Preparation and Performance Analysis of Anion Exchange Membranes Modified with Chromotropic Acid Grafted 18⁃Crown⁃6 Ether on Polyvinyl Alcohol

doi:10.12422/j.issn.1672-6952.2025.05.002

Abstract

Abstract:

The quaternary ammonium group (QA) commonly used in conventional anion exchange membranes (AEMs) has a low dissociation constant with OH^-, resulting in poor conductivity. The crown ether group can significantly enhance the ion exchange capacity (IEC) and OH^- conduction efficiency of AEMs due to its ability to form positively charged complexes with alkali metal cations. Meanwhile, the ether bond in the crown ether ring exhibits good alkali and chemical stability. In view of the above advantages, a series of AEMs grafted with bi?crown ethers were successfully prepared by grafting dibenzo?18?crown?6?ether?modified polyvinyl alcohol (PVA) via metastable acid. The results showed that the bi?crown ether anion?exchange membranes exhibited higher OH^-selectivity and chemical stability compared with the mono?crown ether membrane materials; the prepared AEMs exhibited good OH^- selectivity and chemical stability in terms of electrical conductivity (conductivity of 165.5 mS/cm at 80 ℃), mechanical properties (tensile strength of 47 MPa at room temperature), and alkali stability (only 4.52% decrease in conductivity after immersion in KOH at a concentration of 6 mol/L for 168 h), and the high efficiency electrolysis of water to produce hydrogen based on platinum charcoal as the anode material, and the efficiency of electrolytic reduction reached 80%.

Key words: Electrolysis of water for hydrogen production, Anion exchange membrane, 18?Crown?6 ether, Polyvinyl alcohol, Conductivity

摘要：

传统阴离子交换膜（AEMs）中常用的季铵基（QA）与OH^-解离常数较低，导致其电导率较差。冠醚基团因其能与碱金属阳离子形成带正电荷的络合物，可显著提升AEMs的离子交换容量（IEC）和OH?传导效率。同时，冠醚环中的醚键具有良好的碱稳定性和化学稳定性。鉴于以上优点，通过变色酸接枝二苯并?18?冠?6?醚改性聚乙烯醇（PVA），成功制备了一系列接枝双冠醚的AEMs。结果表明，与单冠醚膜材料相比，双冠醚阴离子交换膜展现了更高的OH^-选择性和化学稳定性；所制备的AEMs在电导率（80 ℃温度下电导率为165.5 mS/cm）、机械性能（室温下拉伸强度为47 MPa）和碱稳定性（在浓度为6 mol/L的KOH中浸泡168 h，电导率仅降低4.52%）方面表现出色，且以铂炭为阳极材料实现了高效的电解水制氢过程，电解还原效率达到80%。

关键词: 电解水制氢, 阴离子交换膜, 二苯并?18?冠?6?醚, 聚乙烯醇, 电导率

CLC Number:

TQ623.7

Ningda ZHANG, Lulu WANG, Yang ZHANG, Fan ZHANG, Jilin WANG. Preparation and Performance Analysis of Anion Exchange Membranes Modified with Chromotropic Acid Grafted 18⁃Crown⁃6 Ether on Polyvinyl Alcohol[J]. Journal of Liaoning Petrochemical University, 2025, 45(5): 9-17.

张宁达, 王璐璐, 张扬, 张帆, 王吉林. 变色酸接枝18⁃冠⁃6⁃醚改性聚乙烯醇阴离子交换膜的制备及性能分析[J]. 辽宁石油化工大学学报, 2025, 45(5): 9-17.

Figures/Tables 14

Fig.1 Synthesis route of D?C

Fig.2 Schematic Structure of D?C X ?P AEMs

Fig.3 1H NMR spectrum of D?C30%?P AEM

Fig.4 Structural sketch of the D?C30%?P AEM

Fig.5 Infrared spectra of D?C, PVA, and D?C30%?P AEMs

Fig.6 D?C30%?P AEM profile and SEM image of the surface of D?C X ?P AEMs

Fig.7 Thermogravimetric curves of D?C X ?P AEMs

Fig.8 Tensile strength and elongation at break of D?C X ?P AEMs

Fig.9 Ion exchange capacity and solubility of D?CX?P AEMs

Fig.10 Water content versus time curve of D?C X ?P AEMs

Fig.11 Conductivity variation curves of D?C X ?P AEMs

Fig.12 Arrhenius curves for D?C X ?P AEMs

Fig.13 Alkali stability versus time curve of D?C X ?P AEMs

Fig.14 Electrolyzed water to hydrogen performance chart

References 30

[1]	COSKUN AVCI A， TOKLU E. A new analysis of two phase flow on hydrogen production from water electrolysis［J］. International Journal of Hydrogen Energy， 2022， 47（11）： 6986⁃6995.
[2]	DOS SANTOS K G， ECKERT C T， DE ROSSI E， et al. Hydrogen production in the electrolysis of water in Brazil， a review［J］. Renewable and Sustainable Energy Reviews， 2017， 68（Part 1）： 563⁃571.
[3]	CHI J， YU H M. Water electrolysis based on renewable energy for hydrogen production［J］. Chinese Journal of Catalysis， 2018， 39（3）： 390⁃394.
[4]	URSUA A， GANDIA L M， SANCHIS P. Hydrogen production from water electrolysis： Current status and future trends［J］. Proceedings of the IEEE， 2012， 100（2）： 410⁃426.
[5]	TERLOUW T， BAUER C， MCKENNA R， et al. Large⁃scale hydrogen production via water electrolysis： A techno⁃economic and environmental assessment［J］. Energy & Environmental Science， 2022， 15（9）： 3583⁃3602.
[6]	卢静，王璐璐，高慧，等. 燃料电池用半互穿网络阴离子交换膜的制备及表征［J］. 辽宁石油化工大学学报， 2024， 44（6）： 51⁃58.
	LU J， WANG L L， GAO H， et al. Preparation and characterization of semi⁃interpenetrating network anion exchange membranes for fuel cells［J］. Journal of Liaoning Petrochemical University， 2024， 44（6）： 51⁃58.
[7]	JANG D， KIM J， KIM D， et al. Techno⁃economic analysis and Monte Carlo simulation of green hydrogen production technology through various water electrolysis technologies［J］. Energy Conversion and Management， 2022， 258： 115499.
[8]	TANG W S， ZHANG L N， QIU T Y， et al. Efficient conversion of biomass to formic acid coupled with low energy consumption hydrogen production from water electrolysis［J］. Angewandte Chemie International Edition， 2023， 62（30）： e202305843.
[9]	TONELLI D， ROSA L， GABRIELLI P， et al. Global land and water limits to electrolytic hydrogen production using wind and solar resources［J］. Nature Communications， 2023， 14（1）： 5532.
[10]	VINCENT I， BESSARABOV D. Low cost hydrogen production by anion exchange membrane electrolysis： A review［J］. Renewable and Sustainable Energy Reviews， 2018， 81（Part 2）： 1690⁃1704.
[11]	SHANG C S， WANG Z， WANG L L， et al. Preparation and characterization of a polyvinyl alcohol grafted bis⁃crown ether anion exchange membrane with high conductivity and strong alkali stability［J］. International Journal of Hydrogen Energy， 2020， 45（33）： 16738⁃16750.
[12]	ZHANG F， ZHANG Y， SUN L X， et al. A π⁃conjugated anion⁃exchange membrane with an ordered ion⁃conducting channel via the McMurray coupling reaction［J］. Angewandte Chemie International Edition， 2023， 62（4）： e202215017.
[13]	ZHANG Y， CHEN W T， YAN X M， et al. Ether spaced N⁃spirocyclic quaternary ammonium functionalized crosslinked polysulfone for high alkaline stable anion exchange membranes［J］. Journal of Membrane Science， 2020， 598： 117650.
[14]	LI Y P， LIU X M， ZHANG Y H， et al. A fluorescent and colorimetric sensor for Al³⁺ based on a dibenzo⁃18⁃crown⁃6 derivative［J］. Inorganic Chemistry Communications， 2013， 33： 6⁃9.
[15]	JACKSON D T， NELSON P N， BOOYSEN I N. Lead ion selective electrodes from dibenzo⁃18⁃crown⁃6 derivatives： An exploratory study［J］. Journal of Molecular Structure， 2021， 1227： 129575.
[16]	PIKE J D， ROSA D T， COUCOUVANIS D. Lipophilic metal⁃salicylideneimine⁃crown ether hybrids⁃ditopic carriers in the facilitated transport of amphiphilic molecules across bulk liquid membranes［J］. European Journal of Inorganic Chemistry， 2001， 2001（3）： 761⁃777.
[17]	PREIHS C， MAGDA D， SESSLER J L. Crown ether functionalized texaphyrin monomers and dimers［J］. Journal of Porphyrins and Phthalocyanines， 2011， 15（7⁃8）： 539⁃546.
[18]	LANCET D， PECHT I. Spectroscopic and immunochemical studies with nitrobenzoxadiazolealanine， a fluorescent dinitrophenyl analog［J］. Biochemistry， 1977， 16（23）： 5150⁃5157.
[19]	徐亚宁，闫佳宁，王璐璐，等. 聚乙二醇改性冠醚功能化聚砜阴离子交换膜的制备及表征［J］. 石油化工高等学校学报， 2024， 37（1）： 59⁃65.
	XU Y N， YAN J N， WANG L L， et al. Preparation and characterization of a functional polysulfone anion exchange membrane of polyethylene glycol modified crown ether［J］. Journal of Petrochemical Universities， 2024， 37（1）： 59⁃65.
[20]	FERREIRA P， PHILLIPS E， RIPPON D， et al. Poly（ethylene glycol）⁃supported nitroxyls： Branched catalysts for the selective oxidation of alcohols［J］. The Journal of Organic Chemistry， 2004， 69（20）： 6851⁃6859.
[21]	ZHUANG J P， ZHOU W D， LI X F， et al. Multiple hydrogen⁃bond⁃induced supramolecular nanostructure from a pincer⁃like molecule and a［60］fullerene derivative［J］. Tetrahedron， 2005， 61（36）： 8686⁃8693.
[22]	刘彬，鄂永胜，王强. 杂多酸法双酚AP的合成及应用［J］. 当代化工， 2024， 53（12）： 2953⁃2956.
	LIU B， E Y S， WANG Q. Synthesis and application of 4，4'⁃（1⁃phenylethylidene）bisphenol by heteropolyacid method［J］. Contemporary Chemical Industry， 2024， 53（12）： 2953⁃2956.
[23]	WANG J L， HE R H， CHE Q T. Anion exchange membranes based on semi⁃interpenetrating polymer network of quaternized chitosan and polystyrene［J］. Journal of Colloid and Interface Science， 2011， 361（1）： 219⁃225.
[24]	WANG D， WANG Y F， WANG J L， et al. Synthesized geminal⁃imidazolium⁃type Ionic liquids applying for PVA⁃FP/［DimL］［OH］ anion exchange membranes for fuel cells［J］. Polymer， 2019， 170： 31⁃42.
[25]	DU X M， ZHANG H Y， YUAN Y J， et al. Semi⁃interpenetrating network anion exchange membranes based on quaternized polyvinyl alcohol/poly（diallyldimethylammonium chloride）［J］. Green Energy & Environment， 2021， 6（5）： 743⁃750.
[26]	YANG Q， LI L， GAO X L， et al. Crown ether bridged anion exchange membranes with robust alkaline durability［J］. Journal of Membrane Science， 2019， 578： 230⁃238.
[27]	SHANG C S， LIU Y X， ZENG X R， et al. Preparation and characterization of organic⁃inorganic hybrid anion exchange membrane based on crown ether functionalized mesoporous SBA⁃NH₂［J］. International Journal of Hydrogen Energy， 2022， 47（30）： 14141⁃14157.
[28]	ADABI H， SHAKOURI A， UL HASSAN N， et al. High⁃performing commercial Fe⁃N⁃C cathode electrocatalyst for anion⁃exchange membrane fuel cells［J］. Nature Energy， 2021， 6（8）： 834⁃843.
[29]	YANG Y， PELTIER C R， ZENG R， et al. Electrocatalysis in alkaline media and alkaline membrane⁃based energy technologies［J］. Chemical Reviews， 2022， 122（6）： 6117⁃6321.
[30]	徐广通，王亚敏，李霄霞. 质子交换膜燃料电池用氢气杂质检测技术进展［J］. 石油炼制与化工， 2025， 56（1）： 1⁃10.
	XU G T， WANG Y M， LI X X. Development and application of impurity detection technologies of hydrogen for proton exchange membrane fuel cells［J］. Petroleum Processing and Petrochemicals， 2025， 56（1）： 1⁃10.