随着离子交换膜技术在工业生产的广泛应用，对于具有特殊性能的离子交换膜需求日益增加。单价选择性离子交换膜作为膜分离行业的新生力量，能实现电渗析过程中一、二价离子的高效分离。本文总结了国内外单价选择性阳离子交换膜的发展历史，探讨了单价阳离子交换膜的制备方法，重点比较了电沉积表面改性、光化学反应表面改性和浸渍法改性法优缺点。并进一步分析了单价选择性阳离子交换膜存在的限制因素和其广阔的应用前景。

 As ion exchange membranes are widely used in industrial production, membranes with special properties are in increasing demand. Monovalent cation selective membranes as a newly emerging technology play an important role in membrane separation industry. It will make a contribution to decrease the leakage of multivalent while applying in electrodialysis. This paper introduces the history of domestic and foreign monovalent cation selective membrane, explores the methods to prepare it. In addition, the advantages and disadvantages of electro-deposition modification, photochemical reaction modification and immersing modification are compared. Further analysis of the constraining factor of monovalent cation selective membrane and its broad application prospects are discussed.

[1] 曾青兰, 李晓宏. 离子交换膜的技术及其应用[J]. 高新技术, 2010, 4: 1-1.
[2] Ghalloussi R, Garcia-Vasquez W, Chaabane L, et al. Ageing of ion-exchange membranes in electrodialysis: A structural and physicochemical investigation[J]. Journal of Membrane Science, 2013, 436: 68-78.
[3] 王汉敏, 高学理, 胡圆, 等. 单价选择性均相阳离子交换膜的制备及性能[J]. 膜科学与技术, 2011, 31(5): 7-33.
[4]邹逸群, 侯克咏. 一价选择性透过膜的研究[J]. 水处理技术, 1983, 9(4): 13-18.
[5] Walton H F, Jordan D E, Samedy S R, et al. Cation exchange equilibria with divalent ions[J]. Journal of Physical Chemistry, 1961, 65(9): 1477-1484.
[6] Sata T. Izuo R. Modification of properties of ion exchange membrane[J]. Colloid and Polymer Science, 1978, 8(256): 757-769.
[7] Sata T, Mizutani Y. Modification of properties of ion exchange membranes, VI-electrodialytic transport properties of cation exchange membrane with a electrodeposition layer of cationic polyelectrolytes[J]. Journal of Polymer Science Part A Polymer Chemistry, 1979, 17: 1199-1213.
[8]Sata T, Izuo R, Takata K. Modification of the transport properties of ion exchange membranes. IX. Layer formation on a cation exchange membrane by acid–amide bonding and transport properties of the resulting membrane[J]. Journal of Membrane Science, 1989, 45: 197-199.
[9]Takata K, Sata T. Modification of transport properties of ion exchange membranes. XIV. Introduction of –SO2Cl groups with ClSO3H–H2SO4 mixture into membrane and formation of acid–amide bonding between polyethyleneimine and –SO2Cl groups[J]. Journal of Macromolecular Science-Pure and Applied Chemistry, 1996, 33: 789-790.
[10]Sata T, Yamaguchi T, Matsusaki K. Preparation and properties of composite membranes composed of anion-exchange membranes and polypyrrole[J]. The Journal of Chemical Physics, 1996, 100: 16633–16640.
[11]Gohil G S, Binsu V V, Shahi V K. Preparation and characterization of mono-valent ion selective polypyrrole composite ion-exchange membranes[J]. Journal of Membrane Science, 2006, 280: 210-218.
[12]Amara M, Kerdjoudj H. Modified membranes applied to metallic ion separation and mineral acid conceration by electrodialysis[J]. Seperation and Purification Technology, 2002, 29: 79-87.
[13]Chamoulaud G, Bélanger D. Modification of ion-exchange membrane used for separation of protons and metallic cations and characterization of the membrane by current–voltage curves[J]. Journal of Colloid and Interface Science, 2005,281: 179-181.
[14]仉琦, 于伯杉, 田秀敏, 等. 阳离子交换膜的表面处理及其对一价阳离子选择透过性的研究[J]. 膜科学与技术, 1981, 2(1): 6-14.
[15]Hu Y, Wang M, Wang D, Gao X L, Gao C J. Feasibility study on surface modification of cation exchange membranes by quaternized chitosan for improving its selectivity[J]. Journal of Membrane Science, 2008, 319: 5–9.
[16]Ge L, Wu L, Wu B, et al. Preparation of monovalent cation selective membranes through annealing treatment[J]. Journal of Membrane Science, 2014, 459: 217-222.
[17]陈大福, 仉琦. 离子交换膜的改性处理及特性研究[J]. 盐湖科技资料, 1978, Z1: 94-108.
[18]湛含辉, 罗娟. 聚偏氟乙烯膜亲水改性的研究进展[J]. 湖南大学学报, 2011, 25(3): 31-34.
[19]穆永信, 王三反, 吴楠. 阳离子交换膜改性的研究进展[J]. 水处理技术, 2013, 39(6): 5-12.
[20]Sata T, Yamaguchi T, Matsusaki K. Interaction between anion polyelectrolytes and anion exchange membrane and change in membrane peoperties[J]. Journal of Membrane Science, 1995, 100: 229-238.
[21]Gohil G S, Nagarale R K, Binsu V V, et al. Preparation and characterization of monovalent cation selective sulfonated poly(ether ether ketone) and poly(ether sulfone) composite membranes[J]. Journal of Colloid and Interface Science, 2006, 298: 845–853.
[22]Balster J, Krupenko O, Punt I, et al. Preparation and characterisation of monovalent ion selective cation exchange membranes based on sulphonated poly(ether ether ketone)[J]. Journal of Membrane Science, 2005, 263: 137-145.
[23]Kumara 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: 95–103.
[24]Sata T, Laforgue A, Belanger D. Characterization of a cation-exchange/polyaniline composite membrane [J]. Langmuir, 2003, 19: 744-751.
[25]许云杰, 吴俊杰. 膜的改性及其在环境领域应用研究进展 [J]. 四川环境. 2009. 28(4). 108-111.
[26]胡圆. 单价选择性阳离子交换膜的制备及应用初探[D]: 山东: 中国海洋大学, 2009. 1-115.
[27]邓会宁, 赵金玲, 陈佳媛, 等. 浓海水电渗析制盐用单多价离子选择性膜的制备及性能[A]. 尤金德. 2012北京国际海水淡化高层论坛[C]. 北京: 2012北京国际海水淡化高层论坛论文集, 2012. 173-180.
[28]刘庆丰, 冯胜山, 褚衡, 等. 光化学固定法表面改性医用高分子材料研究进展[J]. 胶体与聚合物, 2007, 25(4): 30-31.
[29]周忠清. 等离子体化学新进展[J]. 自然杂志, 1984, 8(7): 499-544.
[30]Wang M, Jia Y X, Yao T T, et al. The endowment of monovalent selectivity to cation exchange membrane by photo-induced covalent immobilization and self-crosslinking of chitosan[J]. Journal of Membrane Science, 2013, 442: 39-47.
[31]Gule E, Van Baak W, Saakes M, et al. Monovalent-ion-selective membranes for reverse electrodialysis[J]. Journal of Membrane Science, 2013, 455: 254-270.
[32]张景亚, 张浩勤, 谭翎燕, 等. 浸渍-界面聚合法制备荷电镶嵌膜[J]. 高校化学工程学报, 2008, 22(6): 1020-1025.
[33]宋晓峰, 王建刚, 王策. 浸渍法改性活性炭纤维吸附一氧化氮的研究[J]. 合成纤维工业, 2005, 28(2): 30-32.
[34]Cheng C, White N, Shi H, et al. Cation separations in electrodialysis through membrane coated with polyelectrolyte multilayers[J]. Polymer, 2014, 55(6): 1397-1043.
[35]Mulyati S, Takagi R, Fujii A, et al. Simultaneous improvement of the monovalent anion selectivity and antifouling properties of anion exchange membrane in an electrodialysis process, using polyelectrolyte multilayer deposition[J]. Journal of Membrane Science, 2013, 431: 113-120.
[36]Le X T, Viel P, Jégou P, et al, Palacin S. Diazonium-induced anchoring process: an application to improve the monovalent selectivity of cation exchange membranes[J]. Journal of Materials Chemistry A, B and C, 2010, 20, 3750-3757
[37]Chamoulaud G, Belanger D. Chenical modification of the sulfonated membrane by formation of a sulfonamide bond[J]. Langmuir, 2004, 20: 4989-4995.
[38]Kuniaki T, Yoshihisa Y, Toshikatsu S. Modification of transport properties of ion exchange membranes XIV. Effect of molecular weight of polyethyleneimine bond to the surface of cation exchange membranes by acid-amide bonding on electrochemical properties of the menbranes[J]. Journal of Membrane Science, 2000, 179: 101-107.
[39]Alkan E, Esengul K, Lutfi O. Plasma modification of the anion-exchange membrane and its influence on fluoride removal from water[J]. Separation and Purification Technology, 2008, 61: 455-460.
[40]Yasuda H, Plasma polymerization for protective coatings and composite membranes[J]. Journal of Membrane Science, 1984, 18: 273–284.
[41]Steen M L, Hymas L, Havey E D, et al. Low temperature plasma treatment of asymmetric polysulfone membranes for permanent hydrophilic surface modification[J]. Journal of Membrane Science, 2001, 188: 97–114.
[42]K?r E, Oksuz L, Helhel S. Preparation of poly(2-chloroaniline) membrane and plasma surface modification[J]. Applied Surface Science, 2006, 252: 3574–3579.
[43]Mulyati S, Takagi R, Fujii A, et al. Improvement of the antifouling potential of an anion exchange membrane by surface modification with a polyelectrolyte for an electrodialysis progress[J]. Journal of Membrane Science, 2012, 6: 137-143.
[44]Kim E S, Yu Q, Deng B. Plasma surface modification of anion-exchange electrodialysis membrane[J]. Desalination, 1998, 259: 313-329.
[45]Moghadassi A R, Koranian P, Hosseini S M, et al. Surface modification of heterogeneous cation e xchange membrane through simultaneous using polymerization of PAA and multiwalled carbonnano tubes[J]. Journal of Industrial and Engineering Chemistry, 2014, 20(5): 2710-2718.
[46]Hsu J P, Liu B T. Transport of ions through an elliptic ion-selective membrane[J]. Journal of Membrane Science, 1998, 142: 245-255.
[47]Hosseini S M, Madaeni S S, Heidari A R, et al. Preparation and characterization of ion-selective polyvinyl chloride based heterogeneous cation exchange membrane modified by magnetic iron–nickel oxide nanoparticles[J]. Desalination, 2012, 284: 191-199.
[48]Kumara 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: 95-103.