Académique Documents
Professionnel Documents
Culture Documents
a r t i c l e i n f o a b s t r a c t
Article history: In this study, purple membrane (PM) was applied as a methanol-blocking agent on Nafion® mem-
Received 5 September 2010 branes. A series of well-organized poly(diallyldimethylammonium chloride)/PM multilayer films were
Received in revised form 5 November 2010 obtained on a Nafion® 212 surface (PDDA/PM/Nafion® ) to form composite membranes by the elec-
Accepted 7 November 2010
trostatic layer-by-layer (LbL) self-assembly method. The effect of the PDDA/PM/Nafion® heterogenic
Available online 13 November 2010
interface on proton conductivity and methanol permeability was studied by alternating the deposited
surface. With five PDDA/PM bilayers, double-sided modification (PDDA/PM)DF-5 and single-side modifica-
Keywords:
tion (PDDA/PM)SF-5 resulted in excellent methanol blocking with a 73.4% and 64.7% reduction in methanol
Layer-by-layer
Purple membrane
permeability in comparison with unmodified Nafion® 212, respectively. Indeed, the involvement of PM
Nafion modification suppressed the methanol crossover. With regard to the selectivity factor (PDDA/PM)DF-1 composite mem-
Methanol crossover branes showed approximately 2-fold improvement as compared with unmodified Nafion® membranes.
The cell performance of (PDDA/PM)SF-1 composite membranes achieved a power density of 27.0 mW cm−2
which is 48.4% increase compared to cells using unmodified Nafion® 212 membranes. Moreover, with
(PDDA/PM)DF-1 , we achieved a power density of 34.4 mW cm−2 . This study highlights the potential appli-
cation of PM as multifunctional protein membrane in direct methanol fuel cells.
© 2010 Elsevier B.V. All rights reserved.
1. Introduction [8], zeolite [9], and montmorillonite [10], and various polymers,
such as chitosan [11], poly(vinylidene fluoride) [12], polybenzim-
Direct methanol fuel cells (DMFCs) have received much atten- idazole [13], and poly(vinyl alcohol) [14], to fabricate a composite
tion as power source for vehicles and portable devices due to their membrane.
highly efficient energy conversion, low environmental emissions, The layer-by-layer (LbL) self-assembly method is a powerful and
simple structural design, and convenient fuel storage [1]. Perfluo- simple method for depositing a thin multilayer film on a substrate
rosulfonic polymers such as Nafion® are commonly used in DMFCs using sequential electrostatic adsorption between negatively and
as electrolytes because of their high proton conductivity, thermal positively charged polyelectrolytes [15]. Recently, the LbL tech-
and chemical durability, and oxidative stability [2]. However, the nique has successfully been used in DMFCs to suppress methanol
problem of methanol crossover limits the commercialization of crossover [16–18].
DMFCs. Methanol migrates from the anode through the Nafion® Purple membrane (PM) is localized in the cell membrane of
membrane to the cathode where it not only reduces the open circuit Halobacterium salinarium and consists solely of bacteriorhodopsin
potential (OCP) but also poisons the electrocatalyst in the cathode (BR). PM patches are of irregular shape with a lateral dimensional
[3]. An active approach to suppress methanol crossover involves of up to 5 m and a constant thickness of 5 nm [19]. PM occurs as
exploring new sulfonated aromatic polymers including sulfonated a two-dimensional, hexagonal crystalline array of uniformly ori-
polyimide (SPI) [4], sulfonated poly(ether ether ketone) (SPEEK) [5], ented bacteriorhodopsin trimers. It is a very promising biomaterial
and sulfonated polysulfone (SPSf) [6]. Unfortunately, membranes that has attracted considerable interest in the fields of biooptics
that require a high level of sulfonation to achieve sufficient pro- [20] and bioelectrics [21]. This is because BR exhibits long-term
ton conductivity result in undesirable high swelling and excessive stability against thermal, chemical, and photochemical degrada-
methanol crossover. An alternative approach for blocking methanol tion, and it maintains its biological activity even when immobilized
permeation is the modification of a Nafion® membrane by blend- on a solid substrate. The self-assembly of PM on polyelectrolyte
ing inorganic components, such as silica [7], zirconium phosphate surfaces has been studied in recent years [22]; our laboratory simul-
taneously investigated the properties of PM [23] and used the LbL
method to prepare the biomaterial/polymer composite membrane
∗ Corresponding authors. Tel.: +86 10 82339539; fax: +86 10 82339539. for DMFCs. PM was found to show promise for facilitating proton
E-mail addresses: xiangy@buaa.edu.cn (Y. Xiang), lusf@buaa.edu.cn (S. Lu). transfer in Nafion® 117 membranes by preventing proton linkage
0376-7388/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2010.11.013
326 Y. Xiang et al. / Journal of Membrane Science 367 (2011) 325–331
Fig. 1. Scheme of multilayer formation via electrostatic layer-by-layer self-assembly of PDDA and PM on a Nafion® membrane.
by approximately 8% [24]. These studies encouraged us to explore tightly sandwiched between the compartments for 20 min. Then,
the application of PM in DMFCs. the membrane was washed with pure water and tightly sand-
In the present study, we report a novel approach for prepar- wiched again for 20 min between the compartments; however, the
ing an effective multilayer methanol blocking film on a Nafion® PDDA solution in compartment A was changed to PM solution,
membrane by using the electrostatic LbL self assembly method of while the compartment B still contained pure water. Multiple repe-
polycation PDDA and negatively charged PM. The methanol perme- tition of the adsorption steps lead to the formation of single-surface
ability and selectivity factor of the composite membranes has been self-assembled polyelectrolyte multilayer films (PDDA/PM)SF on
studied in detail for potential application of PM in DMFCs. the supports.
Fig. 2. (A) Zeta-potential of PM solution as a function of pH and (B) UV adsorption spectra of (PDDA/PM)DF-4 with various pH values of PM solution.
poly(tetrafluoroethylene) was used as the gas diffusion layer. The ing from complete electro-oxidation at the membrane/Pt catalyst
MEA was hot-pressed at 135 ◦ C and 4 MPa for 90 s. DMFC perfor- interface at the cathode side was measured by applying a positive
mance tests were performed with single-cell hardware (active area: potential at the cathode side.
4 cm2 ) by feeding methanol solution and dry oxygen at flow rates
of 2.5 and 150 mL min−1 (without backpressure) respectively. The 3. Results and discussion
steady-state fuel cell polarization data were collected after oper-
ating the fuel cell for 2 consecutive days including the shut-down Fig. 1 shows the schematic of the ideal configuration of the poly-
period overnight. Methanol crossover was measured with a voltam- electrolyte and the PM fragment on a Nafion® membrane in order
metric method the steady-state limiting current density arising to inhibit methanol permeation. It is known that Nafion® has a dual
from the oxidation of the permeated methanol at the cathode side. structure with a hydrophobic region interspersed with ion-rich
During the measurement, methanol solution was fed at a flow rate hydrophilic domains; methanol primarily diffuses through these
of 2.5 mL min−1 into the anode side of the MEA, while the cath- domains, which are primarily associated with the sulfonic acid
ode side was kept in an inert humidified N2 atmosphere at a flow group on the Nafion® membrane surface [26]. As shown, a mono-
rate 100 mL min−1 . The steady-state limiting current density result- layer of the polycation, PDDA, was first electrostatically adsorbed
328 Y. Xiang et al. / Journal of Membrane Science 367 (2011) 325–331
3.1. Effect of pH
It is known that the rate of coagulation mainly depends on the Fig. 3. UV–vis adsorption spectra of (PDDA/PM)DF depending on the number of
deposited bilayers. The curves (from bottom to top) correspond to the adsorption
stability of colloid particles and that pH is an important param-
of 0, 1, 3, 5, 10, 15, 20, and 25 alternative PDDA/PM bilayers deposited in dou-
eter that affects colloid stability [27]. The stability of colloid is ble Nafion® membrane surfaces. The inset graph shows the linear increase of the
often investigated in terms of its zeta-potential (), which reflects absorbance at 568 nm (BR characteristic absorbance) with the number of bilayers;
their surface chemical properties and the way in which colloids the linear relative factor = 0.9973.
interact with each other [28]. The -potential of PM solutions of
varying pH values is shown in Fig. 2A; notably, the isoelectric point 3.3. Proton conductivity () and methanol permeability (PM ) of
(IEP) falls at approximately pH 6 where the -potential is 0. The multilayer composite membranes
-potential data are as expected: positive at relatively low pH val-
ues due to excess protons. As the pH value increases above the IEP, The proton conductivity of the Nafion® -based composite mem-
the -potential gradually decreases and becomes negative after the branes was measured at room temperature using a two-probe
solution becomes alkaline; this occurs until a plateau of −66.7 to technique (Tables 1 and 2). The proton conductivity of the unmod-
−70.8 mV is reached at approximately pH 9. This result suggests ified Nafion® 212 was tested in our system and was found to
that PM patches are more readily adsorbed onto the polycation be 19.2 mS cm−1 . The conductivity of the (PDDA/PM)DF mem-
layer as a negatively charged clustered multi-counterion under branes decreased slightly with an increase in the number of the
more alkaline conditions. Thus, pH 9 is sufficient for the PM frag- self-assembled PDDA/PM bilayers. The proton conductivity of the
ments to avoid agglomeration, resulting in their smooth and tight self-assembled (PDDA/PM)SF multilayer films exhibited a similar
assembly on the PDDA layer [29]. Moreover, the absorbance of tendency (Table 2). The reduction in proton conductivity of the self-
(PDDA/PM)DF-4 at 568 nm increases sharply with increases in the assembled composite membranes is attributed to the formation of
pH of the PM solution until it reaches a maximum at pH 9.4 (Fig. 2B). very thick individual polyelectrolyte bilayers deposited on Nafion®
A possible explanation for this behavior is that the charge density membrane surfaces, which hinders the mobility of protons in the
of PM in acidic and neutral media is insufficient to generate enough self-assembled composite membrane [31].
Coulombic force to sufficiently interact with the cationic charges in Methanol permeability is a major drawback that leads to a
the PDDA layer. However, if the negative charge density of the PM marked reduction in cellular efficiency; it is a critical problem that
is great enough at high pH, the electrostatic interaction becomes needs to be solved for DMFC applications. Methanol primarily dif-
the dominant driving force [30]. Thus, we chose a pH of 9.4 for the fuses through the hydrophilic water channels of Nafion® , which are
aqueous PM solution for all of the following experiments, whereas
the pH of the PDDA solution was kept constant at neutral in all
experiments.
3.2. UV measurements
Table 1
Comparison of the proton conductivity (), methanol permeability (PM ), and mem-
brane selectivity (ϕ) values of (PDDA/PM)DF depending on the number of deposited
bilayers.
also used to transport protons. Therefore, the methanol-blocking Fig. 5. The methanol permeability of (PDDA/PM)SF multilayers deposited on Nafion®
effect of PDDA/PM bilayers deposited on Nafion® membranes membranes with modified () and unmodified () surfaces facing the methanol
needs to be evaluated. Table 1 shows the variations in the solution.
The cell performance of DMFCs prepared with an unmodified PDDA/PM multilayer films deposited on Nafion® 212 mem-
Nafion® 212 membrane and Nafion® 212 membranes modified by branes were successfully fabricated using the electrostatic LbL
Y. Xiang et al. / Journal of Membrane Science 367 (2011) 325–331 331
self-assembly technique for both (PDDA/PM)DF and (PDDA/PM)SF posite membrane with low methanol permeability, Electrochim. Acta 50 (2005)
composite membranes. Although PDDA/PM multilayer films have 2639–2645.
[11] Y. Xiang, M. Yang, Z.B. Guo, Z. Cui, Alternatively chitosan sulfate blending
some negative effects on the proton conductivity of compos- membrane as methanol-blocking polymer electrolyte membrane for direct
ite membranes, the methanol crossover is significantly reduced methanol fuel cell, J. Membr. Sci. 337 (2009) 318–323.
with these membranes as compared to unmodified Nafion® mem- [12] S.W. Choi, Y.Z. Fu, Y.R. Ahn, S.M. Jo, A. Manthiram, Nafion-impregnated electro-
spun polyvinylidene fluoride composite membranes for direct methanol fuel
branes. With 5 PDDA/PM bilayers, the methanol permeability of the cells, J. Power Sources 180 (2008) 167–171.
(PDDA/PM)DF and (PDDA/PM)SF composite membranes decreases [13] R. Wycisk, J. Chisholm, J. Lee, J. Lin, P.N. Pintauro, Direct methanol fuel cell mem-
by 73.4% and 64.7% to 3.16 and 4.19 × 10−7 cm2 s−1 , respectively. branes from Nafion-polybenzimidazole blends, J. Power Sources 163 (2006)
9–17.
The main reason underlying this result is that PDDA/PM multilay- [14] N.W. DeLuca, Y.A. Elabd, Nafion® /poly(vinyl alcohol) blends: effect of compo-
ers with PDDA/PM on their Nafion® membranes associate with sition and annealing temperature on transport properties, J. Membr. Sci. 282
SO3 − clusters, thus blocking water channels and plugging the (2006) 217–224.
[15] G. Decher, Fuzzy nanoassemblies: toward layered polymeric multicomposites,
hydrophilic domain; this in turn suppresses methanol crossover.
Science 277 (1997) 1232–1237.
Moreover, both (PDDA/PM)DF and (PDDA/PM)SF multilayer films [16] M. Yang, S.F. Lu, J.L. Lu, S.P. Jiang, Y. Xiang, Layer-by-layer self-assembly of
with a single PDDA/PM bilayer exhibited the greatest membrane PDDA/PWA-Nafion composite membranes for direct methanol fuel cells, Chem.
selectivity. (PDDA/PM)SF-1 multilayer film achieved a power den- Commun. 46 (2010) 1434–1436.
[17] S.C. Mu, H.L. Tang, Z.H. Wan, M. Pan, R.Z. Yuan, Au nanoparticles self-assembled
sity of 27.0 mW cm−2 , which is 48.4% higher than that with an onto Nafion membranes for use as methanol-blocking barriers, Electrochem.
unmodified Nafion® 212 membrane, and (PDDA/PM)DF-1 exhibits Commun. 7 (2005) 1143–1147.
higher performance than (PDDA/PM)SF-1 , achieving a power den- [18] C.J. Zhao, H.D. Lin, Z.M. Cui, X.F. Li, H. Na, W. Xing, Highly conductive, methanol
resistant fuel cell membranes fabricated by layer-by-layer self-assembly of
sity of 34.4 mW cm−2 . Consequently, Nafion® -based PDDA/PM inorganic heteropolyacid, J Power Sources 194 (2009) 168–174.
multilayer films have potential application in DMFCs with low [19] U. Alexiev, T. Marti, M.P. Heyn, H.G. Khorana, P. Scherrer, Surface charge of
methanol permeation and high fuel cell performances. bacteriorhodopsin detected with covalently bound pH indicators at selected
extracellular and cytoplasmic sites, Biochemistry 33 (1994) 298–306.
[20] D. Ho, B. Chu, H. Lee, E.K. Brooks, K. Kuo, C.D. Montemagno, Fabrication of
Acknowledgements biomolecule-copolymer hybrid nanovesicles as energy conversion systems,
Nanotechnology 16 (2005) 3120–3132.
[21] Y.D. Jin, N. Friedman, M. Sheves, D. Cahen, Bacteriorhodopsin-monolayer-based
This project was supported by grants from the National Natural planar metal–insulator–metal junctions via biomimetic vesicle fusion: prepa-
Science Foundation of China (20773008, 21003007, and 21073010), ration, characterization, and bio-optoelectronic characteristics, Adv. Funct.
the National High Technology Research and Development Pro- Mater. 17 (2007) 1417–1428.
[22] M.-b. Saab, E. Estephan, T. Cloitre, R. Legros, F.J.G. Cuisinier, L. Zimaı̌nyi, C.
gram (863 program, 2077AA05Z146), Beijing Novel Program (No.
Gergely, Assembly of purple membranes on polyelectrolyte films, Langmuir
2008B12) and the Fundamental Research Funds for the Central Uni- 25 (2009) 5159–5167.
versities (YWF-10-02-004). [23] Y. Xiang, M. Yang, T. Su, Y.Y. Chen, L.J. Bi, K.S. Hu, Glycolipid biotinylation on
purple membrane with maintained bioactivity, J. Phys. Chem. B 113 (2009)
7762–7766.
References [24] D. Ho, B. Chu, H. Lee, C.D. Montemagno, Protein-driven energy transduction
across polymeric biomembranes, Nanotechnology 15 (2004) 1084–1094.
[1] W. Li, A. Manthiram, Sulfonated poly(arylene ether sulfone) as a methanol- [25] D. Oesterhelt, W. Stoeckenius, Isolation of the cell membrane of Halobacterium
barrier layer in multilayer membranes for direct methanol fuel cells, J. Power halobium and its fractionation into red and purple membrane, Methods Enzy-
Sources 195 (2010) 962–968. mol. 31 (1974) 667–678.
[2] K.A. Mauritz, R.B. Moore, State of understanding of Nafion, Chem. Rev. 104 [26] S.P. Jiang, Z.C. Liu, Z.Q. Tian, Layer-by-layer self-assembly of composite
(2004) 4535–4585. polyelectrolyte-nafion membranes for direct methanol fuel cells, Adv. Mater.
[3] A. Bettelheim, L. Soifer, E. Korin, Electropolymerized porphyrin films as 18 (2006) 1068–1072.
methanol barriers in direct methanol fuel cells, J. Electroanal. Chem. 571 (2004) [27] P. Narong, A.E. James, Effect of pH on the -potential and turbidity of yeast
265–272. suspensions, Colloids Surf. A: Physicochem. Eng. Aspects 274 (2006) 130–137.
[4] Y. Woo, S.Y. Oh, Y.S. Kang, B. Jung, Synthesis and characterization of sulfonated [28] J.A. Brant, A.E. Childress, Assessing short-range membrane-colloid interactions
polyimide membranes for direct methanol fuel cell, J. Membr. Sci. 220 (2003) using surface energetics, J. Membr. Sci. 203 (2002) 257–273.
31–45. [29] T. Jussila, M.L. Li, N.V. Tkachenko, S. Parkkinen, B.F. Li, L. Jiang, H. Lem-
[5] J.C. Tsai, H.P. Cheng, J.F. Kuo, Y.H. Huang, C.Y. Chen, Blended Nafion® /SPEEK metyinen, Transient absorption and photovoltage study of’ self-assembled
direct methanol fuel cell membranes for reduced methanol permeability, J. bacteriorhodopsin/polycation multilayer films, Biosens. Bioelectron. 17 (2002)
Power Sources 189 (2009) 958–965. 509–515.
[6] F. Lufrano, V. Baglio, P. Staiti, A.S. Arico, V. Antonucci, Polymer electrolytes based [30] J.A. He, L. Samuelson, L. Li, J. Kumar, S.K. Tripathy, Oriented bacteri-
on sulfonated polysulfone for direct methanol fuel cells, J. Power Sources 179 orhodopsin/polycation multilayers by electrostatic layer-by-layer assembly,
(2008) 34–41. Langmuir 14 (1998) 1674–1679.
[7] S.Z. Ren, G.Q. Sun, C.N. Li, Z.X. Liang, Z.M. Wu, W. Jin, X. Qin, X.F. Yang, Organic [31] H. Deligoz, S. Yilmazturk, T. Karaca, H. Ozdemir, S.N. Koc, F. Oksuzomer, A.
silica/Nafion® composite membrane for direct methanol fuel cells, J. Membr. Durmus, M.A. Gurkaynak, Self-assembled polyelectrolyte multilayered films
Sci. 282 (2006) 450–455. on Nafion with lowered methanol cross-over for DMFC applications, J. Membr.
[8] M.P. Rodgers, Z. Shi, S. Holdcroft, Ex situ characterisation of composite Nafion Sci. 326 (2009) 643–649.
membranes containing zirconium hydrogen phosphate, Fuel Cells 9 (2009) [32] H.L. Tang, M. Pan, S.P. Jiang, Z.H. Wan, R.Z. Yuan, Self-assembling multi-layer Pd
534–546. nanoparticles onto NafionTM membrane to reduce methanol crossover, Colloids
[9] X. Li, E.P.L. Roberts, S.M. Holmes, V. Zholobenko, Functionalized zeolite A- Surf. A: Physicochem. Eng. Aspects 262 (2005) 65–70.
Nafion composite membranes for direct methanol fuel cells, Solid State Ionics [33] H. Ahmad, S.K. Kamarudin, U.A. Hasran, W.R.W. Daud, Overview of hybrid mem-
178 (2007) 1248–1255. branes for direct-methanol fuel-cell applications, Int. J. Hydrogen Energy 35
[10] R.F. Silva, S. Passerini, A. Pozio, Solution-cast Nafion® /montmorillonite com- (2010) 2160–2175.