一种吲哚基超交联聚合物In-HCP对水中碘的吸附作用

doi:10.16085/j.issn.1000-6613.2022-1647

化工进展 ›› 2023, Vol. 42 ›› Issue (7): 3674-3683.DOI: 10.16085/j.issn.1000-6613.2022-1647

一种吲哚基超交联聚合物In-HCP对水中碘的吸附作用

于静文¹^,²(), 宋璐娜³, 刘砚超⁴, 吕瑞东², 武蒙蒙¹(), 冯宇¹, 李忠¹, 米杰¹()

^1.太原理工大学省部共建煤基能源清洁高效利用国家重点实验室/煤科学与技术教育部和山西省重点实验室，山西太原 030024
^2.潞安化工集团有限公司，山西长治 046204
^3.山西能源学院，山西晋中 030600
^4.太原理工大学化学工程与技术学院，山西太原 030024

收稿日期:2022-09-06 修回日期:2022-11-18 出版日期:2023-07-15 发布日期:2023-08-14
通讯作者: 武蒙蒙,米杰
作者简介:于静文（1988—），男，博士研究生，研究方向为有机合成方法学和多孔有机聚合物的设计、合成及应用。E-mail：469165514@qq.com。
基金资助:
国家自然科学基金(21978188);山西省自然科学基金青年科学基金(20210302123191);山西省高等学校科技创新项目(2022L602)

An indole-bearing hypercrosslinked polymer In-HCP for iodine adsorption from water

YU Jingwen¹^,²(), SONG Luna³, LIU Yanchao⁴, LYU Ruidong², WU Mengmeng¹(), FENG Yu¹, LI Zhong¹, MI Jie¹()

^1.State Key Laboratory of Clean and Efficient Coal Utilization/Key Laboratory of Coal Science and Technology of Shanxi Province and Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.Lu’an Chemical Group Co. , Ltd. , Changzhi 046204, Shanxi, China
^3.Shanxi Institute of Energy, Jinzhong 030600, Shanxi, China
^4.College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received:2022-09-06 Revised:2022-11-18 Online:2023-07-15 Published:2023-08-14
Contact: WU Mengmeng, MI Jie

摘要/Abstract

摘要：

通过傅-克烷基化反应合成了一种原料低廉、工艺简单、比表面积大、可循环利用的吲哚基超交联聚合物（In-HCP），并将其用于I₂的水相吸附。为评估In-HCP的I₂捕获能力，与活性炭（AC）进行了比较。I₂饱和水溶液的吸附动力学实验表明，In-HCP和AC对I₂的吸附行为符合准二级动力学模型，吸附速率受液膜扩散和颗粒内扩散的共同影响。两种材料对I₂的吸附在30min内达到平衡状态，AC对I₂的吸附较快，但吸附饱和时In-HCP对I₂的清除率（94.68%）高于AC（91.56%）。利用滴定法对高浓度KI₃水溶液的吸附结果进行了验证，In-HCP的I₂吸附量（2.066g/g）为AC（1.280g/g）的1.6倍，经5次循环实验后吸附量仍能达到1.762g/g，表明In-HCP有较好的循环使用性能。通过拉曼光谱和紫外-可见吸收光谱研究了吸附机理, 证明吸附过程是以化学吸附为主。

关键词: 吲哚, 超交联聚合物, 碘, 水溶液, 吸附

Abstract:

An indole-containing hypercrosslinked polymer (In-HCP), featuring cheap raw materials, simple operation, large specific surface area and recyclability, was synthesized via Friedel-Crafts alkylation reaction and then applied for iodine adsorption in aqueous solution. In order to assess the I₂ capture ability of In-HCP, activated carbon (AC) was used for comparison. The adsorption kinetics experiments in saturated I₂ aqueous solution showed that the I₂ adsorption behaviors of In-HCP and AC were fitted with pseudo-second-order kinetic model. The adsorption rate was influenced by both liquid-film diffusion and intra-particle diffusion. The I₂adsorption by both materials could reach equilibrium within 30min. The adsorption rate of AC was faster, however, the removal rate of I₂ on In-HCP (94.68%) exceeded that of AC (91.56%) when the adsorption reached saturation state. The sorption results of KI₃ high-concentration aqueous solution were validated by titrimetric analysis. The I₂ uptake capacity of In-HCP (2.066g/g) was 1.6-fold higher than that of AC (1.280g/g). The adsorption capacity of 1.762g/g was still remained after 5 cycles of experiments, indicating a good recycling performance of In-HCP. The adsorption mechanism was studied by Raman spectrum and UV-Vis absorption spectrum, demonstrating that the process was dominated by chemisorption.

Key words: indole, hypercrosslinked polymer, iodine, aqueous solution, adsorption

中图分类号:

TQ424.3

于静文, 宋璐娜, 刘砚超, 吕瑞东, 武蒙蒙, 冯宇, 李忠, 米杰. 一种吲哚基超交联聚合物In-HCP对水中碘的吸附作用[J]. 化工进展, 2023, 42(7): 3674-3683.

YU Jingwen, SONG Luna, LIU Yanchao, LYU Ruidong, WU Mengmeng, FENG Yu, LI Zhong, MI Jie. An indole-bearing hypercrosslinked polymer In-HCP for iodine adsorption from water[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3674-3683.

图/表 14

参考文献 39

1	YU Yanan, YIN Zheng, CAO Lihui, et al. Organic porous solid as promising iodine capture materials[J]. Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2022, 102(5/6): 395-427.
2	SUN Qi, AGUILA Briana, MA Shengqian. Opportunities of porous organic polymers for radionuclide sequestration[J]. Trends in Chemistry, 2019, 1(3): 292-303.
3	TESFAY REDA Alemtsehay, PAN Meng, ZHANG Dongxiang, et al. Bismuth-based materials for iodine capture and storage: A review[J]. Journal of Environmental Chemical Engineering, 2021, 9(4): 105279.
4	XIE Wei, CUI Di, ZHANG Shuran, et al. Iodine capture in porous organic polymers and metal-organic frameworks materials[J]. Materials Horizons, 2019, 6(8): 1571-1595.
5	张晓媛. 处理含碘放射性废水新型吸附剂的制备及组合工艺开发[D]. 天津: 天津大学, 2019.
	ZHANG Xiaoyuan. Synthesis of the novel adsorbent and development of an integrated process for treating iodine-containing radioactive wastewater[D]. Tianjin: Tianjin University, 2019.
6	QIN Jianxian, ZHANG Wei, CHEN Yuantao, et al. Zinc-based triazole metal complexes for efficient iodine adsorption in water[J]. Environmental Science and Pollution Research, 2021, 28(22): 28797-28807.
7	GOGIA Alisha, Prasenjit DAS, MANDAL Sanjay K. Tunable strategies involving flexibility and angularity of dual linkers for a 3D metal-organic framework capable of multimedia iodine capture[J]. ACS Applied Materials & Interfaces, 2020, 12(41): 46107-46118.
8	Mahmoud EL-SHAHAT, ABDELHAMID Ahmed E, ABDELHAMEED R. Capture of iodide from wastewater by effective adsorptive membrane synthesized from MIL-125-NH₂ and cross-linked chitosan[J]. Carbohydrate Polymers, 2020, 231: 115742.
9	LIU Rong, ZHANG Wei, CHEN Yuantao, et al. Highly efficient adsorption of iodine under ultrahigh pressure from aqueous solution[J]. Separation and Purification Technology, 2020, 233: 115999.
10	刘蓉, 张炜, 陈元涛, 等. ZIF材料对碘的吸附特性研究[J]. 无机材料学报, 2020, 35(3): 345-351.
	LIU Rong, ZHANG Wei, CHEN Yuantao, et al. Adsorption of iodine by ZIF materials[J]. Journal of Inorganic Materials, 2020, 35(3): 345-351.
11	QU Guiyang, HAN Ying, QI Junjun, et al. Rapid iodine capture from radioactive wastewater by green and low-cost biomass waste derived porous silicon-carbon composite[J]. RSC Advances, 2021, 11(9): 5268-5275.
12	ZHANG Qingmei, ZHAI Tianlong, WANG Zhen, et al. Hyperporous carbon from triptycene-based hypercrosslinked polymer for iodine capture[J]. Advanced Materials Interfaces, 2019, 6(9): 1900249.
13	HUANG Min, YANG Li, LI Xiuyun, et al. An indole-derived porous organic polymer for the efficient visual colorimetric capture of iodine in aqueous media via the synergistic effects of cation-π and electrostatic forces[J]. Chemical Communications, 2020, 56(9): 1401-1404.
14	LIN Yunxiao, JIANG Xuanfeng, KIM Samuel T, et al. An elastic hydrogen-bonded cross-linked organic framework for effective iodine capture in water[J]. Journal of the American Chemical Society, 2017, 139(21): 7172-7175.
15	XIE Linhuang, ZHENG Zhiye, LIN Qiuyuan, et al. Calix[4]pyrrole-based crosslinked polymer networks for highly effective iodine adsorption from water[J]. Angewandte Chemie (International Ed in English), 2022, 61(1): e202113724.
16	ZHANG Zhizhong, LI Liang, AN Duo, et al. Triazine-based covalent organic polycalix[4]arenes for highly efficient and reversible iodine capture in water[J]. Journal of Materials Science, 2020, 55(4): 1854-1864.
17	AN Duo, LI Liang, ZHANG Zhizhong, et al. Amino-bridged covalent organic Polycalix[4]arenes for ultra efficient adsorption of iodine in water[J]. Materials Chemistry and Physics, 2020, 239: 122328.
18	CAO Jiajun, ZHU Huangtianzhi, SHANGGUAN Liqing, et al. A pillar[5]arene-based 3D polymer network for efficient iodine capture in aqueous solution[J]. Polymer Chemistry, 2021, 12(24): 3517-3521.
19	CHEN Run, HU Tianliang, LI Yongqiang. Stable nitrogen-containing covalent organic framework as porous adsorbent for effective iodine capture from water[J]. Reactive and Functional Polymers, 2021, 159: 104806.
20	WANG Yinghui, ZHAO Meng, ZHANG Lili, et al. Covalent organic polymers are highly effective absorbers of iodine in water under ultra-high pressure[J]. Journal of Radioanalytical and Nuclear Chemistry, 2021, 329(3): 1407-1415.
21	Arunabha SEN, SHARMA Shivani, DUTTA Subhajit, et al. Functionalized ionic porous organic polymers exhibiting high iodine uptake from both the vapor and aqueous medium[J]. ACS Applied Materials & Interfaces, 2021, 13(29): 34188-34196.
22	LI Bin, WANG Bin, HUANG Xiayang, et al. Terphen[n]arenes and quaterphen[n]arenes (n=3-6): One-pot synthesis, self-assembly into supramolecular gels, and iodine capture[J]. Angewandte Chemie International Edition, 2019, 58(12): 3885-3889.
23	ZHENG Baozhan, LIU Xiaoxia, HU Jing, et al. Construction of hydrophobic interface on natural biomaterials for higher efficient and reversible radioactive iodine adsorption in water[J]. Journal of Hazardous Materials, 2019, 368: 81-89.
24	LI Tianze, XU Hui. Recent progress of bioactivities, mechanisms of action, total synthesis, structural modifications and structure-activity relationships of indole derivatives: A review[J]. Mini Reviews in Medicinal Chemistry, 2022, 22(21): 2702-2725.
25	高宇. 洗油中吲哚和喹啉的分离基础研究[D]. 太原: 太原理工大学, 2020.
	GAO Yu. Study on basic separation of indole and quinoline in washing oil[D]. Taiyuan: Taiyuan University of Technology, 2020.
26	SALEH Muhammad, LEE Han Myoung, Christian KEMP K, et al. Highly stable CO₂/N₂ and CO₂/CH₄ selectivity in hyper-cross-linked heterocyclic porous polymers[J]. ACS Applied Materials & Interfaces, 2014, 6(10): 7325-7333.
27	王艳. 吲哚基多孔材料的制备及对水中TNT吸附性能研究[D]. 北京: 中国工程物理研究院, 2020.
	WANG Yan. Preparation of indol-based porous materials and their adsorption properties of TNT in water[D]. Beijing: China Academy of Engineering Physics, 2020.
28	CHEN Dongyang, FU Yu, YU Wenguang, et al. Versatile Adamantane-based porous polymers with enhanced microporosity for efficient CO₂ capture and iodine removal[J]. Chemical Engineering Journal, 2018, 334: 900-906.
29	XIA Yanting, LI Yankai, GU Yuntao, et al. Adsorption desulfurization by hierarchical porous organic polymer of poly-methylbenzene with metal impregnation[J]. Fuel, 2016, 170: 100-106.
30	JIN Tian, AN Shuhao, YANG Xuejing, et al. Efficient adsorptive desulfurization by task-specific porous organic polymers[J]. AIChE Journal, 2016, 62(5): 1740-1746.
31	李和国, 王立莹, 赵越, 等. 一类新型高效捕获碘蒸汽的低成本超交联微孔聚合物[J]. 兵器装备工程学报, 2021, 42(7): 269-273.
	LI Heguo, WANG Liying, ZHAO Yue, et al. A kind of novel low-cost hypercrosslinked polymers with efficient iodine adsorption[J]. Journal of Ordnance Equipment Engineering, 2021, 42(7): 269-273.
32	HUANG Yalin, LI Wei, XU Yuwei, et al. Rapid iodine adsorption from vapor phase and solution by a nitrogen-rich covalent piperazine-triazine-based polymer[J]. New Journal of Chemistry, 2021, 45(12): 5363-5370.
33	WANG Yan, TAO Jian, XIONG Shaohui, et al. Ferrocene-based porous organic polymers for high-affinity iodine capture[J]. Chemical Engineering Journal, 2020, 380: 122420.
34	XU Meiyun, WANG Tao, ZHOU Lei, et al. Fluorescent conjugated mesoporous polymers with N,N-diethylpropylamine for the efficient capture and real-time detection of volatile iodine[J]. Journal of Materials Chemistry A, 2020, 8(4): 1966-1974.
35	WANG Chang, WANG Yu, GE Rile, et al. A 3D covalent organic framework with exceptionally high iodine capture capability[J]. Chemistry (Weinheim an Der Bergstrasse, Germany), 2018, 24(3): 585-589.
36	LIN Jingxiang, LIANG Jun, FENG Jifei, et al. Iodine uptake and enhanced electrical conductivity in a porous coordination polymer based on cucurbit[6]uril[J]. Inorganic Chemistry Frontiers, 2016, 3(11): 1393-1397.
37	WALL S L D, MEADOWS E S, BARBOUR L, et al. Solution- and solid-state evidence for alkali metal cation-π interactions with indole, the side chain of tryptophan[J]. Journal of the American Chemical Society, 1999, 121: 5613-5614.
38	SCHLAMADINGER Diana E, DASCHBACH Megan M, GOKEL George W, et al. UV resonance Raman study of cation-π interactions in an indole crown ether[J]. Journal of Raman Spectroscopy: JRS, 2011, 42(4): 633-638.
39	SVENSSON Per H, KLOO Lars. Synthesis, structure, and bonding in polyiodide and metal iodide-iodine systems[J]. Chemical Reviews, 2003, 103(5): 1649-1684.

吲哚基超交联聚合物	吲哚、FDA和FeCl₃摩尔比	反应温度和时间	干燥方式	比表面积/ m²·g^-1
IN	1∶3∶3	80℃，18h	真空干燥	243
PIN	1∶2∶2	80℃，18h	CO₂超临界干燥	490

吲哚基超交联聚合物	吲哚、FDA和FeCl₃摩尔比	反应温度和时间	干燥方式	比表面积/ m²·g^-1
IN	1∶3∶3	80℃，18h	真空干燥	243
PIN	1∶2∶2	80℃，18h	CO₂超临界干燥	490

吸附剂	准二级动力学模型			颗粒内扩散动力学模型
	准二级动力学模型			第一阶段			第二阶段
	q_e,_cal/g·g^-1	k₂/g·g^-1·min^-1	R²	k_p/g·g^-1·min^-0.5	C/g·g^-1	R²	k_p/g·g^-1·min^-0.5	C/g·g^-1	R²
In-HCP	0.586	4.169	0.99994	0.05362	0.40918	0.85887	0.00391	0.55686	0.88358
AC	0.562	5.164	0.99996	0.02223	0.47633	0.94975	0.00578	0.52570	0.89894

吸附剂	准二级动力学模型			颗粒内扩散动力学模型
	准二级动力学模型			第一阶段			第二阶段
	q_e,_cal/g·g^-1	k₂/g·g^-1·min^-1	R²	k_p/g·g^-1·min^-0.5	C/g·g^-1	R²	k_p/g·g^-1·min^-0.5	C/g·g^-1	R²
In-HCP	0.586	4.169	0.99994	0.05362	0.40918	0.85887	0.00391	0.55686	0.88358
AC	0.562	5.164	0.99996	0.02223	0.47633	0.94975	0.00578	0.52570	0.89894

吸附剂	消耗NaHSO₃溶液体积/mL	滤液中I₂质量/mg	被吸附I₂质量/mg
In-HCP	15.50	196.7	103.3
AC	18.60	236.0	64.0

一种吲哚基超交联聚合物In-HCP对水中碘的吸附作用

An indole-bearing hypercrosslinked polymer In-HCP for iodine adsorption from water

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参考文献 39

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Metrics

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吸附剂	I₂吸附量/g·g^-1	参考文献
H_COF-1	2.1±0.1	[14]
CalCOP1	2.318	[16]
CalCOP2	1.758	[16]
CalCOP3	0.346	[16]
CalCOP4	0.156	[16]
In-HCP	2.066	本文
AC	1.280	本文

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