交联氧化石墨烯膜的制备及离子分离性能
作者： 崔燕峰1,2*， 王盟珍1,3， 马兰英1,2， 刘雪菁1,3， 朱东海1,3*， 冯海涛1,2
单位： 1. 中国科学院青海盐湖研究所，盐湖资源绿色高值利用重点实验室， 西宁 810008；
 2.  青海省盐湖资源综合利用工程技术中心， 西宁 810008；  3. 青海大学 化工学院， 西宁 810016
关键词： 氧化石墨烯膜； 壳聚糖交联； 层间距调控； 离子分离
DOI号： 10.16159/j.cnki.issn1007-8924.2026.03.015
分类号： TQ028
出版年,卷(期):页码： 2026, 46(3):149-161

摘要：

氧化石墨烯（GO）膜的层间距狭窄且固定，难以实现相近尺寸离子的精确分离。本研究采用真空抽滤法依次在GO层间引入壳聚糖（CS），随后通过溶液浸泡法引入金属离子Zn2+，构筑得到一种层间距可调且性能稳定的GO/CS/Zn复合膜，并将其应用于盐湖中一/二价、一/一价金属阳离子的选择性分离。结果表明，在四元混合溶液体系中，GO/CS/Zn复合膜对K+的离子通量为0.25 mol/(m2·h)，K+/Mg2+分离系数达到50.84，Na+/Mg2+、Li+/Mg2+及K+/Li+分离系数分别为25.32、9.97和5.10，较原始GO膜分别提高约11.9倍、8.5倍、5.5倍和2.2倍。此外，GO/CS/Zn复合膜在连续运行15个循环后，仍能保持良好的结构完整性，预示其在一/二价金属离子高选择性分离方面具有良好的应用潜力。

The interlayer spacing of graphene oxide (GO) membranes is intrinsically narrow and fixed, making it difficult to achieve precise separation of ions with similar sizes. In this study, chitosan (CS) and Zn2+ were sequentially introduced into the GO interlayer via vacuum-assisted filtration, a GO/CS/Zn composite film with adjustable interlayer spacing and enhanced structural stability was successfully constructed. In the quaternary mixed solution system, the GO/CS/Zn membrane exhibited a high K+ flux of 0.25 mol/(m2·h) and an outstanding K+/Mg2+ separation factor of 50.84, and the separation factors for Na+/Mg2+, Li+/Mg2+, and K+/Li+ reached 25.32, 9.97, and 5.10, respectively, which were about 11.9-, 8.5-, 5.5-, and 2.2-fold improvements compared with those of the pristine GO membrane. In addition, the GO/CS/Zn composite membrane maintained good structural integrity after 15 consecutive cycles, indicating its promising application potential in high selectivity separation of mono-/di-valent metal ions.

基金项目：

青海省科技厅基础研究计划——应用基础研究（2024-ZJ-732）

作者简介：
第一作者简介： 崔燕峰（1983-），女，河南鲁山人，副研究员，博士，主要研究方向为膜分离技术，盐湖单价离子分离膜材料构筑及应用.  通讯作者，崔燕峰，E-mail：cyf111@isl.ac.cn；朱东海，E-mail：zhudonghai-2001@163.com

参考文献：

［1］郑卓凡, 王保国. 低价离子分离膜及其在提锂领域的应用 ［J］. 膜科学与技术, 2025, 45(5): 191-206.
［2］陈大志, 余亮, 周俊文, 等. 膜分离技术在半导体废水处理领域的应用研究进展 ［J］. 膜科学与技术, 2024, 44（5）: 178-186.
［3］Xu S S, Song J F, Bi Q Y, et al. Extraction of lithium from Chinese salt-lake brines by membranes: Design and practice ［J］. J Membr Sci, 2021, 635: 119441.
［4］李泾贤, 郝嘉劲, 王磊, 等. 氧化石墨烯纳滤膜插层改性研究进展 ［J］. 膜科学与技术, 2025, 45（1）: 156-171.
［5］张桢琳, 王露, 程亮, 等. 表面接枝法荷正电复合纳滤膜制备及其镁锂分离性能 ［J］. 膜科学与技术, 2024, 44（2）: 1-7.
［6］Janjhi F A, Chandio I, Memon A A, et al. Functionalized graphene oxide based membranes for ultrafast molecular separation ［J］. Sep Purif Technol, 2021, 274: 117969.
［7］李剑锋, 王煜, 许召赞, 等. 高稳定性氧化石墨烯净水分离膜的制备和应用进展 ［J］. 净水技术, 2021, 40: 26-31.
［8］汪林, 纪树兰, 王乃鑫, 等. 用于有机溶剂体系分离的氧化石墨烯基复合膜的构筑 ［J］. 膜科学与技术, 2020, 40（1）: 352-359.
［9］Tiwary S K, Singh M, Chavan S V, et al. Graphene oxide-based membranes for water desalination and purification ［J］. NPJ 2D Mater Appl, 2024, 8(1): 27.
［10］刘璇, 李明阳, 余翔, 等. MoS2/RGO复合分离膜的制备及其水处理性能 ［J］. 膜科学与技术, 2023, 43（4）: 145-153.
［11］Jia Z Q, Shi W X. Tailoring permeation channels of graphene oxide membranes for precise ion separation ［J］. Carbon, 2016, 101: 290-295.
［12］Li P S, Jiang L, Liu L F, et al. Chelation-based metal cation stabilization of graphene oxide membranes towards efficient sieving of mono/divalent ions ［J］. J Membr Sci, 2022, 655: 120604.
［13］Zhang W, Huang Q B, Liu S, et al. Graphene oxide membrane regulated by surface charges and interlayer channels for selective transport of monovalent ions over divalent ions ［J］. Sep Purif Technol, 2022, 291: 120938.
［14］Qian Y J, Shang J, Liu D, et al. Enhanced ion sieving of graphene oxide membranes via surface amine functionalization ［J］. J Am Chem Soc, 2021, 143(13): 5080-5090.
［15］Dai L H, Pang S C, Li S Y, et al. Freestanding two-dimensional nanofluidic membranes modulated by zwitterionic polyelectrolyte for mono-/di-valent ions selectivity transport ［J］. J Membr Sci, 2023, 677: 121621.
［16］Zhang M C, Zhao P X, Li P S, et al. Designing biomimic two-dimensional ionic transport channels for efficient ion sieving ［J］. ACS Nano, 2021, 15(3) : 5209-5220.
［17］Lyu  X B, Xie R, Ji J Y, et al. Enhancing stability and ionic sieving efficiencies of GO membranes via copper ion crosslinking and tannic acid intercalation ［J］. Sep Purif Technol, 2024, 336: 126232.
［18］Jabbar A A, Hussain D H, Latif K H, et al. High-efficiency adsorption of uranium from wastewater using graphene oxide/graphene oxide nanoribbons/chitosan nanocomposite aerogels ［J］. ACS Omega, 2024, 9(25): 27260-27268.
［19］Hummers Jr W S, Offeman R E. Preparation of graphitic oxide ［J］. J Am Chem Soc, 1958, 80(6): 1339.
［20］Manzoor Q, Farrukh M A, Qamar M T, et al. Efficient adsorption and photocatalytic removal of hexavalent chromium using chitosan-functionalized graphene oxide-MnO2 nanocomposite ［J］. Int J Biol Macromol, 2025, 331: 144009.
［21］Tang X Y, Wang S Y, Zhang Z H, et al. Graphene oxide/chitosan/potassium copper hexacyanoferrate(Ⅱ) composite aerogel for efficient removal of cesium ［J］. Chem Eng J, 2022, 444: 136397.
［22］Xu S K, Wang Y J, We M R, et al. Removal of Cr (Ⅵ) by crosslinked chitosan adsorbent prepared using simulated copper-containing wastewater ［J］. Int J Biol Macromol, 2024, 282(6) : 137301.
［23］Loncarevic A, Malbasa Z, Kovacic M, et al. Copper-zinc/chitosan complex hydrogels: Rheological, degradation and biological properties ［J］. Int J Biol Macromol, 2023, 251: 126373.
［24］Liu L, Li C, Bao C L, et al. Preparation and characterization of chitosan/graphene oxide composites for the adsorption of Au(Ⅲ) and Pd(Ⅱ) ［J］. Talanta, 2012, 93: 350-357.
［25］El Rouby W M A, Farghali A A, Sadek M A, et al. Fast removal of Sr(Ⅱ) from water by graphene oxide and chitosan modified graphene oxide ［J］. J Inorg Organomet Polym Mater, 2018, 28(6) : 2336-2349.
［26］Miao P P, Gao J, Han X B, et al. Adsorption of levofloxacin onto graphene oxide/chitosan composite aerogel microspheres ［J］. Gels, 2024, 10(1) : 81.
［27］He Y H, Liu Y J, Guo F, et al. Dynamic dispersion stability of graphene oxide with metal ions ［J］. Chin Chem Lett, 2020, 31(6) : 1625-1629.
［28］Huang Q, Li G H, Chen M J, et al. Graphene oxide functionalized O-(carboxymethyl)-chitosan membranes: Fabrication using dialysis and applications in water purification ［J］. Colloids Surf A, 2018, 554: 27-33.
［29］Zeng M, Wu Y, Liu Y, et al. Nacre-inspired graphene oxide/chitosan supported Pd species composite paper-like membrane with superior catalytic performance ［J］. Int J Biol Macromol, 2025, 306(2): 141512.
［30］Guo T, Bulin C, Li C N, et al. Experimental and statistical physics illumination of Pb(Ⅱ) adsorption on magnetic chitosan-graphene oxide surface ［J］. Sep Purif Technol, 2025, 354: 128867.
［31］Li X Y, Ma L Y, Zhou Y N, et al. Graphene oxide membrane with recognition sites for efficient separation of mono-/di-valent metal ions ［J］. Desalination, 2025, 604: 118617.
［32］Lyu X B, Xie R, Ji J Y, et al. A novel strategy to fabricate cation-cross-linked graphene oxide membrane with high aqueous stability and high separation performance ［J］. ACS Appl Mater Interfaces, 2020, 12(50) : 56269-56280.
［33］Huang Q B, Liu S, Guo Y N, et al. Separation of mono-/di-valent ions via charged interlayer channels of graphene oxide membranes ［J］. J Membr Sci, 2022, 645: 120212.
［34］Guan K C, Liu Q, Zhou G Y, et al. Cation-diffusion controlled formation of thin graphene oxide composite membranes for efficient ethanol dehydration ［J］. Sci China Mater, 2019, 62(7) : 925-935.

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