Preparation of imidazole-containing porous organic polymers with micro-mesoporous structure for iodine and iodomethane adsorption

doi:10.16085/j.issn.1000-6613.2024-2007

Abstract

Abstract:

Radioactive iodine adsorption is a link that cannot be ignored in the post-operation treatment of nuclear power plants. At present, solid adsorbents are usually applied to the adsorption of organic iodine vapor. Among them, organic porous polymers have drawn wide attention due to their regular pore channels, high specific surface areas and other characteristics. In this study, several porous organic polymers (POPs) with micro-mesoporous structures were synthesized using 1-vinylimidazole and divinylbenzene (DVB) as monomers by adjusting the porogen/monomer ratio. The structural composition and pore properties of the POPs were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and nitrogen adsorption-desorption isotherms. The adsorption performance of the POPs for iodine (I₂) and methyl iodide (CH₃I) was evaluated through static adsorption, dynamic adsorption and dynamic column breakthrough experiments. The results indicated that the sample prepared with a porogen-to-monomer molar ratio of 2 (referred to as POP-VD2) exhibited the highest specific surface area and a significant proportion of micropores, achieving optimal adsorption capacities for iodine and methyl iodide of 3.10g/g and 1.47g/g, respectively. The outstanding adsorption performance of POP-VD2 for methyl iodide was attributed to the imidazole groups in its framework, which can undergo spontaneous methylation reactions with CH₃I to form stable imidazolium cations. Additionally, molecular adsorption energy simulations and reaction Gibbs free energy calculations provided insights into the adsorption mechanisms of iodine and methyl iodide on POP-VD2. This study offered a promising solution for the development of high-performance adsorbent materials for iodine and methyl iodide capture.

Key words: porous organic polymers (POPs), iodine, iodomethane, adsorption, electron-rich nitrogen

摘要：

放射性碘吸附是乏燃料后处理过程中不可或缺的环节。目前，固体吸附剂通常被应用于气态碘/碘甲烷的吸附研究，其中有机多孔聚合物因其可调节的吸附位点和高比表面积等优势被广泛关注。本文采用1-乙烯基咪唑和二乙烯苯（divinylbenzene，DVB）为共聚单体，通过调整致孔剂与单体比例，制备了几例具有微-介复合孔结构的有机多孔聚合物（porous organic polymers，POPs）。通过傅里叶变换红外光谱（FTIR）、X射线光电子能谱（XPS）、77K氮气吸附-脱附等温线测试深入分析了POPs材料的结构组成和孔道性质。借助静态吸附、动态吸附以及动态穿透等试验评价了POPs材料对碘（I₂）和碘甲烷（CH₃I）的吸附性能。结果表明，在致孔剂与单体摩尔比为2时所制备的样品（称为POP-VD2）不仅具有高的比表面积和丰富的微孔比例，而且对碘和碘甲烷的吸附性能最佳，分别达到3.10g/g和1.47g/g。POP-VD2对碘甲烷出色的吸附表现得益于其骨架结构中的咪唑能够与碘甲烷发生自发的季铵化反应，生成稳定的咪唑阳离子。此外，基于分子吸附能模拟和反应自由能计算结果也揭示了POP-VD2对碘和碘甲烷的吸附机理。本文为开发新型高性能低成本碘及碘甲烷吸附剂材料提供了潜在的解决方案。

关键词: 多孔有机聚合物, 碘, 碘甲烷, 吸附, 富电子氮

CLC Number:

TQ32

DUAN Ran, LI Yinhui, FU Yu, WU Yue, TAO Chunhui, TANG Yufeng, ZHAO Zeyi, ZHANG Gang, ZHANG Wenxiang, MA Heping. Preparation of imidazole-containing porous organic polymers with micro-mesoporous structure for iodine and iodomethane adsorption[J]. Chemical Industry and Engineering Progress, 2025, 44(12): 7103-7116.

段然, 李印辉, 傅钰, 伍岳, 陶春珲, 唐羽丰, 赵泽一, 张罡, 张文祥, 马和平. 具有微-介复合孔结构的含咪唑有机多孔聚合物的制备及其碘/碘甲烷吸附性能[J]. 化工进展, 2025, 44(12): 7103-7116.

Figures/Tables 18

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实验	气体流量/mL·min^-1
实验	氦气	碘甲烷	氮气	水蒸气
25℃，CH₃I穿透	10.00	5.65	0	0
25℃，50%相对湿度，CH₃I穿透	2.50	1.14	48.00	0.85
75℃，CH₃I穿透	10.00	5.65	0	0
75℃，I₂穿透	10.00	0	0	0

实验	气体流量/mL·min^-1
实验	氦气	碘甲烷	氮气	水蒸气
25℃，CH₃I穿透	10.00	5.65	0	0
25℃，50%相对湿度，CH₃I穿透	2.50	1.14	48.00	0.85
75℃，CH₃I穿透	10.00	5.65	0	0
75℃，I₂穿透	10.00	0	0	0

样品编号	元素原子分数/%
样品编号	N	C	H
0	6.744	84.108	6.665
1	7.304	83.260	6.675
2	9.804	78.249	6.674
3	8.047	82.118	6.830
4	7.087	83.476	6.715
5	6.598	84.154	6.749

样品编号	元素原子分数/%
样品编号	N	C	H
0	6.744	84.108	6.665
1	7.304	83.260	6.675
2	9.804	78.249	6.674
3	8.047	82.118	6.830
4	7.087	83.476	6.715
5	6.598	84.154	6.749

样品名称	碘甲烷吸附量	碘蒸气吸附量	参考文献
POP-VD2	1.47g/g，75℃	3.10g/g，75℃	本文
MFU-4l	0.41g/g，150℃	—	[33]
SCU-20	1.84g/g，75℃	—	[34]
TPC-cPS	1.57g/g，25℃	—	[35]
Ag-Tipe	0.55g/g，75℃	3.31g/g，75℃	[36]
Zn-Vlm₆	—	2.47g/g，75℃	[36]
TPTA-BD	0.76g/g，75℃	—	[37]
Ag-ZSM-5	1.1g/g，90℃	—	[38]
SCU-COF-2	1.45g/g，75℃	—	[19]
HIL	0.42g/g，75℃	—	[39]
MHP-P5Q	0.8g/g，25℃	—	[40]
MIL-101-Cr-DMEDA	0.8g/g，150℃	—	[41]
1-Me-2-PhIn-P	—	2.99g/g，75℃	[38]
PAF-24	—	2.76g/g，75℃	[42]
BDP-CPP-1	—	2.83g/g，75℃	[43]
NOP-54	—	2.02g/g，75℃	[44]
TPAPyH	—	1.27g/g，70℃	[45]
PAF-1	—	1.86g/g，25℃	[46]
JUC-Z2	—	1.44g/g，25℃	[46]
HCPs-1	—	2.04g/g，75℃	[47]
HCPs-2	—	2.50g/g，75℃	[47]