基于二苯并-18-冠-6基体改性的K+选择性离子交换膜的制备及性能研究

doi:10.11949/0438-1157.20211846

摘要/Abstract

摘要：

基于18-冠-6醚环腔体可与K⁺形成1∶1型稳定的络合物，通过掺杂的方式将4，4'-二氨基-二苯并-18-冠-6（A18C6）引入离子交换膜基材料中并成膜，然后利用1，3，5-苯三甲酰氯（TMC）对A18C6分子进行交联固定，制得一系列改性阳离子交换膜。通过改变A18C6的含量和TMC的反应时间来调控阳离子交换膜的基体结构，系统考察了改性膜在K⁺/Mg²⁺、K⁺/Na⁺ 和K⁺/Li⁺的二元体系中对K⁺的电渗析选择性。研究结果表明，在电流密度为5.0 mA·cm^-2的条件下，最优膜M-A18C6-10%-T30在K⁺/Mg²⁺和K⁺/Li⁺体系中对K⁺的选择性（ $P M g 2 + K + = 6.96$ ， $P L i + K + = 3.73$ ）高于商业的单价选择性阳离子交换膜CIMS（ $P M g 2 + K + = 5.36$ ）。A18C6的掺杂引入不仅提高了膜基体的致密性（孔径筛分效应），也为K⁺在膜基体中的传输提供了新的离子传输通道（离子-偶极作用）。

关键词: 膜, 电渗析, 离子交换, 4, 4'-二氨基-二苯并-18-冠-6, 选择性

Abstract:

Based on the fact that the 18-crown-6 ether ring cavity can form a 1∶1 stable complex with K⁺, 4,4'-diamino-dibenzo-18-crown-6 (A18C6) was introduced into the ion-exchange membrane-based material and formed into a membrane, and then A18C6 molecules were cross-linked and immobilized with 1,3,5-benzenetricarbonyl chloride (TMC) to obtain a series of modified cation-exchange membranes. By changing the content of A18C6 and the reaction time of TMC to adjust the matrix structure of CEMs, the ED permselectivity to K⁺ for the modified membranes in binary systems of K⁺/Mg²⁺, K⁺/Na⁺ and K⁺/Li⁺ were systematically investigated. At a constant current density of 5.0 mA·cm^-2, the modified membrane M-A18C6-10%-T30 shows prominent permselectivity to K⁺ in K⁺/Mg²⁺ and K⁺/Li⁺ binary systems ( $P M g 2 + K + = 6.96$ , $P L i + K + = 3.73$ ), which is superior to commercial monovalent selective cation exchange membrane (MSCEM) CIMS ( $P M g 2 + K + = 5.36$ ). The introduction of A18C6 improves the compactness of membrane matrix (pore-size sieving effect) and further provides new ion transport channels for K⁺ (ion-dipole interaction).

Key words: membranes, electrodialysis, ion exchange, 4,4'-diamino-dibenzo-18-crown-6, selectivity

中图分类号:

杨珊珊, 姚宇洋, 董云迪, 徐志鹏, 高尚上, 阮慧敏, 沈江南. 基于二苯并-18-冠-6基体改性的K⁺选择性离子交换膜的制备及性能研究[J]. 化工学报, 2022, 73(4): 1781-1793.

Shanshan YANG, Yuyang YAO, Yundi DONG, Zhipeng XU, Shangshang GAO, Huimin RUAN, Jiangnan SHEN. Preparation and performance of ion exchange membrane with K⁺ selectivity based on dibenzo-18-crown-6 modification[J]. CIESC Journal, 2022, 73(4): 1781-1793.

图/表 18

表1 实验中所用商业离子交换膜的基本参数

Table 1 Commercial membranes used in measurement and their characteristic properties

膜名称	厚度/μm	爆破强度/MPa	面电阻/ (Ω·cm²)	迁移数/%
AMX	140	≥ 0.25	1.8	98
CIMS	150	≥ 0.10	2.4	> 96

图1 A18C6的制备过程

Fig.1 Preparation of A18C6

图2 SPES膜的改性过程

Fig.2 The modification process of SPES membrane

图3 离子交换膜的电化学阻抗谱(EIS)测试装置

Fig.3 Schematic diagram of the experimental setup for the measurement of electrochemical impedance spectroscopy (EIS)

图4 离子交换膜迁移数的测试装置

Fig.4 Schematic diagram of the experimental setup for the measurement of transport number

图5 阳离子膜渗透选择性的测试示意图

Fig.5 Schematic diagram of the ED apparatus for measuring the cation permselectivity of the CEMs

图6 18C6、N18C6和A18C6的1H NMR谱图

Fig.6 1H NMR spectra of 18C6, N18C6, and A18C6

图7 样品的FT-IR谱图

Fig.7 FT-IR spectra of samples

图8 改性膜的C 1s窄谱

Fig.8 C 1s narrow-spectrum of modified membranes

表2 由C 1s窄谱获得的改性膜中可能的化学物种和含量

Table 2 The probable chemical species and content in modified membranes obtained from narrow-spectrum of C 1s

膜种类	C 1s窄谱中可能存在的化学基团的含量/%
膜种类	C—C/C—H (284.6 eV)	C—O/C—N (286.2 eV)	OC—O (288.2 eV)
M-A18C6-10%	84.21	14.54	1.25
M-A18C6-5%-T30	73.93	16.20	9.87
M-A18C6-10%-T30	79.81	17.64	2.54
M-A18C6-20%-T30	70.45	25.46	4.09

图9 阳离子交换膜的IEC随膜基体中A18C6含量的变化曲线

Fig.9 IEC of cation exchange membranes as function of the percent of A18C6 in membrane matrix

图10 在不同温度(25和40℃)下阳离子交换膜的WU随A18C6含量的变化

Fig.10 WU of cation exchange membranes as function of the percent of A18C6 in membrane matrix at 25 and 40℃

图11 阳离子交换膜的面电阻和迁移数随A18C6含量的变化

Fig.11 Surface area resistance and transport number of cation exchange membranes as function of the percent of A18C6 in membrane matrix

图12 改性膜在等浓度(0.05 mol·L-1)的K+/Mg2+体系中对阳离子的选择性(电流密度为5.0 mA·cm–2)

Fig.12 Permselectivity of cations for modified membranes in 0.05 mol·L-1 K+/Mg2+ system at current density of 5.0 mA·cm–2

图13 原膜、改性膜和商业单价阳离子交换膜CIMS在ED分离K+/Mg2+过程中的阳离子通量

Fig.13 Cation fluxes of the pristine membrane, modified membranes and commercial monovalent cation exchange membrane CIMS in the ED process for K+/Mg2+ separation

图14 TMC的反应时间对改性膜K+/Mg2+选择性分离的影响

Fig.14 Effect of reaction time of TMC on permselectivity of K+/Mg2+ of modified membranes

图15 原膜M-0、改性膜M-A18C6-10%-T30在K+/Na+(a)和K+/Li+(b)体系中的选择性和离子通量

Fig.15 Selectivity and ion fluxes of pristine membrane (M-0), modified membrane (M-A18C6-10%-T30) in K+/Na+ (a) and K+/Li+ (b) systems

图16 ED过程中改性膜对K+实现特异性分离的可能机理分析

Fig.16 Analysis of the possible mechanisms for the specificity to K+ of the modified membranes in ED process

参考文献 40

1	Zhang W, Miao M J, Pan J F, et al. Process economic evaluation of resource valorization of seawater concentrate by membrane technology[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(7): 5820-5830.
2	Al-Amshawee S, Yunus M Y B M, Azoddein A A M, et al. Electrodialysis desalination for water and wastewater: a review[J]. Chemical Engineering Journal, 2020, 380: 122231.
3	Ahdab Y D, Rehman D, Lienhard J H V. Brackish water desalination for greenhouses: improving groundwater quality for irrigation using monovalent selective electrodialysis reversal[J]. Journal of Membrane Science, 2020, 610: 118072.
4	Wang L, Patel S K, Elimelech M. Correlation equation for evaluating energy consumption and process performance of brackish water desalination by electrodialysis[J]. Desalination, 2021, 510: 115089.
5	Hosseini S M, Alibakhshi H, Jashni E, et al. A novel layer-by-layer heterogeneous cation exchange membrane for heavy metal ions removal from water[J]. Journal of Hazardous Materials, 2020, 381: 120884.
6	Tamersit S, Bouhidel K E, Zidani Z. Investigation of electrodialysis anti-fouling configuration for desalting and treating tannery unhairing wastewater: feasibility of by-products recovery and water recycling[J]. Journal of Environmental Management, 2018, 207: 334-340.
7	蔡媛媛, 郭百涛, 邢卫红, 等. 面向健康产业应用需求的膜技术与膜材料[J]. 化工学报, 2020, 71(7): 2921-2932.
	Cai Y Y, Guo B T, Xing W H, et al. Progress research on development of membrane technology and materials for health industry[J]. CIESC Journal, 2020, 71(7): 2921-2932.
8	Luo T, Abdu S, Wessling M. Selectivity of ion exchange membranes: a review[J]. Journal of Membrane Science, 2018, 555: 429-454.
9	Strathmann H. Electrodialysis, a mature technology with a multitude of new applications[J]. Desalination, 2010, 264(3): 268-288.
10	Patel M, Sheth B K. Electrodialysis in the separation of sulfuric acid from the mixture of sulfuric and hydrochloric acid[J]. International Journal of Advance Research and Innovative Ideas in Education, 2017, 3: 5092-5097.
11	Farrokhzad H, Darvishmanesh S, Genduso G, et al. Development of bivalent cation selective ion exchange membranes by varying molecular weight of polyaniline[J]. Electrochimica Acta, 2015, 158: 64-72.
12	Farrokhzad H, Moghbeli M R, Gerven T V, et al. Surface modification of composite ion exchange membranes by polyaniline[J]. Reactive and Functional Polymers, 2015, 86: 161-167.
13	刘元伟, 董晨初, 廖俊斌, 等. 不同侧链BPPO阴离子交换膜的制备及其抗污染性能[J]. 化工学报, 2021,72(3): 1732-1741.
	Liu Y W, Dong C C, Liao J B, et al. Anti-fouling properties and preparation of anion-exchange membranes based on BPPO modified by different side chain lengths[J]. CIESC Journal, 2021,72(3): 1732-1741.
14	Thakur A K, Manohar M, Shahi V K. Controlled metal loading on poly(2-acrylamido-2-methyl-propane-sulfonic acid) membranes by an ion-exchange process to improve electrodialytic separation performance for mono-/bi-valent ions[J]. Journal of Materials Chemistry A, 2015, 3(35): 18279-18288.
15	Xu T T, Shehzad M A, Yu D B, et al. Highly cation permselective metal-organic framework membranes with leaf-like morphology[J]. ChemSusChem, 2019, 12(12): 2593-2597.
16	潘杰峰, 郑瑜, 丁金成, 等. 膜法电容去离子技术用于水溶液中单/多价阴离子的分离[J]. 化工学报, 2018, 69(8): 3502-3508.
	Pan J F, Zheng Y, Ding J C, et al. Monovalent anions removal by capacitive deionization integrated with monovalent anion permselective exchange membrane[J]. CIESC Journal, 2018, 69(8): 3502-3508.
17	Fertig N, Klau M, George M, et al. Activity of single ion channel proteins detected with a planar microstructure[J]. Applied Physics Letters, 2002, 81: 4865-4867.
18	Liu H M, Jameson C J, Murad S. Molecular dynamics simulation of ion selectivity process in nanopores[J]. Molecular Simulation, 2008, 34(2): 169-175.
19	Pedersen C J. Cyclic polyethers and their complexes with metal salts[J]. Journal of the American Chemical Society, 1967, 89(26): 7017-7036.
20	Zhang B, Wang J, Yu Z Q, et al. Novel optical anisotropy of a liquid crystalline “cubic” phase in a discotic crown ether derivative[J]. Journal of Materials Chemistry C, 2014, 2(26): 5168-5175.
21	Ren C L, Shen J, Zeng H Q, et al. Combinatorial evolution of fast-conducting highly selective K⁺-channels via modularly tunable directional assembly of crown ethers[J]. Journal of the American Chemical Society, 2017, 139(36): 12338-12341.
22	Sata T, Tanimoto M, Kawamura K, et al. Transport properties of cation exchange membranes in the presence of ether compounds in electrodialysis[J]. Journal of Colloid and Interface Science, 1999, 219(2): 310-319.
23	Olsher U, Hankins M G, Kim Y D, et al. Anion effect on selectivity in crown ether extraction of alkali metal cations[J]. Journal of the American Chemical Society, 1993, 115(8): 3370-3371.
24	Bhattacharyya A, Goswami A. Effect of cation driven loading of dibenzo-18-crown-6 in Nafion-117 membrane on the diffusion and transport behavior of alkali metal ions[J]. Journal of Physical Chemistry B, 2009, 113: 12958-12963.
25	Zoetebier B, Tas S, Vancso G, et al. Synthesis of poly(arylene ether ketone)s bearing skeletal crown ether units for cation exchange membranes[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2015, 53: 2786-2793.
26	Chaudhury S, Bhattacharyya A, Goswami A. Electrodriven ion transport through crown ether-Nafion composite membrane: enhanced selectivity of Cs⁺ over Na⁺ by ion gating at the surface[J]. Industrial & Engineering Chemistry Research, 2014, 53: 8804-8809.
27	Chaudhury S, Bhattacharyya A, Goswami A. Electrodriven selective transport of Cs⁺ using chlorinated cobalt dicarbollide in polymer inclusion membrane: a novel approach for cesium removal from simulated nuclear waste solution[J]. Environmental Science & Technology, 2014, 48: 12994-13000.
28	Pethrick R A, Wilson M J, Affrossman S, et al. Synthesis and cation complexation properties of crown ether polyamic acids/imides[J]. Polymer, 2000, 41(19): 7111-7121.
29	Gourdet B, Singh K, Stuart A M, et al. Di(1H,1H,2H,2H-perfluorooctyl)-dibenzo-18-crown-6: a “light fluorous” recyclable phase transfer catalyst[J]. Journal of Fluorine Chemistry, 2010, 131(11): 1133-1143.
30	Ye G, Bai F F, Wei J C, et al. Novel polysiloxane resin functionalized with dicyclohexano-18-crown-6 (DCH18C6): synthesis, characterization and extraction of Sr(Ⅱ) in high acidity HNO₃ medium[J]. Journal of Hazardous Materials, 2012, 225/226: 8-14.
31	Tavangar T, Ashtiani F Z, Karimi M. Morphological and performance evaluation of highly sulfonated polyethersulfone/polyethersulfone membrane for oil/water separation[J]. Journal of Polymer Research, 2020, 27(9): 1-12.
32	Khodabakhshi M R, Goodarzi V. Preparing and analysis an innovative membrane based on polyethersulfone/sulfonated polyethersulfone/organically modified nanoclay: ability to heavy metal removal[J]. Materials Today Communications, 2021, 26: 101957.
33	Wu D Y, Yi C H, Zhang B B, et al. Synthesis and characterization of trans-di(nitrobenzo)- and di(aminobenzo)-18-crown-6 derivatives with high selectivity[J]. Synthetic Communications, 2018, 48(3): 329-335.
34	Yang T, Xu W H, Peng X W, et al. Crown ether-containing polyimides with high dielectric constant[J]. RSC Advances, 2017, 7(38): 23309-23312.
35	Zhang H Q, Li X F, Zhao C J, et al. Composite membranes based on highly sulfonated PEEK and PBI: morphology characteristics and performance[J]. Journal of Membrane Science, 2008, 308(1/2): 66-74.
36	王超, 潘能修, 鲁丹, 等. 电渗析用季铵化聚氯乙烯均相阴离子交换膜的制备[J]. 化工学报, 2019, 70(4): 1620-1627.
	Wang C, Pan N X, Lu D, et al. Preparation of homogeneous anion exchange membrane based on quaternized PVC for electrodialysis[J]. CIESC Journal, 2019, 70(4): 1620-1627.
37	Sata T, Yoshida T, Matsusaki K. Transport properties of phosphonic acid and sulfonic acid cation exchange membranes[J]. Journal of Membrane Science, 1996, 120(1): 101-110.
38	姜玉良, 刘元伟, 韩波, 等. PEI交联的PECH/nylon复合阴离子交换膜的制备及性能研究[J]. 化工学报, 2018, 69(6): 2744-2752.
	Jiang Y L, Liu Y W, Han B, et al. Preparation and properties of PEI crosslinked PECH/nylon composite anion exchange membrane[J]. CIESC Journal, 2018, 69(6): 2744-2752.
39	Nightingale E R. Phenomenological theory of ion solvation. Effective radii of hydrated ions[J]. The Journal of Chemical Physics, 1959, 63(9): 1381-1387.
40	Joshi R K, Carbone P, Wang F C, et al. Precise and ultrafast molecular sieving through graphene oxide membranes[J]. Science, 2014, 343(6172): 752-754.

[1]	邵苛苛, 宋孟杰, 江正勇, 张旋, 张龙, 高润淼, 甄泽康. 水平方向上冰中受陷气泡形成和分布实验研究[J]. 化工学报, 2023, 74(S1): 161-164.
[2]	吴延鹏, 李晓宇, 钟乔洋. 静电纺丝纳米纤维双疏膜油性细颗粒物过滤性能实验分析[J]. 化工学报, 2023, 74(S1): 259-264.
[3]	吴曦, 区祖迪, 张鑫杰, 徐士鸣, 朱晓静. HFO-1243zf爆燃特性实验研究[J]. 化工学报, 2023, 74(S1): 346-352.
[4]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[5]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[6]	赵亚欣, 张雪芹, 王荣柱, 孙国, 姚善泾, 林东强. 流穿模式离子交换层析去除单抗聚集体[J]. 化工学报, 2023, 74(9): 3879-3887.
[7]	何松, 刘乔迈, 谢广烁, 王斯民, 肖娟. 高浓度水煤浆管道气膜减阻两相流模拟及代理辅助优化[J]. 化工学报, 2023, 74(9): 3766-3774.
[8]	胡建波, 刘洪超, 胡齐, 黄美英, 宋先雨, 赵双良. 有机笼跨细胞膜易位行为的分子动力学模拟研究[J]. 化工学报, 2023, 74(9): 3756-3765.
[9]	齐聪, 丁子, 余杰, 汤茂清, 梁林. 基于选择吸收纳米薄膜的太阳能温差发电特性研究[J]. 化工学报, 2023, 74(9): 3921-3930.
[10]	胡亚丽, 胡军勇, 马素霞, 孙禹坤, 谭学诣, 黄佳欣, 杨奉源. 逆电渗析热机新型工质开发及电化学特性研究[J]. 化工学报, 2023, 74(8): 3513-3521.
[11]	张佳怡, 何佳莉, 谢江鹏, 王健, 赵鹬, 张栋强. 渗透汽化技术用于锂电池生产中N-甲基吡咯烷酮回收的研究进展[J]. 化工学报, 2023, 74(8): 3203-3215.
[12]	高燕, 伍鹏, 尚超, 胡泽君, 陈晓东. 基于双流体喷嘴的磁性琼脂糖微球的制备及其蛋白吸附性能探究[J]. 化工学报, 2023, 74(8): 3457-3471.
[13]	张贲, 王松柏, 魏子亚, 郝婷婷, 马学虎, 温荣福. 超亲水多孔金属结构驱动的毛细液膜冷凝及传热强化[J]. 化工学报, 2023, 74(7): 2824-2835.
[14]	李盼, 马俊洋, 陈志豪, 王丽, 郭耘. Ru/α-MnO₂催化剂形貌对NH₃-SCO反应性能的影响[J]. 化工学报, 2023, 74(7): 2908-2918.
[15]	韩奎奎, 谭湘龙, 李金芝, 杨婷, 张春, 张永汾, 刘洪全, 于中伟, 顾学红. 四通道中空纤维MFI分子筛膜用于二甲苯异构体分离[J]. 化工学报, 2023, 74(6): 2468-2476.