy aging and easy decomposition at high temperature. Covalent organic frameworks (COFs), as a new type of crystalline porous material connected by covalent bonds, show excellent iodine adsorption performance due to the high specific surface area, ordered structure, structure designability and physical and chemical stability. In this review, the adsorption mechanisms of different kinds of iodine in COFs were discussed. The iodine adsorption performances and their influencing factors of various COFs were summarized systematically. The construction principles of COFs with high iodine adsorption performance were proposed. Finally, the key challenges and development strategies of COFs for industrial applications were prospected. It pointed out the importance of developing universal low-cost preparation methods of COFs and strengthening research on adsorption performance under real industrial conditions.

Key words: covalent organic frameworks, radioactive iodine, adsorption, adsorption mechanism, porous materials

中图分类号:

TQ424.3

梁书玮, 俞杰, 谢钟音, 裴鉴禄, 林中鑫, 陈泽翔. 共价有机框架吸附放射性气态碘的研究进展[J]. 化工进展, 2025, 44(7): 3965-3975.

LIANG Shuwei, YU Jie, XIE Zhongyin, PEI Jianlu, LIN Zhongxin, CHEN Zexiang. Covalent organic frameworks for radioactive gaseous iodine adsorption[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 3965-3975.

图/表 9

图1 共价有机框架碘吸附性能强化研究

图2 吸附I2前后TGDM（25℃、150℃）的化学表征图[11]

图3 COF-TAPB和COF-TAPT的CH3I吸附机理[8]（TFPA-T是用于计算COF-TAPA的模型分子，1kcal=4.19kJ）

图4 使用不同催化剂合成的CTF-1的表征和吸附性能[16]

图5 FAL-COF-1和RIL-COF-1的单质碘吸附和解吸性能曲线[18]

图6 选择性位点合成策略合成Th-Bta-COF、NH2-Th-Bta-COF和NH2-Dbt[30]

图7 iCOF-AB-X的合成和碘吸附性能[40]

图8 两种路线制备COFs凝胶示意图[41]

表1 COFs材料及碘吸附性能汇总

COFs材料	种类	比表面积/m²·g^-1	孔径/nm	孔容/cm³·g^-1	I₂饱和吸附时间/h	饱和吸附容量/g·g^-1	参考文献
COF-TAPT	二维亚胺COFs	2348	1.92	0.97	96	8.61，1.53^① 2.38^②，1.30^③	[8]
TPB-DMTP	二维亚胺COFs	1927	3.3	1.28	96	6.26	[9]
SCU-COF-2	联吡啶基COFs	413.4	—	—	96	6.0，1.45^① 0.979^④，0.564^⑤	[10]
TGDM	胍基离子COFs	645.8	0.66	0.46	10	0.29^⑥	[11]
OM-COF-300	大孔单晶三维COFs	1410	0.5	0.63	36	3.15	[14]
micro-COF-1	微孔二维亚胺COFs	816	1.7	0.59	75	2.9	[15]
CTF-1@ZnCl₂	二维三嗪COFs	1476	2.0	—	24	4.31	[16]
TPT-DHBD	羟基修饰亚胺COFs	297	3.43	—	46	4.03	[17]
FAL-COF-1	柔性胺类COFs	168	3.69	0.32	75	4.94	[18]
Hz-COF	腙类COFs	145	2.16	—	70	2.05	[19]
NH-COF	胺类COFs	78	2.16	—	70	2.60	[19]
QTD-COF-1	准三维COFs	—	1.36/1.66	—	5	4.62	[20]
JUC-561	三维COFs	2359	2.46	1.92	18	8.19	[21]
SIOC-COF-7	二维亚胺COFs	618	0.50/1.18	0.41	48	4.81	[23]
TJNU-201	二维亚胺COFs	2510	1.4	—	96	5.625	[24]
COF-p-NEU1	C $̿$ C连接COFs	186	4.93	—	30	4.58	[25]
肼-MTH-TFPB	酰胺类COFs	364.3	2.9	0.23	61	3.05	[26]
COF-LZU-1	π共轭COFs	858	1.6	0.48	48	5.30	[27]
TFPB-PyTTA-COF	芘环COFs	1897	1.20	1.78	36	5.62	[28]
TTA-FMTA-COF	甲氧基COFs	1985	1.97	1.12	24	5.07	[29]
NH₂-Th-Bta	氨基COFs	10	2.4	—	37	3.58	[30]
TJNU-204	羟基COFs	2048	0.89	—	48	5.34	[31]
TAPD-DHTA	羟基COFs	213.6	1.56/2.73	—	44	4.02	[32]
BTT-TAPT	噻吩基COFs	864	1.0-2.0	0.56	50	2.76	[33]
PB-TT	吡啶基COFs	1306.3	3.67	0.986	30	5.97	[34]
C-TP-PDA	吡啶基离子COFs	133	1.3	0.08	24	3.05	[35]
COF-PA	苯炔基COFs	1471	2.1	—	16	4.47	[36]
CPOF-2	炔基三维COFs	580	1.1	—	68	5.40	[37]
P-COF	磷基COFs	1056	1.0-2.0	0.60	66	6.19	[38]
TTF-TAPT	四硫富瓦烯基COFs	461	—	0.28	18	5.02	[39]
iCOF-AB-50	阳离子COFs	1390	3.3	1.21	30	10.21，2.79^②，0.44^⑦	[40]
TAPB-PDA	晶态COFs气凝胶	2273	3.3	—	90	7.7	[41]
TPB-DMTP-COF	COFs薄膜	—	—	—	4	6.87	[42]
COF@棉纤维	COFs@棉纤维	124	—	—	20	0.534	[43]
CF/COF	COFs@棉纤维	166	—	—	12	0.824	[44]

表1 COFs材料及碘吸附性能汇总

COFs材料	种类	比表面积/m²·g^-1	孔径/nm	孔容/cm³·g^-1	I₂饱和吸附时间/h	饱和吸附容量/g·g^-1	参考文献
COF-TAPT	二维亚胺COFs	2348	1.92	0.97	96	8.61，1.53^① 2.38^②，1.30^③	[8]
TPB-DMTP	二维亚胺COFs	1927	3.3	1.28	96	6.26	[9]
SCU-COF-2	联吡啶基COFs	413.4	—	—	96	6.0，1.45^① 0.979^④，0.564^⑤	[10]
TGDM	胍基离子COFs	645.8	0.66	0.46	10	0.29^⑥	[11]
OM-COF-300	大孔单晶三维COFs	1410	0.5	0.63	36	3.15	[14]
micro-COF-1	微孔二维亚胺COFs	816	1.7	0.59	75	2.9	[15]
CTF-1@ZnCl₂	二维三嗪COFs	1476	2.0	—	24	4.31	[16]
TPT-DHBD	羟基修饰亚胺COFs	297	3.43	—	46	4.03	[17]
FAL-COF-1	柔性胺类COFs	168	3.69	0.32	75	4.94	[18]
Hz-COF	腙类COFs	145	2.16	—	70	2.05	[19]
NH-COF	胺类COFs	78	2.16	—	70	2.60	[19]
QTD-COF-1	准三维COFs	—	1.36/1.66	—	5	4.62	[20]
JUC-561	三维COFs	2359	2.46	1.92	18	8.19	[21]
SIOC-COF-7	二维亚胺COFs	618	0.50/1.18	0.41	48	4.81	[23]
TJNU-201	二维亚胺COFs	2510	1.4	—	96	5.625	[24]
COF-p-NEU1	C $̿$ C连接COFs	186	4.93	—	30	4.58	[25]
肼-MTH-TFPB	酰胺类COFs	364.3	2.9	0.23	61	3.05	[26]
COF-LZU-1	π共轭COFs	858	1.6	0.48	48	5.30	[27]
TFPB-PyTTA-COF	芘环COFs	1897	1.20	1.78	36	5.62	[28]
TTA-FMTA-COF	甲氧基COFs	1985	1.97	1.12	24	5.07	[29]
NH₂-Th-Bta	氨基COFs	10	2.4	—	37	3.58	[30]
TJNU-204	羟基COFs	2048	0.89	—	48	5.34	[31]
TAPD-DHTA	羟基COFs	213.6	1.56/2.73	—	44	4.02	[32]
BTT-TAPT	噻吩基COFs	864	1.0-2.0	0.56	50	2.76	[33]
PB-TT	吡啶基COFs	1306.3	3.67	0.986	30	5.97	[34]
C-TP-PDA	吡啶基离子COFs	133	1.3	0.08	24	3.05	[35]
COF-PA	苯炔基COFs	1471	2.1	—	16	4.47	[36]
CPOF-2	炔基三维COFs	580	1.1	—	68	5.40	[37]
P-COF	磷基COFs	1056	1.0-2.0	0.60	66	6.19	[38]
TTF-TAPT	四硫富瓦烯基COFs	461	—	0.28	18	5.02	[39]
iCOF-AB-50	阳离子COFs	1390	3.3	1.21	30	10.21，2.79^②，0.44^⑦	[40]
TAPB-PDA	晶态COFs气凝胶	2273	3.3	—	90	7.7	[41]
TPB-DMTP-COF	COFs薄膜	—	—	—	4	6.87	[42]
COF@棉纤维	COFs@棉纤维	124	—	—	20	0.534	[43]
CF/COF	COFs@棉纤维	166	—	—	12	0.824	[44]

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