<strong>PPy-GO</strong>共沉积改性阴离子交换膜的制备和性能

doi:10.11901/1005.3093.2025.099

材料研究学报

2026, Vol. 40

Issue (3): 225-233 DOI: 10.11901/1005.3093.2025.099

研究论文

本期目录 | 过刊浏览

PPy-GO共沉积改性阴离子交换膜的制备和性能

刘俏君¹^,², 周键¹^,²(

), 张航飞¹^,², 黄魁¹

^1.兰州交通大学环境与市政工程学院兰州 730070
^2.寒旱地区水资源综合利用教育部工程研究中心兰州 730070

Modification of Anion Exchange Membrane via Co-deposition of Polypyrrole and Graphene Oxide

LIU Qiaojun¹^,², ZHOU Jian¹^,²(

), ZHANG Hangfei¹^,², HUANG Kui¹

^1.College of Environmental and Municipal Engineering, Lanzhou Jiaotong University, Lanzhou 730070, China
^2.Ministry of Education Engineering Research Center of Water Resource Comprehensive Utilization in Cold and Arid Regions, Lanzhou 730070, China

引用本文:

刘俏君, 周键, 张航飞, 黄魁. PPy-GO共沉积改性阴离子交换膜的制备和性能[J]. 材料研究学报, 2026, 40(3): 225-233.
Qiaojun LIU, Jian ZHOU, Hangfei ZHANG, Kui HUANG. Modification of Anion Exchange Membrane via Co-deposition of Polypyrrole and Graphene Oxide[J]. Chinese Journal of Materials Research, 2026, 40(3): 225-233.

全文: PDF(6264 KB) HTML

摘要:

用聚吡咯(Polypyrrole, PPy)和氧化石墨烯(Graphene oxide, GO)对异质阴离子交换膜(Anion exchange membrane, AEM)进行共沉积表面改性，使用GO进行“碳催化”制备了PPy-GO复合层透过性膜。使用扫描电子显微镜(SEM)、电子衍射X射线光谱(EDX)、红外光谱(FTIR)、X射线光电子能谱(XPS)等手段表征了改性膜的表面形貌和理化性质。结果表明，随着GO浓度的提高改性膜的含水率、离子交换容量均有所提高，接触角明显减小；适当的提高NaCl溶液的浓度有利于提高改性效果；1~5 mA/cm²的电流密度有利于制备出性能优异的改性膜。在电流密度为5 mA/cm²、PPy∶GO = 2∶1、NaCl的浓度为0.3 mol/L和沉积时间为20 min的条件下制备的PPy-GO-M膜，其离子交换容量比原膜提高0.85 mmol/g，接触角下降42.7°，膜电阻下降3.58 Ω，选择透过性提高4.66%。

关键词 ：材料合成与加工工艺, 高选择透过性, 共沉积, 氧化石墨烯, 聚吡咯

Abstract：

A composite material (PPy-GO) film with high selectivity for permeability was prepared on an anion exchange membrane (AEM) via co-deposition method with polypyrrole (PPy) and graphene oxide (GO) as raw material, resulting in a new type of composite anion exchange membrane, while the "carbon catalysis" effect of GO also played a significant role during the process. The surface morphology and physicochemical properties of the membrane were characterized using scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy, so that to determine the optimal conditions for the co-deposition of PPy-GO on the membrane surface. The results show that with the increasing GO concentration, the water content and ion exchange capacity of the modified membrane increased, while the contact angle significantly decreased. An appropriate increase in the NaCl solution concentration was found to be beneficial for improving the modification effect. The current density in the range of 1-5 mA/cm² had a positive impact on the performance of the modified membrane. Under optimized deposition conditions (current density of 5 mA/cm², PPy:GO ratio of 2:1, 0.3 mol/L NaCl, deposition time of 20 min), compared to the unmodified membrane, the PPy-GO modified membrane exhibited an increase in ion exchange capacity by 0.85 mmol/g, a decrease in contact angle by 42.7°, a reduction in membrane resistance by 3.58 Ω, and a 4.66% increase in selectivity for permeability.

Key words： synthesizing and processing technics for materials highly selective permeability co-deposition graphene oxide polypyrrole

收稿日期: 2025-03-07

ZTFLH:

TQ317

基金资助:国家自然科学基金(52364055);甘肃省教育厅：高校科研创新平台重大培育项目(2024-CXPT-14);甘肃省高校产业支撑计划(2024CYZC-26)

通讯作者: 周键，教授，zhoujian@mail.lzjtu.cn，研究方向为水处理功能材料制备

Corresponding author: ZHOU Jian, Tel: 13609344897, E-mail: zhoujian@mail.lzjtu.cn

作者简介: 刘俏君，女，1998年生，硕士

	服务

	把本文推荐给朋友
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	刘俏君
	周键
	张航飞
	黄魁
44.8K

链接本文:

https://www.cjmr.org/CN/10.11901/1005.3093.2025.099 或 https://www.cjmr.org/CN/Y2026/V40/I3/225

图1 迁移数测试装置示意图

图2 四电极体系电化学阻抗测试系统

图3 PPy-GO配比对改性膜表面性质的影响

图4 氯化钠浓度对改性膜表面性质的影响

图5 电流密度对改性膜表面性质的影响

表1 原膜和改性膜的基础性能

图6 原膜和改性膜表面、断面的SEM照片、碳和氮元素EDX

表2 原膜和改性膜表面元素的含量

图7 原膜和改性膜的红外光谱、改性膜的Raman光谱、原膜C 1s光谱和改性膜的C 1s光谱

图8 共沉积反应机理示意图

[1]	Campione A, Cipollina A, Bogle I D L, et al. A hierarchical model for novel schemes of electrodialysis desalination [J]. Desalination, 2019, 465: 79 doi: 10.1016/j.desal.2019.04.020
[2]	Zhou J, Wang S F, Song X S. Electrodeposition of cobalt in double-membrane three-compartment electrolytic reactor [J]. Trans. Nonferrous Met. Soc. China, 2016, 26(6): 1706 doi: 10.1016/S1003-6326(16)64279-6
[3]	Zhou J, Xia M Y, Zhang H F, et al. Preparation of dopamine and polyethyleneimine co-deposition modified cation exchange membrane [J]. Chin. J. Mater. Res., 2024, 38(8): 585 doi: 10.11901/1005.3093.2024.033
[3]	周键, 夏蒙玥, 张航飞等. DA-PEI共沉积表面改性阳离子交换膜的制备 [J]. 材料研究学报, 2024, 38(8): 585
[4]	Luo T, Abdu S, Wessling M. Selectivity of ion exchange membranes: a review [J]. J. Membr. Sci., 2018, 555: 429 doi: 10.1016/j.memsci.2018.03.051
[5]	Kononenko N, Nikonenko V, Grande D, et al. Porous structure of ion exchange membranes investigated by various techniques [J]. Adv. Colloid Interface Sci., 2017, 246: 196 doi: 10.1016/j.cis.2017.05.007
[6]	Li Y J, Hu X M, Tian J N, et al. Mussel-inspired co-deposition of catechol-amine and graphene oxide (GO) modified anion exchange membranes (AEMs) for antifouling [J]. Mater. Lett., 2025, 378: 137554 doi: 10.1016/j.matlet.2024.137554
[7]	Qiu M, Zhang B, Wu H, et al. Preparation of anion exchange membrane with enhanced conductivity and alkaline stability by incorporating ionic liquid modified carbon nanotubes [J]. J. Membr. Sci., 2019, 573: 1 doi: 10.1016/j.memsci.2018.11.070
[8]	Zhou Y, Hu C Z, Liu H J, et al. Potassium-ion recovery with a polypyrrole membrane electrode in novel redox transistor electrodialysis [J]. Environ. Sci. Technol., 2020, 54: 4592 doi: 10.1021/acs.est.9b06665
[9]	Ehrenbeck C, Jüttner K. Ion conductivity and permselectivity measurements of polypyrrole membranes at variable states of oxidation [J]. Electrochim. Acta, 1996, 41(11-12): 1815 doi: 10.1016/0013-4686(95)00500-5
[10]	Xing S X. Chapter 10-Nanomaterials of conducting polymers and its application in energy conversion and storage [A]. RanF, ChenS W. Advanced Nanomaterials for Electrochemical-Based Energy Conversion and Storage [M]. Amsterdam: Elsevier, 2020: 325
[11]	Wang W L, Lv Y P, Liu H J, et al. Recent advances in application of polypyrrole nanomaterial in water pollution control [J]. Sep. Purif. Technol., 2024, 330: 125265 doi: 10.1016/j.seppur.2023.125265
[12]	Kumar M, Khan M A, Alothman Z A, et al. Polyaniline modified organic-inorganic hybrid cation-exchange membranes for the separation of monovalent and multivalent ions [J]. Desalination, 2013, 325: 95 doi: 10.1016/j.desal.2013.06.022
[13]	Salmeron-Sanchez I, Asenjo-Pascual J, Avilés-Moreno J R, et al. Chemical physics insight of PPy-based modified ion exchange membranes: a fundamental approach [J]. J. Membr. Sci., 2022, 643: 120020 doi: 10.1016/j.memsci.2021.120020
[14]	Sun M M, Mu C L, Wang S, et al. Monovalent cation exchange membranes prepared by Fe³⁺-assisted coupled surface modification of PEI-PPy for potassium extraction from simulated brine [J]. Desalination, 2024, 586: 117835 doi: 10.1016/j.desal.2024.117835
[15]	Paseta L, Luque-Alled J M, Malankowska M, et al. Functionalized graphene-based polyamide thin film nanocomposite membranes for organic solvent nanofiltration [J]. Sep. Purif. Technol., 2020, 247: 116995 doi: 10.1016/j.seppur.2020.116995
[16]	Moayeri A, Ajji A. Fabrication of polyaniline/poly(ethylene oxide)/non-covalently functionalized graphene nanofibers via electrospinning [J]. Synth. Met., 2015, 200: 7 doi: 10.1016/j.synthmet.2014.12.020
[17]	Tang L, Yang Z K, Duan F, et al. Fabrication of graphene sheets/polyaniline nanofibers composite for enhanced supercapacitor properties [J]. Colloids Surf., 2017, 520A: 184
[18]	Zhao W Q, Cui M H, Zhou Y S, et al. Enhancing electrochemical performance of graphene oxide/polyaniline composite through plasma-assisted chemical cross-linking and surface modification [J]. J. Energy Storage, 2024, 99: 113471 doi: 10.1016/j.est.2024.113471
[19]	Varain L, Larisegger S, Nelhiebel M, et al. Simultaneous measurement and ODE-modeling of ion- and water permeability through ion exchange membranes [J]. J. Membr. Sci., 2023, 684: 121847 doi: 10.1016/j.memsci.2023.121847
[20]	Pandey J, Mir F Q, Shukla A. Synthesis of silica immobilized phosphotungstic acid (Si-PWA)-poly(vinyl alcohol) (PVA) composite ion-exchange membrane for direct methanol fuel cell [J]. Int. J. Hydrog. Energy, 2014, 39(17): 9473 doi: 10.1016/j.ijhydene.2014.03.237
[21]	Shahi V K, Thampy S K, Rangarajan R. Studies on transport properties of surfactant immobilized anion-exchange membrane [J]. J. Membr. Sci., 1999, 158(1-2): 77 doi: 10.1016/S0376-7388(99)00029-0
[22]	Chen X J, Kong Q Q, Wu X Q, et al. V₂O₃@C optimized by carbon regulation strategy for ultra long-life aqueous zinc-ion batteries [J]. Chem. Eng. J., 2023, 451: 138765 doi: 10.1016/j.cej.2022.138765
[23]	Cao R Q, Shi S Y, Cao H B, et al. Surface composite modification of anion exchange membrane by electrodeposition and self-polymerization for improved antifouling performance [J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 648:129402 doi: 10.1016/j.colsurfa.2022.129402
[24]	Li Y J, Shi S Y, Cao H B, et al. Modification and properties characterization of heterogeneous anion-exchange membranes by electrodeposition of graphene oxide (GO) [J]. Applied Surface Science, 2018, 442: 700 doi: 10.1016/j.apsusc.2018.02.166
[25]	Wu L, Liu L, Gao B, et al. Aggregation kinetics of graphene oxides in aqueous solutions: experiments, mechanisms, and modeling [J]. Langmuir, 2013, 29(49): 15174 doi: 10.1021/la404134x pmid: 24261814
[26]	Jiang Y, Raliya R, Fortner J D, et al. Graphene oxides in water: correlating morphology and surface chemistry with aggregation behavior [J]. Environ. Sci. Technol., 2016, 50(13): 6964 doi: 10.1021/acs.est.6b00810
[27]	Arunkumar I, Kim A R, Lee S H, et al. Enhanced fumion nanocomposite membranes embedded with graphene oxide as a promising anion exchange membrane for fuel cell application [J]. Int. J. Hydrog. Energy, 2024, 52: 139 doi: 10.1016/j.ijhydene.2022.10.184
[28]	Kumar P, Suhag S, Mandal J R, et al. Surface modification of inter-polymer cation exchange membrane by controlled loading of polyaniline/metal particles for improved electrodialytic performance during mono-/bi-valent ions separation [J]. J. Membr. Sci., 2024, 711: 123168 doi: 10.1016/j.memsci.2024.123168
[29]	Jiang L, Syed J A, Zhang G L, et al. Enhanced anticorrosion performance of PPY-graphene oxide/PPY-camphorsulfonic acid composite coating for 304SS bipolar plates in proton exchange membrane fuel cell [J]. J. Ind. Eng. Chem., 2019, 80: 497 doi: 10.1016/j.jiec.2019.08.032
[30]	Zhu C Z, Zhai J F, Wen D, et al. Graphene oxide/polypyrrole nanocomposites: one-step electrochemical doping, coating and synergistic effect for energy storage [J]. J. Mater. Chem., 2012, 22(13): 6300 doi: 10.1039/c2jm16699b
[31]	Qi K, Qiu Y B, Guo X P. Pulse electrochemical incorporation of graphene oxide into polypyrrole films for supercapacitor electrode materials [J]. Electrochim. Acta, 2014, 137: 685 doi: 10.1016/j.electacta.2014.06.083
[32]	Zhao J L, Li J, Chen Q B, et al. Fabrication of PVDF cation exchange membrane for electrodialysis: influence and mechanism of crystallinity and leakage of co-ions [J]. J. Membr. Sci., 2024, 695: 122389 doi: 10.1016/j.memsci.2023.122389
[33]	Kumar P, Suhag S, Mandal J R, et al. Polyaniline encapsulated sulphonated graphene oxide based cation exchange membrane for electrodialytic separation of mono- and bi-valent ions [J]. Sep. Purif. Technol., 2023, 326: 124752 doi: 10.1016/j.seppur.2023.124752
[34]	Venancio E C, Wang P C, MacDiarmid A G. The azanes: a class of material incorporating Nano/micro self-assembled hollow spheres obtained by aqueous oxidative polymerization of aniline [J]. Synth. Met., 2006, 156(5-6): 357 doi: 10.1016/j.synthmet.2005.08.035
[35]	Garfias-García E, Romero-Romo M, Ramírez-Silva M T, et al. Mechanism and kinetics of the electrochemical formation of polypyrrole under forced convection conditions [J]. J. Electroanal. Chem., 2008, 613(1): 67 doi: 10.1016/j.jelechem.2007.10.013
[36]	Rosseinsky D R, Morse N J, Slade R C T, et al. Mechanisms of the chemical and electrochemical polymerizations of pyrrole compared by product spectrometry and conductivity loss effected by pyridine inhibition or by over-oxidation [J]. Electrochim. Acta, 1991, 36(3-4): 733 doi: 10.1016/0013-4686(91)85164-3
[37]	Ghosh S, Bowmaker G A, Cooney R P, et al. Infrared and Raman spectroscopic studies of the electrochemical oxidative degradation of polypyrrole [J]. Synth. Met., 1998, 95(1): 63 doi: 10.1016/S0379-6779(98)00034-4

[1]	代宇航, 王月苗, 白英伯, 张瑞, 张伟红, 周子荐, 陶稀鹏, 崔传勇. GH4151高强镍基高温合金的热压缩变形[J]. 材料研究学报, 2026, 40(3): 169-178.
[2]	杨言言, 刘堰, 杨颂, 汪紫彤, 朱峰, 余钟亮, 郝晓刚. 石墨烯掺杂的聚吡咯/钴镍双氢氧化物电控分离低浓度磷酸盐的性能[J]. 材料研究学报, 2025, 39(6): 425-434.
[3]	段玉, 王倩, 刘宏臣, 车远军, 石磊, 白慧娟. 油页岩灰基磁性分子筛的制备及其对亚甲基蓝的吸附性能[J]. 材料研究学报, 2025, 39(6): 463-473.
[4]	李颖, 聂学童, 钱立国, 朱忆仁. Co₃O₄/ZnO@MG-C₃N_x 催化剂的合成及其可见光降解亚甲基蓝的性能[J]. 材料研究学报, 2025, 39(4): 241-250.
[5]	彭怡和, 欧宝立, 彭勇洁, 温乜一, 程天宇, 陈迪名. CeO₂-GO/EP防腐复合涂层的制备和性能[J]. 材料研究学报, 2025, 39(4): 259-271.
[6]	周键, 夏蒙玥, 张航飞, 刘俏君. DA-PEI共沉积表面改性阳离子交换膜的制备[J]. 材料研究学报, 2024, 38(8): 585-592.
[7]	赵勇, 刘腾远, 贾春妮, 杨朕聃, 陈响军, 王培, 李殿中. 冷拉拔钢丝横截面应变不均匀性的晶体塑性研究[J]. 材料研究学报, 2024, 38(2): 81-91.
[8]	李福禄, 韩春淼, 高嘉望, 蒋健, 许卉, 李冰. 氧化石墨烯的变温发光[J]. 材料研究学报, 2022, 36(8): 597-601.
[9]	闫福照, 李静, 熊良银, 刘实. FeCr-ODS铁素体合金的氧化+粉锻工艺制备及其微观结构[J]. 材料研究学报, 2022, 36(6): 461-470.
[10]	周海涛, 侯湘武, 汪彦博, 肖旅, 袁勇, 孙京丽. 高Nb-TiAl合金的高温变形行为及其板材的性能[J]. 材料研究学报, 2022, 36(6): 471-480.
[11]	黄欢, 张迅韬, 杨尚科, 肖刘鑫, 张兆鑫, 严磊, 蔺海兰, 卞军, 陈代强. 氧化石墨烯/苯甲酸钠复合成核剂协同改性PA6纳米复合材料的性能[J]. 材料研究学报, 2022, 36(6): 416-424.
[12]	曾强, 王荣超, 刘绮, 彭化南, 陈平. 磁功能化石墨烯改性环氧树脂及其复合材料的性能[J]. 材料研究学报, 2022, 36(12): 881-886.
[13]	阙爱珍, 朱桃玉, 郑玉婴. 中空磁性氧化石墨烯的制备及其对亚甲基蓝吸附性能[J]. 材料研究学报, 2021, 35(7): 517-525.
[14]	夏傲, 赵晨鹏, 曾啸雄, 韩曰鹏, 谈国强. B掺杂MnO₂的制备及其电化学性能[J]. 材料研究学报, 2021, 35(1): 36-44.
[15]	王永鹏, 贾治豪, 刘梦竹. 二维CdO纳米棒的制备及其用于葡萄糖传感器的可行性[J]. 材料研究学报, 2021, 35(1): 53-58.

Viewed

Full text

Abstract

Cited

Shared

Discussed