兩性膜(Bipolar membrane)在工業上的應用甚廣。一般來說，常用於酸/鹼水溶液的製造、汙染控制/資源回收(如：無機酸/鹼、有機酸及有機物分離回收和純化) ，因此，相當受到工業和學術界的關注。而於先前研究發現實驗室所製備的兩性膜可以有效降低水解離電位，且將其應用在電解產氫系統上有提高氫氣產率及節省能量的效果。所以本研究利用兩性膜本身具有電場加強水解離的獨特特性，以電漿表面改質技術，於PVDF膜表面的兩側分別誘導接枝不同陰/陽離子型的單體製備四種兩性膜，探討其應用在電解產氫的效能。
本研究使用電漿表面處理技術分別將陰離子型單體N,N-Dimethyl amino ethyl acrylate (DMAEA)、4-Vinyl pyridine (4-VP)和陽離子型單體4-Styrene sulfonic acid sodium salt hydrate (SSS)、acrylic acid (AA) 誘導接枝在PVDF膜兩側形成 DMAEA-PVDF-SSS、DMAEA-PVDF-AA、4VP-PVDF-SSS及4VP-PVDF-AA四種兩性膜。同時，也使用Poly-ethersulfonate (PES) 隔離膜當比較對照組。在電解產氫實驗裡，當使用自製四種兩性膜為隔膜時，其工作電位都明顯低於PES系統，由此可證明兩性膜具有降低工作電位的能力。其中，以使用DMAEA-PVDF-SSS 兩性膜當作電解水隔膜時，可將水解離成H+與OH-的電位降低至0.92 V。另一方面，當改變KCl濃度時，電解水的臨界電位不會隨之改變，但電解水的極限電流密度會隨著KCl濃度增加而增加。因為兩性膜具有電場加強水解離的效應，其產氫效率也因而提升10-30 %左右。其中，以 DMAEA-PVDF-SSS 兩性膜當隔膜時，其產氫效率最高可達92%，但當將陰離子交換層改變為4VP-PVDF-SSS 兩性膜時，產氫效率僅剩下74%。其原因為兩性膜本身造成水解離的電場大小、水解離常數大小以及本身物裡性質所影響。而於產氫氣所需能量消耗方面，以DMAEA-PVDF-SSS 兩性膜當作隔膜節能的效果最佳，最高可降低48%的能量消耗。所以，本系統中之兩性膜的結構對電解產氫之影響，以改變陰離子交換層的結構最為顯著。

Bipolar membranes are widely used in industry. They were usually used to produce the acid/base solutions and water treatment. Therefore, bipolar membranes have been attracted industrial and academic research. Reducing the cell voltage of water electrolysis by using bipolar membrane had proved by our laboratory. Consequently, the aim of this research is to investigate the surface modification of PVDF membranes by plasma treatment and alter various ionic monomers to form four kinds of bipolar membranes for hydrogen production from water electrolysis.
In this study, the N,N-Dimethyl amino ethyl acrylate (DMAEA)、4-Vinyl pyridine (4-VP), 4-Styrene sulfonic acid sodium salt hydrate (SSS)、acrylic acid (AA) monomers were grafted onto the respective side of the PVDF membranes through the plasma treatment. Four kinds of bipolar membranes, DMAEA-PVDF-SSS、DMAEA-PVDF-AA、4VP-PVDF-SSS and 4VP-PVDF-AA bipolar membranes, have been successfully prepared by plasma-induced polymerization method after characteristic of FTIR and SEM. Poly-ethersulfonate (PES) membranes were used as background experiment (Water). In water electrolysis experiment, the cell voltage using four kinds of bipolar membranes is lower than PES membrane (Water). Among those bipolar membranes, DMAEA-PVDF-SSS bipolar membrane has lowest critical voltage of water splitting to H+ and OH- as 0.92V. On the other hand, the limiting current density was increased with the increasing of KCl concentration. Furthermore, H2 production efficiency can be improved 10-30% (compared with Water). When using the DMAEA-PVDF-SSS bipolar membranes in water electrolysis, the H2 production efficiency can be as high as 92% but it is just only 74% by 4VP-PVDF-SSS bipolar membranes. The result is attributed from the electrical field, water dissociation constant ratio and their physical properties. In the energy consumption of H2 production, DMAEA-PVDF-SSS bipolar membranes have great outcome, it can save 48% energy. Consequently, the effect of anion exchange layer on the water electrolysis is larger than that of cation exchange layer of bipolar membranes.

1.P. Haussinger, R. Lohmuller, A. M. Watson, Hydrogen, 1. Properties and Occurence, Encyclopedia Of Industrial Chemistry.
2.Das D and Veziroğlu TN, International Journal of Hydrogen Energy 26:13-28 (2001).
3.毛宗強, 氫能－21世紀的綠色能源, 化學工業出版社, 2006.
4.K. Hashimoto, H. Irie, A. Fujishima, Japanese Journal of Applied Physics, 44, 8269, 2005.
5.R.L. LeRoy, M.B.I. Janjua, R. Renaud, U. Leuenberger, J.
Electrochem. Soc., 126, 1674, 1979.
6.S. Kim, N. Koratkar, Appl. Phys. Lett., 88, 263106, 2006.
7.Z. Hu, M. Wu, Z. Wei, S. Song, P.K. Shen, J. Power Sources, 166, 458, 2007.
8.A.T. Marshall, S. Sunde, M. Tsypkin, R. Tunold, Int. J. Hydrogen Energy, 32, 2320, 2007.
9.S. Grigoriev, V. Porembsky, V. Fateev., Int. J. Hydrogen Energy, 31, 171, 2006.
10.E. Rasten, Electrocatalysis in water electrolysis with solid polymerelectrolyte, PhD thesis, NTNU, Trondheim, Norway; 2001.
11.J. Sedlak, R. Lawrence, J. Enos, Int. J. Hydrogen Energy, 6,159, 1981.
12.H. Takenaka, E. Torikai, Y. Kawami, N. Wakabayashi, Int. J. Hydrogen Energy, 7, 397, 1982.
13.M. Yamaguchi, K. Okisawa, T. Nakanori, Development of high performance solid polymer electrolyte water electrolyzer in WE-NET, In: Proceedings of the 32nd intersociety energy conversion engineering conference, vol. 3, p. 1958-65, 1997.
14.P. Millet, R. Durand, R. Pineri, Int. J. Hydrogen Energy, 15, 245, 1990.
15.M. Yamaguchi, K. Yagiuchi, K. Okisawa, R&D of high performance solid polymer electrolyte water electrolyzer in WE-NET. In: Proceedings of the 11th world hydrogen energy conference, vol. 11, p. 781–6, 1996.
16.D.L. Stojic, A.D. Maksic, M.P.M. Kaninski, B.- Ð. Cekic, S.S. Miljanic, J. Power Sources, 145, 278, 2005.
17.M.P.M. Kaninski, D.L. Stoji´c, Ð.– de P. Saponji, N.I. Potkonjak, S.S. Miljani´c, J. Power Sources, 157, 758, 2006.
18.R.F. de Souza, J.C. Padilha, R.S. Goncalves, M.O. de Souza, J. Rault-Berthelot, J. Power Sources, 164, 792, 2007.
19.T. Take, K. Tsurutani, M. Umeda, J. Power Sources, 164, 9, 2007.
20.F. Vitse, M. Cooper, G.-G. Botte, J. Power Sources, 142, 18, 2005.
21.M.S. Seehra, S. Ranganathan, A. Manivannan, Appl. Phys. Lett., 90, 044104, 2007.
22.L. Soler, J. Macanás, M. Muňoz, J. Casado, Int. J. Hydrogen Energy, 31, 129, 2006.
23.H. Cheng, K. Scott, C. Ramshaw, J. Electrochem. Soc., 149, D172, 2002.
24.T. Iida, H. Matsushima, Y. Fukunaka, J. Electrochem. Soc., 154, E112, 2007.
25.T. Ohmori, K. Tachikawa, K. Tsuji, K. Anzai, Int. J. Hydrogen Energy, 32, 5094, 2007.
26.S. Lu, L. Zhuang, J. Lu, J. Membr. Sci., 300, 205, 2007.
27.F.G. Donnan, Z. Electrochem., 17, 572, 1911.
28.S. Mafé, P. Ramìrez, Acta Polymer, 48, 234, 1997.
29.B. Bauer, F.J. Gerner, H. Strathmann, Desalination, 68, 279, 1988.
30.R. Simons, J. Membr. Sci., 78, 13, 1993.
31.H. Strathmann, H.J. Rapp, B. Bauer, C.M. Bell, Desalination, 90, 303, 1993
32.K. Shimizu, A. Tanioka, Polymer, 38, 5441, 1997.
33.N. Ya. Pivovarov, V.P. Greben, S.A. Ponomarenko, Russ. J. Electrochem., 30, 1113, 1994.
34.R. Simons, Electrochim. Acta, 30, 275, 1985.
35.J.C. Bassignana, H. Reiss., J. Membr. Sci, 15, 27, 1983.
36.A. Alcaraz, P. Ramìrez, S. Mafé, H. Holdik, B. Bauer, Polymer, 41, 6627, 2000.
37.G. Grossman, J. Phys. Chem., 80, 1616, 1976.
38.R. Simons, G. Khanarian, J. Membr. Biol., 38, 267, 1978.
39.L.C., Bassignana, H. Reiss, J. Membr. Sci., 15, 27, 1983.
40.S. Mafé, J.A. Manzanares, P. Ramìrez, Phys. Rev. A, 42, 6245, 1990.
41.R. Simons, J. Membr. Sci., 82, 65, 1993.
42.B. Kunst, B. Loverecek, Croat. Chem. Acta, 34, 219, 1962.
43.L. Onsager, J. Chem. Phys., 2, 599, 1934.
44.J.J. Krol, M. Jansink, M. Wessling, H. Strathmann, Sep. Purif. Technol., 14, 41, 1998.
45.R. Simons, Nature, 280, 824, 1979.
46.R. Simons, Electrochim. Acta, 29, 151, 1984.
47.T.J. Chou, A. Tanioka, J. Colloid Interf. Sci., 22, 576, 1999.
48.T.J. Chou, A. Tanioka, J. Electroanal. Chem., 462, 12, 1999.
49.T.J. Chou, A. Tanioka, J. Phys. Chem. B, 102, 7866, 1998.
50.T.J. Chou, A. Tanioka, J. Colloid Interf. Sci., 212, 293, 1999.
51.R. Simons, G. Khanarian, J. Membr. Sci., 38, 11, 1978.
52.V. Frilette, J. Phys. Chem., 60, 435, 1956.
53.F. Wilhelm, N.V.D. Vegt, M. Wessling, H. Strathmann, Bipolar membrane preparation, in: A.J.B. Kemperman (Ed.), Handbook Bipolar Membrane Technology, Twente University Press, Enschede, 2000, pp. 79–108.
54.J.H. Hao, C.X. Chen, L. Li, L.X. Yu, W.J. Jiang, J. Appl. Polym. Sci., 80, 1658, 2001.
55.F. de Körösy, Israel J. Chem., 3, 22, 1965.
56.R.Q. Fu, T.W. Xu, W.H. Yang, Z.X. Pan, J. Appl. Polym. Sci., 90, 572, 2003.
57.A. Jendrychowska-Bonamour, J. Chim. Phys. Phys. Chim. Biol., 70, 16, 1973.
58.Z. Xu, H. Gao, M. Qian, Y. Yu, G. Wan, B. Chen, Radiat. Phys.Chem., 42, 963, 1993.
59.E.A. Hegazy, H. Kamal, N. Maziad, A. Dessouki, Nucl. Instrum. Meth. Phys. Res. B, 151, 386, 1999.
60.R. El Moussaoui, H. Hurwitz, Single-film membrane-process for obtaining it and use thereof, U.S. Patent 5,840,192, 1998.
61.彭郁仁, 接枝型兩性膜的製備與性質之研究, 成大化工所碩士論文, 2000.
62.Y. Yokoyama, A. Tanioka, K. Miyasaka, J. Membr. Sci., 43, 165, 1989.
63.C.L. Hsueh, Y.J. Peng, C.C. Wang, C.Y. Chen, J. Membr. Sci., 219, 1, 2003.
64.C. Carmen, Desalin. Water Reuse, 4, 46, 1995.
65.R. Audinos, Chem. Eng. Technol., 20, 247, 1997.
66.A.T. Che´rif, J. Mole´nat, A. Elmidaoui, J. Appl. Electrochem., 27, 1069, 1997.
67.M. Paleogou, A. Thibault, P.Y. Wong, R. Thompson, R.M. Berry, Sep. Purif. Technol., 11, 159, 1997.
68.G. S. Trivedi, B.G. Shah, S.K. Adhikary, V.K. Indusekhar, R. Rangarajan, React. Funct. Polym., 28, 243, 1996.
69.G.S.Trivedi, B.G.Shah, S.K. Adhikary, R. Rangarajan, React. Funct. Polym., 39, 91, 1999.
70.N. Drouiche, H. Grib, N. Abdi, H. Lounici, A. Pauss, N. Mameri, J. Hazard. Mater., 170, 197, 2009.
71.A.J.B. Kemperman, 雙極膜技術手冊, 化學工業出版社，2004.
72.C.H. Huang, T.W. Xu, Y.P. Zhang, Y.H. Xue, G.W. Chen, J. Membr. Sci., 288, 1, 2007.
73.Y.H. Kim, S.H. Moon, J. Chem. Technol. Biotechnol., 76, 169, 2001.
74.Q.H. Wang, G.S. Cheng, X.H. Sun, B. Jin, Process Biochem., 41, 152, 2006.
75.C. Akerberg, G. Zacchi, Bioresour. Technol., 75, 119, 2000.
76.J.S.J. Ferrer, S. Laborie, G. Durand, M. Rakib, J. Membr. Sci., 280, 509, 2006.
77.G.S. Trivedi, B.G. Shah, S.K. Adhikary, V.K. Indusekhar, R. Rangarajan, React. Funct. Polym., 32, 209, 1997.
78.S. Koter, A.Warszawski, Pol. J. Environ. Stud., 9, 45, 2000.
79.V. Habova, K. Melzoch, M. Rychtera, B. Sekavova, Desalination, 163, 361, 2004.
80.E.G. Lee, S.H. Moon, Y.K. Chang, I.K. Yoo, H.N. Chang, J. Membr. Sci., 145, 53, 1998.
81.L. Madzingaidzo, H. Danner, R. Braun, J. Biotechnol., 96, 223, 2002.
82.H. Li, R. Mustacchi, C.J. Knowles,W. Skibar,G. Sunderland, I. Dalrymple, S.A. Jackman, Tetrahedron, 60, 655, 2004.
83.S. Novalic, T. Kongbangkerd, K.D. Kulbe, J. Membr. Sci., 166, 99, 2000.
84.G. Pourcelly, C. Gavach, Electrodialysis water splitting—application of electrodialysis with bipolar membranes, in: A.J.B. Kemperman (Ed.), Handbook on Bipolar Membrane Technology, Twente University Press, Enschede, The Netherlands, 2000, pp. 17–46.
85.T.W. Xu,W.H. Yang, Chem. Eng. Process, 41, 519, 2002.
86.T.W. Xu, W.H. Yang, J. Membr. Sci., 203, 145, 2002.
87.S. Novalic, K.D. Kulbe, Food Technol. Biotechnol., 36, 193, 1998.
88.P. Pinacci, M. Radaelli, Desalination, 148, 177, 2002.
89.S. Novalic, J. Okwor, K.D. Kulbe, Desalination, 105, 277, 1996.
90.L.X. Yu, J. Su, J. Wang, Desalination, 177, 209, 2005.
91.F. Alvarez, R. Alvarez, J. Coca, J. Sandeaux, R. Sandeaux, C. Gavach, J. Membr. Sci., 123, 61, 1997.
92.H. Strathmann, Ion-exchange Membrane Separation Processes, Elsevier, Amsterdam, 2004.
93.L.X. Yu, A.G. Lin, L.P. Zhang, C.X. Chen, W.J. Jiang, Chem. Eng. J., 78, 153, 2000.
94.V. Cauwenberg, J. Peels, S. Resbeut, G. Pourcelly, Sep. Purif. Technol., 22/23, 115, 2001.
95.J.S. Tronc, `Inhibition des réactions de brunissement enzymatique du jus de pomme frais non clarifié par électro-dialyse' in Thése de Maítrise no. 14431, Université Laval: Sainte-Foy, QueÂbec, 1996.
96.J.S.Tronc, F. Lamarche, J. Makhlouf, J. Agric. Food Chem., 46,829, 1998.
97.J.S.Tronc, F. Lamarche, J. Makhlouf, J. Food Sci., 1, 75, 1997.
98.L. Bazinet, F. Lamarche, R. Labrecque, R. Toupin, M. Boulet, D. Ippersiel, `Systematic Study on the Preparation of a Food Grade Soyabean Protein' in Report for the Canadian Electricity Association
no 9326 U 987, Research and Development, Montreal, 1996.
99.L. Bazinet, F. Lamarche, R. Labrecque, D. Ippersiel, J. Agric. Food Chem., 45, 2419, 1997.
100.L. Bazinet, F. Lamarche, R. Labrecque, R. Toupin, M. Boulet, D. Ippersiel, Food Technol., 51, 52, 1997.
101.L. Bazinet, F. Lamarche, R. Labrecque, D. Ippersiel, `Optimization of Bipolar Membrane Electroacidification' in The Electrochemical Society, Proceedings Volume 97-6, 1997.
102.B. Nagel, `Kontinuierliche Herstellum von Hochwertingen Naturtruben Apfelsaften unter Einbeziehung der Zen-trifugaltechnik' FluÈssiges Obst. 1, 6-8, 1992.
103.J.J. Macheix, A. Fleuriet, J. Billot, Fruit Phenolics, pp. 10098, CRC Press, Boca Raton, FL, 1990.
104.A. Janovitz-Klapp, F. Richard, P.M. Goupy, J. Nicolas, J. Agric. Food Chem., 38, 926, 1990.
105.G.M. Saper, M.A. Ziolkowski, J. Food Sci., 52, 1732, 1987.
106.G.P. Zemel, C.A. Sims, M.R. Marshall, M. Balaban, J. Food Sci., 55, 562, 1990.
107.J.D. McCord, A. Kilara, J. Food Sci., 48, 1479, 1984.
108.L. Bazinet, F. Lamarche, D. Ippersiel, Trends Food Sci. Tech., 9, 107, 1998.