Layer Layer PEM

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Layer-by-layer self-assembly in the development of electrochemical

energy conversion and storage devices from fuel cells to supercapacitors
Yan Xiang,*ac Shanfu Lua and San Ping Jiang*b
Received 20th February 2012
DOI: 10.1039/c2cs35048c
As one of the most effective synthesis tools, layer-by-layer (LbL) self-assembly technology can
provide a strong non-covalent integration and accurate assembly between homo- or hetero-phase
compounds or oppositely charged polyelectrolytes, resulting in highly-ordered nanoscale
structures or patterns with excellent functionalities and activities. It has been widely used in the
developments of novel materials and nanostructures or patterns from nanotechnologies to medical
fields. However, the application of LbL self-assembly in the development of highly efficient
electrocatalysts, specific functionalized membranes for proton exchange membrane fuel cells
(PEMFCs) and electrode materials for supercapacitors is a relatively new phenomenon. In this
review, the application of LbL self-assembly in the development and synthesis of key materials of
PEMFCs including polyelectrolyte multilayered proton-exchange membranes, methanol-blocking
Nafion membranes, highly uniform and efficient Pt-based electrocatalysts, self-assembled
polyelectrolyte functionalized carbon nanotubes (CNTs) and graphenes will be reviewed.
The application of LbL self-assembly for the development of multilayer nanostructured materials
for use in electrochemical supercapacitors will also be reviewed and discussed (250 references).
1 Introduction
a
Key Laboratory of Bio-Inspired Smart Interfacial Science and
Technology of Ministry of Education, School of Chemistry and Layer-by-layer (LbL) self-assembly technology is one of the
Environment, Beihang University, Beijing 100191, P. R. China. most effective synthesis tools to fabricate highly-ordered
E-mail: xiangy@buaa.edu.cn; Fax: +86 10 8233 9539;
Tel: +86 10 8233 9539
nanoscale structures or patterns with extended functionalities
b
Fuels and Energy Technology Institute & Department of Chemical and activities. The LbL technique was established by Iler
Engineering, Curtin University, Perth, WA 6102, Australia. in 19661 based on the LB membrane invented by Blodgett2
E-mail: S.Jiang@curtin.edu.au; Fax: +61 8 9266 1138; and Langmuir.3 However, the concept did not attract great
Tel: +61 8 9266 9804
c
Beijing Key Laboratory for Advanced Functional Materials and Thin attention until pioneering works on the development of self-
Film Technology, Beihang University, Beijing, 100191, P. R. China assembly techniques and applications by Decher4–6 in the 1990s.
Prof. Yan Xiang received her Dr Shanfu Lu received his

PhD in Physical Chemistry PhD in Physical Chemistry
from Sichuan Univ., China in (Electrochemistry) from Wuhan
2001. She joined Beihang Uni- University, in 2008. After one
versity in 2001 and spent one and half years as a post-
year on green catalysis as a doctoral fellow at Nanyang
postdoc in Carnegie Mellon Technological University,
University, USA. Now she is Singapore, working with Prof.
the full professor of Materials S. P. Jiang, he joined Prof.
Chemistry at School of Chem- Xiang’s group, and is currently
istry & Environment, Beihang an associate professor in
University, and is a chief Electrochemistry and Energy
faculty member of Beijing Materials at School of
Key Laboratory for Advanced Chemistry and Environment,
Yan Xiang Functional Materials and Thin Shanfu Lu Beihang University, China.
Film Technology. Her main His main current research
current research interests involve key energy materials develop- interests involve nanomaterials and polyelectrolytes for energy
ment and its application. storage and conversion.
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 7291–7321 7291
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conventional PEs and block polymers,13–15 various biomaterials,

especially water-soluble proteins, have charged sites on their
surface, can be self-assembled by electrostatic LbL adsorption,
such as proteins,16,17 DNA18–20 and charged polysaccharides.21,22
LbL self-assembly has emerged as a powerful tool for the
immobilization of biomolecules with preserved bioactivity.23
and responsive materials for drug release.24 Charged inorganic

substances, including colloidal nanoparticles,25–27 clays,28,29
heteropolyacids (HPAs),30,31 and metal nanoparticles,32–34 can
also been used for the LbL self-assembly process. The unique
advantages of the LbL self-assembly techniques are its great
adaptability with precise microstructural control and high
repeatability, extensive possibility in wide range applications,
liquid–liquid phase reaction and its nontoxic and environmental-
friendly nature.35,36
Fig. 1 Schematic of layer-by-layer (LbL) self-assembly of a multi-
Energy is one of the biggest challenges that mankind faces
layer coating by sequential adsorption of oppositely charged PEs.
over the next 50–100 years. The ever-growing demand for
energy is coupled with environmental concerns associated with
The LbL self-assembly deposition at a surface is largely
the excessive and accelerated use of fossil fuels such as coal, oil
controlled by a charge compensation mechanism.7 In this
and gas. Consequently there are urgent needs to increase
technique, two oppositely charged polymers or polyelectro-
electricity generation efficiency and to develop clean and
lytes (PEs) dissolved in aqueous solution are alternatively
efficient means of energy conversion and storage such as solar
deposited on a support surface by means of electrostatic
cells, fuel cells, supercapacitors and advanced batteries. As a
attraction. After each dipping cycle, the surface charge is
versatile bottom-up nanofabrication technique, the LbL self-
reversed, which enables deposition of a subsequent layer.
assembly technique has been explored in the development of
The process leads to the formation of a final multilayer
multiscale and highly active materials such as nanostructured
structure that is stabilized primarily by strong electrostatic
titania for solar cells,37,38 hierarchically structured mesoporous and
force. Fig. 1 shows a typical LbL self-assembly process of a
nanosheet electrodes for lithium-ion batteries,39–41 mesoporous
multilayer thin film structure by sequential adsorption of
carbon supports and catalysts for fuel cells42,43 and hierarchical
oppositely charged PEs. LbL deposition can also be driven
and porous carbon or oxide nanostructure for supercapacitors.44–46
by hydrogen bonding.8–10
As a remarkable example, Li et al.47 constructed a self-assembled
LbL has quickly received growing attention as an effective,
nanofilm of graphene/quantum dots as a photovoltaic device
simple and environmentally benign way to develop advanced
which reached the best performance of carbon/quantum dot
surface coatings, novel materials with nanoscopically controlled
solar cells, with IPCE of 16% and 1.08 mA cm 2 under light
structure and nanopatterns, and mesoporous and nanoparticles-
illumination of 100 mW cm 2. For recent development of
based materials for catalytic applications.11,12 The major advan-
advanced and nanostructured materials via LbL self-assembly
tage of the LbL self-assembly is its simplicity and low cost.
technique for solar cells and batteries, readers are encouraged
The variability of the applicable materials is another of the
to refer to recent reviews.15,48,49
most prominent advantages of this method. In addition to
Fuel cells are one of the leading technologies for future
power generation.50 Fuel cells are electrochemical energy
conversion devices which transform the chemical energy of
Prof. San Ping Jiang is a full fuels such as hydrogen, natural gas, methanol, etc. to electri-
professor in Chemical Engi-
city, and hence, fuel cells inherently have a significantly higher
neering and deputy director
of Fuels and Energy Techno- efficiency than that of conventional energy conversion tech-
logy Institute, Curtin Univer- nologies such as the internal combustion engine (ICE). Fuel
sity, Australia. Dr Jiang obtained cells are considered to be the most efficient and less polluting
his BEng in Materials Science power-generating technology, and are thus potential and viable
and Engineering from South candidates to moderate the fast increase in power requirements and
China University of Techno- to minimize the impact of the increased power consumption on the
logy and PhD in Electro- environment. Fuel cells are also versatile devices ranging from
chemistry from The City room-temperature fuel cells such as proton exchange membrane
University, London under fuel cells (PEMFCs) to high-temperature (500–1000 1C) solid oxide
Prof, Alfred C. C. Tseung. fuel cells (SOFCs). The other advantages of fuel cells are their
Before joining Curtin in
quiet operation and flexible modulability.
San Ping Jiang 2010, he worked in CSIRO
Materials Science and Manu- Among various fuel cells, PEMFCs are considered to be the
facturing in Melbourne, Australia and Nanyang Technological most promising power sources for applications ranging from
University in Singapore. His main research interests are on the portable electronic devices, vehicle transportation to station
fundamentals understanding and development of nanostructured power due to their low operating temperature and fast start-up
materials for use in fuel cells and supercapacitors. and shut-down cycle.51,52 The core component of a PEMFC is
7292 Chem. Soc. Rev., 2012, 41, 7291–7321 This journal is c The Royal Society of Chemistry 2012
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a membrane-electrode assembly (MEA) with the electrocatalytic This review will start with the brief outline of the LbL
anode and cathode separated by a proton exchange membrane. self-assembly processes commonly used in fuel cells and super-
The challenges in PEMFCs arise from the need for inexpensive, capacitors. The synthesis of new PEMs based on LbL
more active and durable proton exchange membranes (PEM) self-assembled multilayer films and surface modification of
and electrocatalysts. The PEM has the essential function of a PFSA-based PEMs such as Nafion to enhance the resistance
proton-conductive medium as well as a barrier to prevent the to the methanol crossover will be reviewed in detail. This is
mixing between fuel and oxidant. The state-of-the-art PEMs followed by the most recent developments in the synthesis and
are based on perfluorosulfonic acid (PFSA) such as Nafions, demonstration of new and highly effective electrocatalysts
invented in the 1970s by DuPont.53 The structure of Nafion, based on LbL self-assembled Pt-based nanoparticles on functiona-
with a unique skeleton of a hydrophobic C–F backbone lized carbon nanotubes and graphenes. The development of novel
combined with hydrophilic –SO3H graft chains, imparts high-temperature PEMs for operation at elevated temperatures and
exceptional oxidative and chemical stability and high proton new electrode materials for electrochemical supercapacitors
conductivity. However, in the case of PEMFCs using liquid via the self-assembly synthesis principle will also be discussed.
methanol fuel or direct methanol fuel cells (DMFCs), methanol
readily migrates from the anode, through the Nafion 2 Factors in LbL self-assembly process
membrane, to the cathode, reducing the open-circuit potential
(OCP) by as much as 0.15–0.2 V and poisoning the electro- Self-assembly is essentially driven by non-bonding interactions
catalysts at the cathode.54 The methanol crossover of Nafion (electrostatic, dispersive, hydrogen bonding, coordination
based membranes can be suppressed by use of conventional interactions) without the disruption of the existing bonds
hybrid composites or surface modification such as by surface within the organic or inorganic molecular building block.
deposition with a Pd-based thin film,55 recasting with inorganic Although the practical application of LbL self-assembly has
nanoparticles to form Nafion/sulfonated montmorillonite progressed very rapidly due to its simplicity and high versati-
composite,56 formation of multilayered Nafion/sulfonated lity, the interactions that drive the self-assembly process, such
poly(ether ether ketone) (SPEEK),57 and composite membranes as electrostatic and hydrogen bonding, are still not fully
such as Nafion/silica.58 The modification of Nafion membrane understood from the theoretical point of view. For example, it
in general reduces the methanol crossover. However, the is still open to question as to the extent to which the stabilization
incorporation of inorganic nanoparticles such as montmorillo- energy of such an assembly is governed by electrostatic inter-
nite and silica inevitably alter the microstructure of Nafion, actions, or whether charge-transfer between proton donating and
resulting in the deterioration in mechanical properties and accepting groups is an essential factor for hydrogen bonding.65
proton conductivity, particularly in the case of non-conducting Fundamental and theoretical understanding of the self-assembly
inorganic particles. Pt-based electrocatalysts synthesized with is beyond the scope of the present review. In this context, a recent
conventional techniques such as sol–gel method59,60 generally review by Otero et al. on the extensive use of scanning tunneling
show poor microstructure and high agglomeration with little microscopy offers some insight on the molecular arrangement
control on the nanoparticle distribution. and interactions of organic materials on solid surfaces.66 Thus in
Compared with conventional hybrid and synthesis methods, this section, only the main factors such as the molecular structure
LbL self-assembly provides an alternative technique to develop of PEs, as well as the pH and ionic strength on the electronic
and synthesize multiscale and nanostructured films or nanosized and/or ionic conducting properties, multilayer structure and
catalysts particles with molecular level control. For example, it stability of LbL self-assembled multilayers will be discussed.
has been demonstrated that LbL self-assembly of polyelectrolyte
2.1 PEs
multilayered thin films is very effective to substantially suppress
the methanol permeability of Nafion membranes with minimum There are a significant number of PEs which can be used as
detrimental effect on the proton conductivity properties, as building blocks in the LbL self-assembly process. Fig. 2 shows
compared to conventional hybrid composite methods.61–63 some of the most common PEs used in fuel cells and electro-
Under acidic environments, only Pt-based electrocatalysts chemical supercapacitors. PEs with different degrees of hydro-
have the high catalytic activity and stability to meet the philicity, basicity and charge density will significantly affect
requirement of PEMFC. However, the high cost and scare their assembly behavior. In general, the less hydrophobic the
resources of precious metals impose serious challenges of the PEs, the more conductive to H+ they are. For instance, the
commercial viability of the electrochemical energy conversion PDDA–PSS couple (proton conductivity, s o 10 9 S cm 1) is
and storage technologies. How to reduce the loading of characterized by a strong hydrophobic electrostatic interaction
precious metal catalysts or to find alternative non-precious between the ternary ammonium group [–N–+] of PDDA and
metal catalysts is a most critical issue for PEMFC development. the sulfonate group [–SO32 ] of PSS, leaving no space for proton
LbL self-assembly offers alternative approaches for the develop- conduction across the PE segments. Replacing the PDDA by
ment and synthesis of highly dispersed and novel Pt-based LPEI, which has a heteroatomic backbone consisting of secondary
electrocatalysts, which would significantly reduce the usage of Pt ammonium groups [–NH–+] that are more hydrophilic, induces
and thus the cost of PEMFCs. For instance, Jiang et al.64 reported weaker interactions with the sulfonate group of PSS and proton
the development of uniformly distributed Pt nanoparticles on transportation is moderately facilitated across the medium. Farhat
carbon nanotubes (CNTs) with average size of 2 nm and high and Hammond showed that when PSS was replaced by PAA,
Pt loading of 60–80 wt% using a self-assembly process, which LPEI/PAA deposited on a nucleopore substrate has a conductivity
would not be possible with conventional deposition methods. of 3.26 10 5 S cm 1, higher than 1.23 10 5 S cm 1, measured
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Fig. 2 Chemical structures of polyelectrolytes commonly used to assemble multilayer films. Polycations: poly(allylamine hydrochloride) (PAH),
linear poly(ethylene imine) (LPEI), poly(4-vinylpyridiine) (P4VP), poly(diallydimethylammonium chloride) (PDDA). Polyanions: Nafion,
poly(sodium styrene sulfonate) (PSS), poly(1-(4-(3-carboxy-4-hydroxyphenylazo)benzene sulfonaimdo)-1,2-ethanediyl, sodium salt) (PAZO),
sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (sPPO), poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS), poly(acrylic acid)
(PAA), poly(vinyl sulfate) (PVS).
at 23 1 1C, 100% RH on LPEI/PSS films, as PAA is more proton conductivity of LbL self-assembled Nafion membranes.
hydrophilic than PSS.67 In addition, the amide group would Jiang and Tang71 studied LbL self-assembly of PEs on Nafion
also act as a hydrating agent, adsorbing water molecules membrane by UV-vis spectroscopy. Fig. 3 shows the UV-vis
generated at the cathode and thus enriching the LbL film with spectra of LbL self-assembly of PE bilayers on Nafion 112 with
water channels across which the hydronium ions can readily PDDA (polycation) and polyanions of PSS, PAZO, PAMPS
propagate.67 PDDA/PAMPS possesses a hydrophobic electro- and PAA as a function of the number of bilayers.71 For
static interaction between the tertiary ammonium group of PDDA–PSS bilayers (Fig. 3a), absorbance at 229 nm is most
PDDA and the sulfonate group of PAMPS, however, it delivers likely related to the characteristic wavelength of 228 nm for the
approximately four times the power of LPEI/PSS with the same sodium styrene sulfonate ionomers.72 Since PDDA is almost
thickness of multilayers, as PAMPS possesses a polar amide transparent in the UV-vis spectral range, the increase in absor-
group [–CO–NH–] that is strongly hydrophilic.68 bance was attributed to the absorption of PSS on the previously
Moreover, the proton conductivity of a LbL self-assembled self-assembled PDDA layer. The absorbance at 229 nm as a
multilayer composite membrane is influenced by both the function of the number of PDDA–PSS bilayers increases
concentration and mobility of the proton carrier. Highly linearly with the number of LbL self-assembled PDDA–PSS
charged PEs would lead to an improvement in the number bilayers, which indicates that the same amount of PE is
of proton carriers which will promote proton conduction deposited in each dipping cycle and the multilayer is formed
along the membrane.69 The charge density can be expressed in a regular manner. A linear dependence of the absorbance
in terms of the number of ion pairs per number of carbon on the number of bilayers was also observed for the LbL self-
atoms in the repeating unit of the complex formed by the assembled PDDA–PAZO and PDDA–PAMPS bilayers on
polycation and polyanion. Recently, Yilmaztürk et al.70 Nafion (Fig. 3b and c).
pointed out that the proton conductivity of self-assembled However, in the case of LbL self-assembly of PDDA–PAA
PAH/PVS with five bilayers, (PAH/PVS)5 was nearly twice bilayers on Nafion, the intensity of the absorbance does not
that obtained on (PAH/PSS)5 due to the higher charge density follow the linear relationship as observed for other PDDA–
of PAH/PVS as compared to that of PAH/PSS. polyanion bilayers. Rather, the absorbance increases exponen-
On the other hand, the growth mechanism of the LbL self- tially with the number of self-assembled PDDA–PAA bilayers,
assembled PE multilayer is related to the structure of the PEs, which suggests the exponential growth of the self-assembled
and this in turn strongly affects the methanol permeability and bilayer. In other words, subsequently deposited layers contain
Fig. 3 UV-Vis spectra of a LbL self-assembly of PE bilayers on Nafion 112 with PDDA polycation and polyanions of (a) PSS, (b) PAZO, (c)
PAMPS and (d) PAA. The inset is the plot of the intensity of characteristic absorbance as a function of number of PE bilayers. Reproduced with
permission from ref. 71. r2012, Elsevier.
more PE material than the previous one, which indicates a bilayers of PAH (pH 5.5)/PSS (pH 1.8) was 2.02 10 2,
very different structure of the multilayers in comparison with 1.65 10 2 S cm 1 deposited in assembly solutions of 10 1,
that of the linear growth.73,74 Consequently, the exponential 10 3 PE monomol concentrations, respectively. That is con-
growth process of PDDA–PAA bilayer films on Nafion resulted tributed to the reduced concentration of sulfonic groups
in the best methanol-blocking ability among the polyanions of PSS that would facilitate the proton transfer through the
investigated. Overall, in the case of linear growth process, the self-assembled composite membrane.77
PEs from the solution interact solely with the outer layers of The exponential growth of thickness of bilayers is mainly
the film without diffusing into its multilayer architecture.75 caused by the interdiffusion of building blocks during the
However, in the case of the exponential growth process, the assembly, and diffusivity is determined by interactions that
thickness and mass of the bilayers increase exponentially with can be controlled by assembly conditions such as pH and
the number of the deposition steps.76 This shows that methanol salt concentration, as shown recently by Yuan and Li on the
migration or diffusion through the LbL self-assembled PE LbL self-assembly of pH-sensitive hierarchical nanoporous
bilayer on Nafion is very much dependent on the PE bilayer polymeric films for enhanced responsive drug release.78
structures.
Besides PDDA–PSS multilayers, PAH/PSS multilayers
2.2 pH
deposited on Nafion 117 membrane also exhibit a linear increase
absorbance with the number of the deposited bilayers. Moreover, Modulating assembly pH can influence film composition as
the UV-vis absorbance value of the self-assembled composite well as morphology and cross-link density due to changes in
membranes increase in the order of 10 1 4 10 2 4 10 3 degree of ionization with pH. Increasing the charges of PEs by
monomol PE concentration, which due to the fact that more reducing the pH values results in an extended chain conforma-
concentrated PE solutions provide more electrostatic adsorption in solution; this leads to changes in its composition in the
tion of PSS and Nafion molecules.77 In other words, the higher LbL film. In LPEI/PAA films, PAA ionization increases and
the concentration of the PE, the thicker will be the deposited LPEI ionization decreases with raised pH, which in turn
bilayers. On the other hand, with the increase in thickness of increases the proportion of LPEI in the bilayer and decreases
deposited bilayers, the proton conductivity of the composite the proportion of PAA. Therefore, at low pH, LPEI is fully
membrane would decrease due to effectively blocked charge ionized, and thick PAA layers will be deposited, and on the
carriers. Thus, it is expected that a high monomol concen- other hand at high pH PAA ionization increases and thick
tration would cause a reduction on proton conductivity of LPEI layers will be deposited. It was found that at an
Nafion-based multilayer composite membranes. Nevertheless, optimum pH of 4, both LPEI and PAA are partially ionized,
the proton conductivity of self-assembled membranes with five and thick bilayers can be formed through adsorption.68
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Low pH is beneficial to the degree of ionization of the polar

groups of many PEs such as the amino groups in PAH and
LPEI.79 The amino groups of PAH dissolved at low pH are all
protonated80 so that the adsorption of PAH leads to high
concentration of positive charges at the membrane surface.
Consequently, more polyanions such as PSS, will be absorbed
in the subsequent dipping step. Furthermore, a higher pH

value of PAH results in partial protonation80 and adsorption
of less negatively charged PE on the membrane surface so that
the self-assembled multilayers will be thinner, which in turn
leads to minimal detrimental effect on proton conductivity
of the composite membrane. For instance, multilayer films
with 10 bilayers deposited on Nafion at PAH (pH 1.8)/PSS
(pH 1.8) were much thicker than that of films of PAH
(pH 5.5)/PSS (pH 1.8), whereas the proton conductivity is
1.37 10 2 S cm 1, 1.88 10 2 S cm 1 at 25 1C, respectively.77
Similarly, at low pH, LPEI charge density increases due to
increasing secondary amine protonation, whereas at more basic
pH, LPEI charge density decreases. Thus, when pH is less than
2 in a strong polyacid system, LPEI/PAMPS and LPEI/Nafion
LbL films were thinner than 1 nm per bilayer, while when pH
increased to the most favorable value at pH 4, the films were
5–20 nm per bilayer.68
Self-assembly of biomaterials is also very sensitive to pH of
the assembly solutions. Xiang et al.61 showed that the pH of
the assembly solution impacts both the charge and attitude of
purple membrane (PM) pitches via zeta potential (Fig. 4a).
The zeta-potential value is positive at relatively low pH values
while as the pH values reaches above the isoelectric point, the
zeta-potential gradually decreases and becomes negative after
the solution becomes alkaline. On the other hand, as the pH
value increased from 6 to 10, the absorbance of PDDA/PM
bilayers at 568 nm increased sharply with increase of the pH of
the PM solution until it reaches a maximum at pH 9.4, as
shown in Fig. 4b, and a dense, homogenous multilayers was Fig. 4 (a) Zeta-potential of PM solution as a function of pH,
(b) UV-vis adsorption spectra of (PDDA/PM)4 with various pH values
formed on both sides of Nafion membrane after alternating
of PM solution and (c) SEM cross-sectional image of (PDDA/PM)DF
assembly of PDDA and PM (Fig. 4c). Either higher or lower
multilayer film with 30 bilayers deposited on Nafion membrane
pH caused the PM fragments to agglomerate or shrink, which surface at pH 9.4 of PM solution. Reproduced with permission from
results from the fact that PM in acidic and neutral media is ref. 61. r2011, Elsevier.
insufficient to generate enough coulombic force to sufficiently
interact with the cationic charges in the PDDA layer.81 of the films without salt but lower than that when 0.5 M NaCl
was present in assembly solutions.82 The increase in thickness
is termed screening-enhanced adsorption, and is generally
2.3 Ionic strength
attributed to a change in PE solution conformation; upon
Ionic strength and types are also essential factors that affect the charge screening, the PE transforms from an extended
film growth, proton conductivity and methanol permeability of conformation to a more globular, coiled conformation that
assembled multilayer films. The addition of salt to the assembly deposits more quickly. The reduction in thickness is called
solutions shields charge on the deposited PE film, resulting in screening-reduced adsorption, and it is generally attributed to
thicker bilayers and higher growth rates as well as lower ionic binding competition and Coulombic shielding at the deposi-
cross-linking densities. Fig. 5 shows the growth rate of PDDA/ tion surface from highly concentrated small ions, which
sPPO films on glass slides.82 The growth rate increased from effectively block PE adsorption.68
6.91 nm/bilayer with no salt in either assembly solution to The proton conductivity could be simply varied by salt
42.9 nm/bilayer when assembled in 0.2 M NaCl in both condition during the LbL self-assembly process. Durstock
assembly solutions. Films assembled in 0.5 M salt in assembly and Rubner studied self-assembly of PAH/PSS films and
baths have a growth rate of 62.2 nm/bilayer, showing the achieved a maximum conductivity of 3.0 10 8 S cm 1 at
variation of the growth of this system through modulation of 90% RH and 21 1C.83 The results indicate the dependence of
the ionic strength of the assembly solutions. In addition, when ion transport on assembly conditions and water plasticization
0.5 M NaCl was added to sPPO assembly solution, PDDA/ in those systems. Farhat and Schlenoff84 showed that doping
sPPO films grew at 24.0 nm/bilayer which is higher than that the multilayers with additional ions after self-assembly could
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to the PE solutions has a positive effect on reducing the

methanol crossover.92 Thus, the methanol permeation rates
of the composite membranes containing salt decrease with the
number of adsorbed layers.70 Furthermore, different salt ions
also affect the methanol permeation in multilayered composite
membranes. Buron et al. showed that divalent ions have a
strong influence on the amount of PE adsorbed. Despite

the significant differences in the nature of the divalent ions
(e.g., Ba2+ or Zn2+), divalent salt ions form thicker multilayers
than monovalent salt ions.93 However, the increase of the salt
concentration may reduce the methanol blocking effect, as the
presence of high amounts of salt ions on the membrane surface
will cause more uptake of water and methanol.92
Fig. 5 Growth curves for PDDA/sPPO at several different assembly 3 PEMs by LbL self-assembly
conditions. The salt concentration given is for all assembly baths, both
polymer solution and all rinse water, except for one film made with In the development of DMFCs technologies, high methanol
only salt in the sPPO solution (*). All films exhibit linear growth after permeation of PEM is a critical concern, which not only
a delayed growth period of 5–10 bilayers. Reproduced with permission reduces the cell voltage due to a mixed potential at the
from ref. 82. r2010, The Royal Science of Chemistry. cathode, but depresses fuel cell efficiency and poisons cathode
catalysts.94 Although increase of thickness of the membrane
accelerate the ion transport. Under conditions of high salt can lead to the reduction in methanol crossover, use of thick
concentration and strong polymer ion pairing, the exchanger membranes will increase the membrane cost and also increase
site concentration is proportional to the solution salt concen- the membrane resistance and swelling.95 There is a continuing
tration. When multilayers were deposited with salts, the effort in the modification on Nafion based PEMs to suppress
proton conductivity was significantly improved because of the methanol permeability based on the conventional hybrid
the reduction of ionic cross-linking. Moreover, the proton composite membrane approach.56–58 The modification of
conductivity of multilayers would decrease when the ion type Nafion membranes in general reduces the methanol crossover.
was inverted from the proton form to the salt form. The However, the incorporation of inorganic nanoparticles such
transportation mechanism of methanol molecules and protons as montmorillonite and silica inevitably alters the microstruc-
through Nafion-like perfluorosulfonated ionomers depends on ture of Nafion, resulting in the deterioration in mechanical
the ion type and equivalent weight of membranes,85–87 and the properties and proton conductivity, particularly in the case of
proton transport by the hopping mechanism is facilitated by non-conducting inorganic particles. Recent results showed that
the increase of the alcohol content and the decrease of the negative-charged microscale protein patches, for example purple
molecular weight.88 The mobility of proton forms is 6–9 times membrane (PM), polypeptide self-assembly on the surface or in
higher than that of other alkali cations, such as Na+ and the bulk of Nafion membrane, are very effective to inhibit
Mg2+. Yilmazturk et al.89 observed significant improvements methanol crossover through the membrane.96,97 In this section,
on conductivity from 2.1 10 2 to 8.8 10 2 S cm 1 when the modifications and fabrication of PEMs via electrostatic
the LbL self-assembled (PAH/PSS)5 composite membranes LbL self-assembly technique are reviewed with respect to the
were inverted from (PAH/PSS)5–Na+ in salt form to (PAH/ enhanced properties towards the methanol crossover and
PSS)5–H+ in proton form at 22 1 1C. On the other hand, the proton conductivity.
higher the salt concentration, the lower the proton conductivity Table 1 lists various self-assembled PEs multilayers and their
of the multilayer films would be, because the number of proton effect on proton conductivity and methanol-blocking properties.
carriers and the mobility of the inverted salt form are reduced.
3.1 Standalone PEMs
That is probably the reason why the proton conductivity of
(PAH/PSS)5–Na+ containing 1.0 M NaCl is 1.3 10 2 S cm 1, The simplicity and efficiency of the LbL technique has resulted
lower than 2.1 10 2 S cm 1 measured on (PAH/PSS)5–Na+ in a wide range of applications of multilayers for fuel cells.
containing 0.1 M NaCl at 22 1 1C.89 With the LbL self-assembly technique, a ultrathin composite
Besides film growth and proton conductivity, the methanol PEM structure of self-assembled LPEI/PAA on plasma-etched
diffusion rate also changes with ion concentration and salt nucleopore membrane was synthesized as supporter for use in
types. In Nafion-based PEMs, methanol diffusion rate and the a hydrogen fuel cell.67 The LPEI/PAA membrane multilayer
proton conductivity are in a trade-off relationship with each films deposited on the nucleopore membrane with regular
other as they have a similar transportation mechanism in the 100 nm diameter pores has a total membrane thickness of
Nafion membrane.90 Salt ions are primarily associated with 10 mm. At 100% RH, water fills the pores of the nucleopore
–SO3 clusters on the Nafion membrane surface, and would membrane, enhancing ion conduction within the PEM, while
block the channel of methanol transportation. It is reported the LPEI/PAA multilayers isolate hydrogen and air and
that the cationic form (Na+ etc.) of Nafion strongly reduces conduct protons efficiently. The resulting hydrogen–air fuel
the methanol and water permeability values as compared to cell, operating at 55–75% RH, yields a power density of
that of the proton form.91 Therefore, the addition of salt ions 5.5 mW cm 2 and PEM conductivity of 3.26 10 5 S cm 1.
View Article Online
Table 1 Various PEs combinations for self-assembly multilayers and their effect on proton conductivity and methanol crossover
Proton Methanol
1
Substrate PE Test conditions conductivity/m S cm permeability/cm2 s 1
Ref.
a 4
Nucleopore (LPEI/PSSM)40 23 1 1C, 90–95% RH 9.6 10 67
(LPEI/PSS)40 0.012
(LPEI/PAMPS)40 0.016
(LPEI/PAA)40 0.033
8
Nafion 117b (PAH/PVS)5 22 1 1C in water 68.8 41.6 10 70
8
Nafion 112b (PAH/PSS)5 30 1 1C in water 27.0 7.67 10 92
Nafion 1135b (PDDA–PSS)8 30 1C in water 106 63
(PDDA/PAZO)5 71.0
8
(PDDA/sPPO)30 30 1C, 98% RH 35.3 2.18 10 98
8
(PAH/sPPO)30 4.23 0.57 10
8
(LPEI/sPPO)30 2.12 1.38 10
8
(P4VP/sPPO)30 1.65 0.84 10
8
Nafion 117b (CS/SPAEK-C)5 25 1C in water 77.0 79.0 10 99
8
c-(CS/SPAEK-C)5 70.0 27.0 10
8
Nafion 212a (PDDA/PM)5 23 1C in water 3.29 31.6 10 61
8
(PDDA/HPW)3 4.10 110 10 62
b 8
SPAEK-C (CS/HPW)4 25 1C, 100% RH 81.0 15.0 10 30
8
(PPy/HPW)4 20 1C in water 21.0 2.53 10 100
8
(PANI/HPW)5 25 1C, 100% RH 93.0 4.60 10 101
a b
Through-plane conductivity. In-plane conductivity.
Fig. 6 shows an SEM image of the LbL self-assembled LPEI/ multilayer modified Nafion membrane cells in methanol.63
PAA multilayers and the corresponding performance of Nafion has a dual structure with hydrophobic regions inter-
the cell in H2.67 Though the reported LPEI/PAA proton spersed with ion-rich hydrophilic domains, and methanol diffuses
conductivity is three orders of magnitude less than that of primarily through the hydrophilic water-rich domains.106 Thus,
Nafion at similar conditions, it produces higher power than blocking the water-rich domains, which are primarily associated
a conventional single cell based on volume. Patterned layer- with –SO3 clusters on the Nafion-membrane surface, would
by-layer fuel cells are attractive as power sources for micro- inhibit methanol crossover. Owing to the existence of a
electronic processes. negatively charged sulfonic acid group, SO3 , on the surface
of the Nafion membrane, self-assembly of positively charged
polycation occurs as the result of the electrostatic interaction
3.2 Surface engineering and enhancement of PEMs
(Fig. 7a).
3.2.1 PE multilayer modified PEMs. Jiang and co-workers63 With an increasing number of PDDA–PSS bilayers, the
applied LbL self-assembly techniques to modify the surface of OCP is 0.56 V, slightly higher than 0.54 V for the cell with
Nafion membranes to reduce the methanol permeation. Very an unmodified N1135 membrane. This is most likely owing to
different from the conventional approaches to incorporate the reduction of methanol crossover. The best performance
hygroscopic metal oxide particles such as SiO2, TiO2 and was observed for the DMFC that used an N1135 membrane
zirconium phosphate into the hydrophilic domains of the PFSA with four self-assembled PDDA–PSS bilayers, achieving a
membranes to enhance the resistance to methanol permeability power density of 37 mW cm 2 (Fig. 7b). This is an increase
at the cost of durability,102–105 the LbL self-assembled PE of 42% in power output when compared to the cell using an
multilayer films on Nafion has no detrimental effect on the unmodified N1135 membrane (26 mW cm 2).
thermal and chemical stability of the Nafion membranes. Fig. 7 The proton conductivity of Nafion membrane normally declines
shows the scheme of the LbL self-assembled multilayer on Nafion with the increase of LbL self-assembly of PE multilayers. How-
membranes and the power output from LbL self-assembled ever, compared to other methanol blocking methods, the loss with
Fig. 6 (a) An LbL film absorbed on a nucleopore membrane with pore size 100 nm; (b) polarization curve for a hydrogen fuel cell using an LbL-
nucleopore membrane as PEM; (J) PEO-PAA, (m) PDAC-PAMPS, (n) LPEI-PAA LbL films. Reproduced with permission from ref. 67.
r2005, John Wiley and Sons.
Fig. 7 (a) Schematic diagram of the structure of a LbL self-assembly of oppositely charged polycations and polyanions on a Nafion electrolyte
membrane, showing blocking of the methanol crossover; (b) polarization curves and power output of a DMFC using an unmodified N1135
membrane, and N1135 membranes modified with LbL self-assembled PDDA–PSS and PDDA–PAZO bilayers, measured at 30 1C in 2 M CH3OH,
0 psi; cathode, oxygen, 10 psi. Reproduced with permission from ref. 63. r2006, John Wiley and Sons.
LbL self-assembly multilayer in the proton conductivity be reduced by an appropriate combination of polycation and
appears to be relatively small. After the self-assembly of eight polyanion pairs.
PDDA–PSS bilayers, the proton conductivity was 1.06 Hammond et al.98 assembled sPPO on Nafion with different
10 1 S cm 1, a decrease of 15% compared with that of a polyanions with various degrees of hydrophilicity and basicity
pristine Nafion 1135 membrane.63 However, the detrimental ranging from LPEI, PAH, PDDA (or PDAC) and P4VP (Fig. 8).
effect of the LbL self-assembled polyelectrolyte bilayers on the With the optimized assembly conditions, the sPPO/PDAC
conductivity of the membrane also depends on the nature of achieved high conductivity values of 3.53 10 2 S cm 1
the polyelectrolyte bilayers. In the case of a Nafion 1135 and methanol permeability values two orders of magnitude
membrane modified with self-assembly of five PDDA–PAZO lower than Nafion 1135. Assembly of a LbL film of sPPO and
bilayers, the reduction in conductivity is 43%, significantly PDAC to a Nafion 1135 membrane resulted in the DMFC
higher than that with PDDA–PSS bilayers. The most likely power output at 0.3 V improving by 53.2%.
reason could be that PAZO is a comb-like polymer, and its Although sulfonated PEs are often used in LbL self-assembly
layer thickness is greater than that of PSS, which contains processes due to their high proton conductivity and low methanol
smaller monomeric blocks.107 The much smaller decrease on permeability, high proton conductivity is often accompanied
the conductivity in the case of self-assembled PDDA–PSS with high water swelling because of the high sulfonation
bilayers could also result from the fact that the PSS contains degree, which means a loss of membrane mechanic strength
a sulfonic acid group, which may serve as a proton conductor. and stability. Cross-linking is an effective method to increase
Overall, the negative effect on the proton conductivity can strength and stability of the LbL self-assembled multilayers.
Fig. 8 (a) SEM cross-sectional image of Nafion 1135 coated with 50 bilayers of PDAC/sPPO and (b) power curves of single MEA DMFCs
comparing unmodified Nafion devices with Nafion membranes coated with LbL films of LPEI/sPPO and PDAC/sPPO. Reproduced with
permission from ref. 98. r2008, John Wiley and Sons.
View Article Online
For instance, PAH/PAA could be cross-linked by heating Chitosan with both amino and hydroxyl groups and polypyr-
these membranes forming amide bonds.108 Similarly, chitosan role (PPy) that has high catalytic activity for the methanol
(CS) and sulfonated poly(aryl ether ketone) bearing carboxyl oxidation, have been assembled with PWA respectively onto
groups (SPAEK-C) also has been assembled as effective the surface of SPAEK-C membrane. The CS/PWA30 and PPy/
methanol blocking agents on the Nafion surface followed by PWA100 multilayers on SPAEK-C have a similar effect to
cross-linking treatment. Cross-linking between ammonium PDDA/PWA in the Nafion system in proton conductivity and
groups of CS and carbon groups of SPAEK-C occurs by methanol blocking properties. On the other hand, polyaniline
formation of an amide bond. After cross-linking between CS (PANI), an electro-conducting polymer, when self-assembled
and SPAEK-C, the water swelling and methanol permeability with PWA to SPAEK-C, exhibited a proton conductivity
were drastically reduced as compared to PEC-coated and of 9.3 10 2 S cm 1 with five PANI/PWA bilayers while
Nafion membranes.99 the proton conductivity of pristine SPAEK-C was only 7.4
Besides PEs, some proteins also can be oriented on the 10 2 S cm 1.101 Since PANI and PWA have strong affinity
membrane surface as effective methanol-blocking agents. toward water, the PANI/PWA multilayers can give rise to
Purple membrane was first self-assembled onto Nafion 212 hydrophilic regions on the membrane support and the hydro-
surface via LbL self-assembly technique. A linear increase at philic areas formed around the cluster of polycation and
568 nm with typical protein UV-vis absorbance and SEM polyanion lead to absorption of water, enabling easy proton
morphology suggested highly-ordered PM multilayers, as transfer. Therefore, protons passing through the hydrophilic
shown in Fig. 4.61 Xiang et al. studied the effects of two-sides regions of the multilayers are responsible for the increase in
and only anode-side PM modification on conductivity and cell proton conductivity for the modified SPAEK-C membranes in
performance and reported a substantial reduction in methanol comparison with pristine SPAEK-C membrane.
crossover up by 73.4%.61 Cell performance with PM single- Some metal nanoparticles, such as palladium, gold and
layer modified Nafion membrane was improved by 48.4%. platinum have been used as methanol-blocking agents for
This is probably the first report about successful application of Nafion membranes. Palladium has the unique properties that
functional proteins on fuel cell membranes. This biological are permeable to protons, but resistant to methanol transport.
composite membrane demonstrated performance stability Protons can be discharged at the interface between the anode
over 400 h operation time which further identified its stability catalytic surface and electrolyte. The discharged protons can
and feasibility in self-assembly modification of PEMs for use be chemically absorbed as hydrogen onto the surface of the
in fuel cells. hydrogen permeable metal and the metal is transformed into
the metal hydride. In order for the hydride system to maintain
3.2.2 Nanoparticles (NPs) modified PEMs. Although individual neutrality, a proton is ejected. Hydrogen atoms diffuse across
PE bilayers self-assembled on PEMs have effective methanol these metal hydrides, and the protons are generated when
blocking properties, it is generally achieved at the cost of the hydrogen molecule is stripped of two electrons.112 Thus, Pd
reduced proton conductivity of the composite membranes. films sandwiched between Nafion membranes113 or coated on
However, the negative effect on the proton conductivity can the Nafion surfaces114,115 act as a methanol barrier. Never-
be reduced or eliminated by using an appropriate combination theless, Pd films increased the overall cell resistance, and
of polycation and polyanion. One class of highly proton unavoidable phase boundary and separation also reduce the
conducting agents is heteropolyacids. HPAs are supersonic cell performance and stability. Pd NPs through ion exchange
conductors in their fully hydrated states.109,110 HPAs are solid and chemical reduction were also added into Nafion to reduce
crystalline materials with polyoxometalate inorganic cage the methanol permeation. Unfortunately, the Pd NPs dispersed
structures, which may adopt the Keggin form with general in the Nafion membrane altered the microstructure of the
formula H3MX12O40, where typically M = P or Si, and X = W or Nafion membrane resulting in the deterioration of cell perfor-
Mo. The highest stability and strongest acidity is observed for mance and stability.112
phosphotungstic acid (H3PW12O40, abbreviated as HPW or PWA). A more effective route is to self-assemble Pd NPs onto
PWA exhibits high proton conductivity up to 0.1 S cm 1 at the surface of Nafion membrane. Charged Pd NPs can be
25 1C.111 Therefore, HPAs could substitute the non-proton prepared by reducing the metallic ions with alcohol in the
conducting PEs in the LbL self-assembled multilayer through presence of a PE such as PDDA. The Nafion membrane was
electrostatic interaction to suppress the methanol diffusion alternately dipped into the Pd–PDDA solution and Nafion
while maintaining high proton conductivity. solution. The self-assembly of Pd–PDDA NPs occurs due
Yang et al.62 self-assembled PWA and PDDA onto the to the electrostatic interaction between the positively
surface of Nafion membrane, and found that the reduction in charge Pd–PDDA NPs and negatively charged sulfonic acid
proton conductivity is relatively low as compared with PE functional sites at the membrane surface. Once the sulfonic
multilayer without proton conductor constituent, while the sites were covered by the Pd NPs, the methanol diffusion
methanol permeability decreased sharply with three PDDA– channels would be obstructed.116 Fig. 9 shows general principle
PWA bilayers. The cell performance was increased by 103% of the self-assembly of metallic NPs on the PEM surface via
with the self-assembled PDDA/PWA-Nafion membrane as electrostatic attraction.
compared to that of the pristine Nafion. Besides Nafion Au NPs functionalized with PDDA were also self-assembled
membranes, other sulfonated polymers, for example sulfo- onto the Nafion surface (PDDA/Au–Nafion) as methanol
nated poly(aryl ether ketones) bearing carboxylic pendant crossover barriers.117 Au–PDDA NPs with appropriate size
groups can be considered as supports for the assembly of PEs. (4 nm) can be anchored onto the sulfonic group clusters upon
Fig. 9 Self-assembly mechanism of metallic NPs via electrostatic on PEM substrate surface.
entering into the Nafion membrane, and effectively block polyelectrolyte membrane surface with LbL self-assembled
methanol crossover; after Au–PDDA NP modification, multilayers. Furthermore, cross-linking increases strength and
the methanol limiting current density of Nafion membrane stability of the LbL self-assembled multilayers, while assembly
decreasing from 168 to 18 mA cm 2, measured in 2 M of proton conductor heteropolyacids or metallic nanoparticles
methanol at 60 1C. Moreover, the Au-PDDA self-assembled onto the substrate can significantly reduce the negative effect on
Nafion PEMs have higher OCV and better performance than the proton conductivity of modified PEMs.
pristine Nafion 212 membrane.117
Moreover, PE functionalized Pt NPs can also be self-assembled 4 Novel PEMs structures synthesized via self-
to the sulfonic acid functional sites, SO3 at the Nafion membrane
assembly techniques
surface, forming a MEA with ultralow Pt loading (Fig. 10).118,119
Such MEA structure is also denoted as a catalyst coated The self-assembly principle has also been applied in the develop-
membrane (CCM). In conventional MEA structure, not all ment of novel PEMs structure with high proton conductivity and
Pt NPs supported on high surface area carbon are accessible to stability under elevated temperatures. High-temperature
the Nafion electrolyte and the reactant gases, leading to low proton exchange membrane fuel cells (HT-PEMFC) operated
utilization of Pt catalyst.120,121 When Pt NPs were self- at temperatures above 100 1C has several advantages compared
assembled directly to the surface of Nafion membrane and with conventional PEMFC with operation temperatures
then sandwiched between two carbon gas diffusion electrodes o80 1C, including fast electrode kinetics, high CO tolerance,
as backing layer and hot pressed to form the membrane- better heat efficiency and thermal management and simplified
electrode assembly, the self-assembled PE-stabilized Pt NPs humidification systems.126 However, the performance of
are essentially in intimate contact with Nafion electrolyte and PFSA membrane deteriorates at elevated temperatures (above
reactant gases (see Fig. 10), which is close to the ideal situation 90 1C) and under relatively low humidification because of the
of the triple access of the Pt catalyst to the protons, electrons loss of water in the membrane.127 Considerable efforts have
and reactants.122,123 For instance, MEA with Pt loading of been conducted to improve the proton conductivity of the
2.8 mg cm 2 achieved a power output of 2.3 mW cm 2 under membrane in low humidification and high temperatures. One
H2/O2 at room temperature, corresponding to a Pt utilization effective way is to recast Nafion membrane with hygroscopic
of 821 W g 1.118,124 The self-assembled Pt–PDDA/Nafion oxides128–130 to increase the water retention at high temperatures.
PEMs also showed an excellent ability in reducing the methanol Nafion-based composite membranes are usually prepared
crossover.119 Overall, the performance of the self-assembled either by recasting of mixture of Nafion ionomer and inor-
MEA was comparable to that prepared by sputtering deposi- ganic particles,131,132 or by impregnation of membranes with a
tion,125 indicating the promising potential of the development solution of inorganic precursors, followed by in situ sol–gel
of highly efficient Pt catalysts in fuel cells via the self-assembly reaction.133,134 The distribution of inorganic particles is not so
technology. However, one limitation of the self-assembled homogeneous so that the agglomeration of inorganic fillers
MEA is that the positively charged PE-stabilized Pt NPs are and formation of cracks on the surface of the composite
electrostatically attracted to the negatively charged sulfonic membrane is often observed.135 In contrast, the electrostatic
acid sites on Nafion membrane surface, that is, further assembly self-assembly LbL technique can effectively control the micro-
of additional Pt NPs would be retarded due to the coverage of structure of the composite membrane via building organized
the acid sites. aggregates, networks, or patterns with hierarchical structure
In summary, it is effective to inhibit methanol permeation of inside the matrix and avoid the aggregation of nanoparticles
PEM by blocking the water-rich domains on the sulfonated and improve the uniformity of inorganic additives, which is in
Fig. 10 Nafion 1135 membrane (a) before and (b) after self-assembly process in Pt-PDDA colloid solutions and cleaning process. (c) Schematic
diagram of the self-assembled monolayer structure of Pt NPs on Nafion membrane surface. Reproduced with permission from ref. 118. r2005,
The Electrochemical Society.
favor of improving the transportation of protons as well as low to prevent the interaction between initially formed silica
increasing the water retention under high temperature and low NPs, further aggregation of silica NPs would occur. With the
humidification. increase of Nafion concentration, self-assembled Nafion layer
on the silica surface stabilizes the initially formed silica
nanoparticles, forming uniformly distributed Nafion-silica
4.1 Oxide NPs composite PEMs
NPs. Further increasing concentration of Nafion resulted
It is well known that incorporation of hygroscopic metal in the formation of silica NP clusters.139 Moreover, the
oxide particles could improve the thermal stability and water- hydrolysis procedure has also significant influence on the size
retention properties of PFSA membranes such as Nafion at and distribution of SiO2 NPs and the quality and performance
elevated temperatures. However, interface compatibility between of the composite membrane. Although water acts as both
the inorganic NPs and the PEM is critical for the water-retention reagent and solvent in the hydrolysis reaction, excess water
property and durability of the composite membranes. Well in the solution would dilute the Nafion content, reducing the
developed hybrid membranes require the uniformly and well self-assembly between the silica particles and Nafion ionomers. Best
distributed additives in the membrane to minimize the interfacial results were obtained on the Nafion–SiO2 composite membrane
resistance of the matrix and doped agents. The Nafion composite recast from Nafion–SiO2 (5 wt%) NPs with a H2O : TEOS
membranes prepared by the conventional blending method ratio of 4 : 1.140
reduce the methanol crossover and improve the water retention Besides silica, other metal oxide NPs141–143 such as zirconia
properties, however, the distribution of inorganic particles is and titania formed through sol–gel process in Nafion disper-
not satisfactory and phase segregation is a serious concern.136 sion via self-assembly technique also showed promising results
Tang et al.137 developed a novel Nafion–SiO2 composite in high-temperature PEMs. The doped metal oxide NPs did not
membrane based on self-assembled Nafion–SiO2 NPs with affect the crystallinity and structure of Nafion in the membrane
average size of 2.8 0.5 nm (see Fig. 11). With the assistance significantly while the inorganic–organic hybrid membranes
of Nafion ionomers, self-assembly occurs between the positively exhibited better water maintain properties in comparison
charged inorganic particles (SiOH2+ etc.) and Nafion with with pure Nafion membrane. For example, at a temperature
negatively charged sulfonated end groups, –SO3 , by electro- of 100 1C, the proton conductivity of ZrO2 doped PEM is
static forces in acidic conditions.138 The Nafion assembled on close to 0.01 S cm 1 without external humidification,141 while
the silica NPs surface reverses the surface charge, stabilizing the proton conductivity of TiO2 doped Nafion membrane is
the nanoparticles and preventing particle cohesion and five times higher than that of recast Nafion membrane.143
grain growth. An intimate interface between the Nafion–SiO2 Compared with TiO2 NPs, the addition of TiO2 nanotubes
particles and the Nafion matrix was achieved, which resulted changes more markedly the physical properties of the composite
in much better durability of the composite membrane than electrolyte, a feature which is probably related to the intrinsic
that of Nafion 212 and conventional Nafion–SiO2 composite hydration and proton conductivity of the nanotubes.144 Titania
membranes under an accelerated wet/dry RH cycling test. nanotubes contain a large amount of hydroxyl groups that
Moreover, the cell performance of the self-assembled Nafion–SiO2 contribute to the higher water absorption of TiO2 nanotubes
composite membrane were significantly enhanced by 46.3% as than TiO2 NPs.145 More specifically, TiO2 nanotubes, with a
compared to that of Nafion 212 membranes at cell/humidifying stacking of lamellar TiO2 octahedra intercalated with alkali
temperatures of 100/60 1C under a current density of 600 mA cm 2 cations or protons, stores water in different configurations,
in H2/air. either as crystallographic or physically adsorbed molecules.146,147
The size of Nafion–SiO2 NPs mainly depends on the Moreover, TiO2 is dispersed uniformly in TiO2 nanowire-reinforced
concentration of Nafion. Pan et al. investigated the relation- Nafion composite membranes by self-assembly between TiO2 and
ship between formation of silica NPs and the Nafion concen- Nafion at low pH condition. Proton conductivity of pure recast
tration.139 Silica NPs were formed in Nafion dispersions by Nafion membrane drastically decreased from 1.37 10 1 S cm 1
in situ hydrolysis of tetraethoxysilane (TEOS) precursor in an (80 1C, 100% RH) to 8.9 10 2 S cm 1 (90 1C, 50% RH),
acidic environment. When the concentration of Nafion is too whereas the conductivity of the nanowires-TiO2–Nafion composite
Fig. 11 Scheme illustration for the synthesis of Nafion-stabilized SiO2 NPs by the self-assembly route. The inset shows the TEM image of
Nafion–SiO2 NPs. Reproduced with permission from ref. 137. r2007, Elsevier.
membrane was stable at 1.21 10 1 S cm 1 under the same surface charge density. PWA was then self-assembled on the
conditions.148 Self-assembled TiO2 nanowires also enhance the PDDA-functionalized PhSiO3/2 particles. Then the resultant
stability of the composite membrane during fuel cell operation. core–shell particles were pressed to form an almost transparent
and monolithic pellet membrane. The proton conductivity
of PWA-deposited samples is B10 4 S cm 1 at 80 1C and
4.2 Novel proton conductor composite PEMs
80% RH, four orders of magnitude higher as compared with
Self-assembled HPA particles, being both hydrophilic and unmodified samples.151 PWA can be substituted by Nafion,
proton conducting, are effective to increase the water retention however, the proton conductivity of PDDA/Nafion-multilayer-
of PEMs in high-temperature and low-humidity conditions, coated PhSiO3/2 particles is still too low to be used as PEMs for
which would increase the proton conductivity and cell performance fuel cell.152 In order to increase the proton conductivity of the
of the composite PEM under elevated temperatures. Honma hybrid nanoparticles, a high proton conducting polymer of
and Yamada149 constructed the PWA-encapsulated material poly(2-acrylamido-2-methyl-1-propane sulfonic acid) (PAMPS)
by the self-assembly of PSS on to the PWA surface through was deposited on the (Ph2SiO) particles via LbL self-assembly.
recasting the PWA–PSS mixed solution onto a Teflon plate at A flexible sheet-like electrolyte was obtained from the resulting
70 1C for 24 h. In the PSS matrix, PWA molecules were PAMPS deposited particles by pressing, which showed a proton
encapsulated by –SO3H in PSS with a self-assembled structure conductivity of 1.0 10 1 S cm 1 at 80 1C and 80% humidity.153
and fast anhydrous proton transportation occurred between However, no cell performance was reported for PAMPS func-
–SO3H and PWA. The –SO3H in the PSS molecule accepts the tionalized Ph2SiO membranes.
free proton from the PWA molecule and forms the protonated Mesoporous materials such as mesoporous silica have
sulfonic acid group, such as –SO3H2+ (Fig. 12a) and the attracted a great deal of attention because of the tunable
transport of the proton also occurs from the protonated mesoporous structure. High specific surface area, nanosized
–SO3H to a nonprotonated –SO3H (Fig. 12b). The encapsulated channels or frameworks with an ordered and interconnected
material demonstrated a high anhydrous proton conductivity of internal structure, and high structural stability allow for their
1.0 10 2 S cm 1 at 180 1C and a maximum power density of potential applications as proton exchange membranes operating
approximately 3 mW cm 2 was obtained at 160 1C.149 at elevated temperatures.154–159 The key issue is, how to anchor
Sakamoto et al.150 developed an inorganic proton conductor and assemble proton conducting carriers into the mesopores or
based on self-assembly of PWA and PDDA on negatively charged channels of the host. Lu et al. developed PEMs based on highly
phenylsilsesquioxane PhSiO3/2 particles. Before the deposition ordered mesoporous MCM-41 functionalized with proton
of the PWA layer, (PDDA–PSS)2 layers were deposited onto conducting HPW (i.e., PWA) nanoparticles by the vacuum-
the surface of PhSiO3/2 particles in order to increase the assisted impregnation method (VIM).160 The HPW Keggin
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HPW decreases the pH of the precursor, significantly increasing

the proton adsorption of SiOH groups and forming positively
charged SiOH2+. When HPW molecules, silica precursor and
TEOS are mixed in water, self-assembly will occur between the
positively charged silica and the negatively charged HPW by
electrostatic forces. With the addition of structure-directing
block copolymer, Pluronic P123, the tube-cumulated meso-

porous HPW-silica with the template of P123 surfactant is
formed through the cooperative hydrogen bonding and electro-
static interaction between the HPW-silica structure and P123
surfactant.165 With the phase separation of P123, the colloidal
complex forms ordered mesoporous silica with the HPW self-
assembled in the mesoporous structure. The surfactant template
is then removed by heat treatment at 400 1C. The conductivity
Fig. 12 (a) Anhydrous proton-conducting mechanism at the interface of the HPW–meso-silica nanocomposite membrane depends
between PWA and –SO3H. (b) Proton conduction of nanodispersed strongly on the HPW content, the threshold of the HPW
PWA-encapsulated material. Arrows indicate the proton transfer of
content in the nanocomposite is 5 wt% with best conductivity
molecular rotation on the PWA nanoparticles of the encapsulated
materials. The backbone of PSS chains have been omitted in this model
obtained on 25 wt% HPW with a proton conductivity of 6.0
for clarity. Reproduced with permission from ref. 149. r2006, The 10 2 S cm 1 at 75 1C and 100% RH. The conductivity also
American Chemical Society. depends on the microstructure of the meso-silica framework. A
large pore size of the host meso-silica would lead to a high loss
unit contains three negative charges, which are neutralized in of the conductivity as the HPW was leached by water.161
the acid solution by protons in the form of acidic hydroxyl Fuel cells with self-assembled HPW-silica mesoporous
groups at the exterior of the structure. As a result, HPW nanocomposite PEMs also showed high proton conductivity
molecules are negatively charged in water.160 On the other and performance. Tang et al. studied the conductivity and
hand, the presence of the highly acidic HPW would significantly performance of self-assembled HPW-silica mesoporous nano-
increase the proton adsorption reaction of Si–OH, forming composite PEMs for direct methanol and ethanol fuels.166
positively charged SiOH2+ groups.138 Thus, HPW molecules/ When the temperature was increased to 200 1C without
clusters would be self-assembled into a positively charged inner external humidification, the proton conductivity reached
surface of the mesoporous of MCM-41, forming anchored 5.0 10 2 S cm 1. A fuel cell based on a 165 mm thick
HPW nanoparticles/clusters. Fig. 13 shows the procedure for HPW-silica nanocomposite membrane achieved a maximum
the synthesis of mesoporous silica and HPW-functionalized power output of 128.5 and 112.0 mW cm 2 for methanol and
meso-silica by impregnation.161 ethanol fuels at 200 1C, that is 6.6 and 3 times higher than that
Fig. 14 shows TEM micrographs of siliceous MCM-41 host and at 80 1C, respectively (see Fig. 16).166 The DMFC performance
MCM-41 with self-assembled HPW by VIM and conventional based on a high-temperature HPW/silica nanocomposite
impregnation method (CIM).160 MCM-41 is characterized by proton conducting membrane and low Pt catalyst loading
highly ordered 2D nanochannels and the wall thickness of nano- (1.0 mg cm 2) is close to that of advanced DMFCs
channels is B2 nm (thick black lines in the inset in Fig. 14a). In the (100–200 mW cm 2).167 The cell performance is stable for
case of vacuum-assisted HPW-assembled MCM-41, the TEM direct alcohol fuels with no noticeable change in the cell
images clearly provide direct observation of the morphology and voltage, in contrast to the commonly observed significant drop
distribution of HPW nanoparticles in the MCM-41 host, indicated in performance for direct alcohol fuel cells at low temperatures.168
by the ordered but not continuous black dots sandwiched between These results show the promising potential of the self-assembly
continuous channels. However, for the HPW/MCM-41 meso- of the HPW/meso-silica with uniformly distributed HPW as
porous silica assembled under normal conditions without vacuum novel PEMs for operation at elevated temperatures and low
treatment, HPW nanoparticles/clusters are mainly distributed at humidity conditions.
open ends or edges of the nanochannels of mesoporous silica In conclusion, hygroscopic oxides can be dispersed homo-
(Fig. 14e). The proton conductivity of HPW/MCM-41 composite genously via a self-assembly technique in the bulk of PFSA,
PEMs is quite stable (Fig. 14f), indicating the stability of which increases the water retention at high temperature.
assembled HPW nanoclusters in the mesoporous silica by electro- Besides, proton conducting HPA can be assembled with
static attractive forces. Best conductivity is 4.5 10 2 S cm 1 at polyelectrolyte or mesopores of meso-silica matrix to form
150 1C and the cell performance with a 30 wt% HPW/MCM-41 inorganic composite membrane for HT-PEMFC, which not
nanocomposite PEMs achieved a maximum power density of only improve the water retention, but also enhance the proton
95 mW cm 2 in H2/O2 at 100 1C and 100% RH.160 conduction of the composite membrane at high temperatures.
Further development demonstrated that the HPW/meso-
silica nanocomposite PEMs with an ordered framework can be 5 Self-assembly of NP electrocatalysts for
obtained through a one-step self-assembly route assisted with
PEMFC applications
a structure-directing block copolymer surfactant.162,163 Fig. 15
shows the principle of the self-assembly of the HPW/meso- Owing to their unique electric, magnetic, optical and catalytic
silica via a one-step synthesis route.164 The presence of acidic properties, precious metal NPs have been regarded as the most
Fig. 13 Synthesis of mesoporous silica and HPW-functionalized meso-silica by impregnation. Reproduced with permission from ref. 161. r2011,
The American Chemical Society.
active catalyst material of fuel cells and supercapacitors. To and the distribution and dispersion of Pt NPs appear to be
maximize precious metal utilization, the particle size, distribu- related to the PEs applied. Fig. 17 shows that the electro-
tion and electrocatalytic activity of NPs need to be optimized. chemical activity of PE-stabilized Pt NPs for MOR depends
Traditionally, precious metal NPs such as Pt and Pt alloys strongly on the nature of PEs.171 The electrocatalytic activities
dispersed on high surface area carbon are used as electro- of PE-stabilized Pt NPs and Pt black reference catalysts
catalysts for low-temperature fuel cells. Many kinds of high decreases in the order of PDDA–Pt 4 PSS–Pt 4 Pt black 4
surface area carbon materials have been investigated as Nafion–Pt 4 PAMP–Pt 4 PAA–Pt 4 PVP–Pt 4 PAH–Pt.
catalyst supports, such as carbon blacks, CNTs, carbon Thus PDDA–Pt and PSS–Pt NPs showed better electrocatalytic
nanofibers, carbon microspheres and graphene. Among them, properties than that of the commercial Pt black catalysts. The
CNTs and graphene have been considered as the most promising results indicate the significant enhancing effect of the NH4+ and
potential catalyst supports for low-temperature fuel cells due to SO3 functional groups of the PEs on the electrocatalytic
their excellent properties such as high specific surface area, high activities of Pt NPs for both MOR and ORR.173 Self-assembled
electronic conductivity, and outstanding chemical and electro- PDDA–Pt nanoparticles not only show high electroactivity
chemical stability. for the O2 reduction and H2 or methanol oxidation reactions
In this section, recent progress in the preparation of precious- for PEMFC,118 but also dramatically reduce the methanol
metal NPs/CNTs and precious-metal NPs/graphene electrocatalysts crossover while having little detrimental effect on the high
via the self-assembly technique is reviewed and discussed. proton conductivity and microstructure of the membrane for
direct methanol fuel cells.119
Moreover, the electrocatalytic activity, dispersion and
5.1 Standalone precious-metal NPs catalysts
distribution of PE–Pt NPs are a strong function of PE
Polymer or PE-stabilized precious metal NPs often act as concentration.174 It has been reported that the optimal molar
excellent homogeneous catalysts and show interesting catalytic ratio of PDDA to Pt is 3 : 1 for the best morphology and
properties. For low-temperature fuel cell applications, distribution of PDDA–Pt NPs. PDDA–PT NPs synthesized
the polymer matrix might provide an efficient pathway for with PDDA to Pt ratio of 3 : 1 shows better catalytic activity
electron and protonic species. Ye and Crooks studied hydroxyl- for the methanol oxidation reaction in comparison to a
terminated PAMAM dendrimer-encapsulated Pt NPs and commercial Pt/C catalyst, while the excess PDDA will inhibit
found that dendrimer-encapsulated Pt NPs were electrocataly- the electrocatalytic activity of Pt NPs due to a shielding effect.175
tically active for oxygen reduction reaction (ORR).169 Bensebaa Pt NPs chains prepared by EDTA-directed self-assembly was
et al. synthesized poly(pyrroledi(2-ethylhexyl) sulfosuccinate) also reported by Chen et al.176
(PPyDEHS) stabilized PtRu catalysts and the polymer-
embedded PtRu catalyst showed certain activity for methanol
5.2 Metal NPs supported on CNTs
oxidation reaction (MOR).170 Jiang et al. studied systematically
the effect of various PEs such as PSS, PAH, PAA, PAMP and CNTs have received extensive attraction after their discovery
PVP, stabilized Pt NPs, on the NP formation and electro- by Iijima in 1991.177 In recent years, CNTs have been increasingly
catalytic activity of PE-stabilized Pt NPs for methanol oxida- considered as an advanced catalyst support for PEMFCs, owing
tion and oxygen reduction reactions.171,172 The self-assembly to their outstanding physical and mechanical characteristics.178
of PE on Pt NPs reduced in situ stabilizes the Pt NPs However, it is well known that for CNTs without surface
and improves the distribution and dispersion of Pt NPs. modification or functionalization, there are insufficient active sites
PE-stabilized Pt NPs have a particle diameter range of 2–4 nm for anchoring the precursors of metal ions or metal nanoparticles,
Fig. 14 TEM image of MCM-41 (a, b) and 30 wt% HPW/MCM-41 electrolyte by VIM (c, d), viewed either normal (a, c) or along (b, d) the pore
axis; inset: high-resolution images. Reproduced with permission from ref. 160. r2010, John Wiley and Sons.
which usually leads to poor dispersion and large metal nano- surface modification or functionalization of CNTs by PDDA
particles, especially under high loading conditions. Chemical oxida- via self-assembly technique occurs through non-bonding inter-
tion using a concentrated mixture of HNO3 and H2SO4 is generally action without detrimental effects on its intrinsic physical and
used to functionalize and generate active sites on the CNTs side- electronic properties.182 PDDA is a water-soluble quaternary
walls and tube tips.179,180 However, such harsh chemical oxidation ammonium salt and strong PE. The strong adsorption of the
method also reduces the electrical conductivity and corrosion positively charged PDDA on CNTs is believed to be due to
resistance of CNTs which would decrease the catalyst performance. the p–p interaction between PDDA and the basal plane of
One of the better alternative approaches is non-covalent graphite of CNTs.183 Pt NPs were then in situ synthesized on
functionalization via PE self-assembly. Hsin et al. reported the PDDA-functionalized CNTs (PDDA-MWCNTS) via the
in situ polymerization of poly(vinyl pyrrolidone) (PVP) whose self-assembly between negatively charged Pt precursors and
main chains are linked with CNTs through breaking the positively charged functional groups of PDDA. As illustrated
double bonds of MWCNTs, and then used this PVP-functio- in Fig. 18, because of the high density and positive surface
nalized CNTs as supports to deposit Pt and Pt–Ru NPs.181 charge, a large amount of negatively charged Pt precursor can
Using PDDA as functionalizing agent it was found that be anchored onto MWCNTs surface via electrostatic interaction.
Fig. 15 Scheme of the synthesis route of HPW–meso-silica nanocomposites via self-assembly assisted with a structure-directing Pluronic P123
surfactant. The inset is the structure of Keggin unit of HPW. Reproduced with permission from ref. 164. r2011, The Royal Society of Chemistry.
The subsequent reduction by ethylene glycol (EG) gives Pt NPs polymer to self-assemble HPW onto CNTs187 and Pt/C.188 The
with uniform distribution and high density. obtained PtRu/HPW-CS-CNTs and Pt/C-CS-HPW catalyst
Further development showed that non-covalent functiona- showed high electrocatalytic activity for methanol oxidation.
lization using PDDA can produce Pt NPs/PDDA/MWCNTs Zhang et al.189 also self-assembled Pt NPs onto PAH-
catalysts with average particle size of Pt NPs of 1.8 0.4 nm, functionalized CNTs and showed very good catalytic activity
uniform distribution and Pt loading of 10–93 wt% (see Fig. 19).64 towards oxygen reduction reaction. Nakashima’s group190,191
The results show that the increase in the Pt NP loading on synthesized Pt/PBI/MWCNTs with self-assembly technology,
MWCNTs leads to the enhancement of the electrocatalytic and the as-synthesized Pt catalysts exhibited higher utilization
activity for CO oxidation, methanol oxidation and oxygen efficiency of Pt NPs as compared to the Pt/MWNT, as well as
reduction, demonstrating a close correlation between the electro- commercially available Pt/C catalyst.
catalytic activities of Pt NPs catalysts and the interconnectivity of CNTs were also functionalized with a hemimicelle self-
Pt NPs on CNTs. PtRu and PtSn NPs can also be self-assembled assembly of amphiphilic molecules based on hydrophobic inter-
to non-covalent functionalized CNTs.184,185 action, which showed extremely good solubility and stability
In addition to Pt, PtRu and PtSn NPs, HPAs such as HPW when used as the supports for metal NPs.192–194 CNTs were
can also be self-assembled to PDDA-functionalized MWCNTs decorated with dense and uniform Pd NPs with a mean diameter
to enhance the electrocatalytic activity of precious metal of 2 nm; these Pd-coated CNTs193 showed superiority toward
catalysts.186 In this method, negatively charged HPW was methanol electrocatalytic oxidation and the current intensity was
self-assembled on positively charged PDDA-MWCNTs via nearly 25 times higher (3540 mA cm 2 mg 1) than that of
electrostatic forces, followed by Pd deposition and reduction previously reported MWCNT-Pd assemblies.195
onto the HPW assembled PDDA-MWCNTs (Pd/HPW-PDDA- The high conductivity, chemical and thermal stability of
MWCNTs) (Fig. 20). The Pd NPs (average particle size about ionic liquids (ILs) as well as their wide electrochemical window
2 nm) in the HPW assembled PDDA-MWCNTs showed a make them attractive for research in fuel-cell technology.
homogeneous dispersion with narrow particle size distribution. Niu’s group developed an effective method to attach IL
The assembly and incorporation of HPW significantly reduced to CNTs.196 In this method amine-terminated ionic liquids
the size and enhanced the distribution of Pd NPs on MWCNTs. (NH2-IL) were grafted to the carboxyl-functionalized MWCNTs
The electrocatalytic activity of Pd/HPW-PDDA-MWCNTs for (MWCNTs-COOH) by formation of the amide linkage between
oxygen reduction reaction is compatible to that of Pt/C.186 MWCNTs-COOH and NH2-IL (Fig. 21). Then a gold salt
Besides PDDA, chitosan was also used as positively changed [AuCl4] was self-assembled and absorbed on the IL-functionalized
View Article Online
produced by in situ reduction on CNTs. Imidazolium-salt-based

ionic liquids (IS-ILs) were used as linkers.
Guo et al. also used IS-ILs-functionalized CNTs as supports
for Pt NPs.197 It was found that IS-ILs on the surface of CNTs
could effectively enrich PtCl62 by a coupling effect and
promote the nucleation of Pt NPs due to their low interface
energy and enhance the eletron transport pathway between

CNTs and NPs. The as-prepared Pt/IS-ILs/CNTs nano-
hybrids exhibited 2.9 times higher electrocatalytic activity
(0.47 A mg 1) towards the methanol oxidation reaction than
the commercial E-TEK Pt/C catalyst due to fine Pt NPs with
uniform particle size (B3 nm) on IS-ILs/CNTs.
It is well known that alloying Pt with another metal or
depositing Pt on the surface of another metal can modify the
electronic structure and enhance the electrocatalytic activity of
Pt-based NPs, based on the d-band center theory developed by
Norskov et al.198,199 For example, PtSn alloy nanoparticles have
been demonstrated to show significantly improved electrocatalytic
activity for the methanol oxidation reaction.200 Due to their
different electronegativities, Sn will donate electrons to Pt
leading to a downshifted d-band center of Pt, which thus
would weaken the chemisorption energy with poisoning CO
intermediates. However, there are limited studies on the anchoring
groups connecting metal NPs and the support material, which
may be equally important in tuning the electroactivity of Pt NPs.
Wang et al. investigated the modification of the electronic
structure of Pt NPs via charge transfer by specific functional
groups on CNTs (see Fig. 22).201 Electrochemical character-
ization and DFT calculation revealed that polyanions having
Fig. 16 Performance and stability of single cells assembled by 25 wt% electron-rich functional groups would donate electrons to
HPW/silica mesoporous nanocomposite electrolyte membranes for direct Pt-atoms, causing a substantial increase in electron density
alcohol fuel cells in the absence of external humidification. The stability around the Pt-site and downshift of d-band center of Pt. This
of the cell was measured at a constant current of 300 mA cm 2 at 200 1C.
results in a weaker chemisorption of oxygen-containing species
Pt black (1.0 mg cm 2) was used as the anode and cathode electro-
or CO. On the other hand, polycations having electron-poor
catalysts. Reproduced with permission from ref. 166. r2011, The Royal
Society of Chemistry. functional groups would have the opposite effect. The results
show that the electrocatalytic activity of methanol oxidation
could be tuned by modifying the electronic structures of Pt
NPs via functional groups of attached PEs.
5.3 Metal NPs supported on graphene

Graphene, a new kind of two-dimensional (2D) carbon material
with a single (or a few) atomic layers, has attracted the great
attention of researchers worldwide for both fundamental science
and applied research since its discovery in 2004.202,203 Due to its
high surface area, high conductivity and unique graphitized basal
plane structure, graphene and graphene derivatives such as
graphene oxide (GO) and reduced graphene oxide (rGO) are
regarded as promising alternative catalyst supports for fuel cell
applications. Similar to CNTs, in order to uniformly disperse the
metal NPs, graphene needs to be functionalized.
Zhang et al.204 used positively charged PDDA as both a
reducing agent and a stabilizer during the formation of graphene
Fig. 17 Cycle voltammograms of PE-stabilized Pt, PVP-Pt and Pt
nanosheets. Pt NPs were then self-assembled on PDDA-
black NPs for the methanol oxidation reaction in 1 M H2SO4 + 2 M
CH3OH under a scan rate of 50 mV s 1 at 25 1C. Reproduced with
functionalized graphene nanosheets, forming Pt NPs by
permission from ref. 171. r2007, Elsevier. reduction in situ by NaBH4. Pt NPs on PDDA–graphene exhibited
excellent activity toward formic acid oxidation. PtAu bimetallic
CNTs via electrostatic interaction and ion exchange. Au NPs with NPs were also self-assembled on the PDDA-functionalized
uniform dispersion and narrow size distribution were then graphene and high electrocatalytic activity and stability for formic
Fig. 18 PDDA functionalization of CNTs and in situ synthesis of Pt NPs on PDDA-functionalized CNTs. Reproduced with permission from
ref. 182. r2008, Institute of Physics.
acid oxidation were demonstrated.205 Meanwhile, Wang et al.206 nanomaterials exhibited higher electrocatalytic activity than
deposited Pt and Au NPs simultaneously on PDDA-functionalized hollow AuPd NPs, IL-graphene–hollow-Pd NPs and solid Pd
graphene catalysts using a self-assembly method. The results NPs for electrooxidation of formic acid, indicating that gra-
suggested that a low Pt : Au NPs ratio and high PtAu NPs loading phene is a good candidate as a support for building high
are the most important factors for substantial enhancement of the performance catalysts for fuel cell applications. Li et al. found that
electrocatalytic activity of simultaneously assembled PtAu/PDDA- chemically converted graphene or rGO, displays better tolerance
graphene catalysts for formic acid oxidation reaction. towards CO poisoning during methanol oxidation compared to
In addition to PDDA, other polycations such as PVP,207 CNTs because the residual oxygenated functional groups of rGO
PPy208 and poly[2,20-(p-oxydiphenylene)-5,50-bibenzimidazole] can react and remove carbonaceous species.212 The better perfor-
(OPBI)209 were also used to functionalize graphene for the self- mance arises from the large specific area of graphene and its high
assembly of metallic NPs. Guo et al. demonstrated for the first time conductivity for electron and ion transport. However, Brownson’s
a wet-chemical approach for the synthesis of high-quality three- group213 observed that graphene exhibits slow electron transfer
dimensional (3D) Pt-on-Pd bimetallic NPs supported on PVP- towards the electrochemical probes studied, effectively blocking
functionalized graphene, forming Pt-on-Pd nanodendrites underlying electron transfer of the supporting electrode substrate,
(Fig. 23).207 The Pt-on-Pd nanodendrite catalysts exhibited likely due to its large basal and low edge plane content.
an enlarged ECSA and had a much higher catalytic activity Table 2 lists selected reports on the particle sizes and activity
than conventional E-TEK Pt/C electrocatalysts for methanol of precious-metal NPs supported on CNTs and graphene via
electrooxidation. The Pd/PPy–graphene catalyst synthesized the self-assembly technique.
by Zhao and co-workers208 showed higher electrocatalytic activity
and stability for methanol oxidation, probably due to the high
5.4 Self-assembly of novel catalysts structures
utilization of Pd NPs on the PPy–graphene supports.
Similarly to CNTs, ionic liquids (IL) have also been utilized Self-assembly of NPs by electrostatic interaction has been investi-
to functionalize graphene. Zhu et al.210 succeeded in constructing gated as an effective approach in the synthesis and development of
a hybrid 3D nanocomposite film [(G-IS-IL/Pt NPs)n] by novel macroscopic structures.217–221 The interplay of repulsive
alternatively assembling graphene modified by IS-IL and Pt interactions among NPs with the same charge and attractive
NPs. The nanocomposite film exhibited high electrocatalytic interactions between outer and inner layer NPs with opposite
activity towards oxygen reduction. Hollow AuPd alloy nano- charges result in the self-assembly of these NPs into highly
structures were self-assembly fabricated onto graphene with ordered structures. In contrast to atomic systems, electrostatic
the assistance of ionic liquid units under moderate conditions self-assemblies are not limited by charge neutrality, which
in a one-step method (Fig. 24).211 The resulting hybrid allows us to obtain a great diversity of new binary structures.217
Fig. 19 TEM micrographs of Pt NPs on PDDA/MWCNTs with Pt loadings of (a) 10, (b) 20, (c) 30, (d) 40 , (e) 50, (f) 69, (g) 81.6, (h) 86 and
(i) 93 wt%. Reproduced with permission from ref. 64. r2009, The American Chemical Society.
Fig. 20 Scheme of self-assembly of HPW onto PDDA-functionalized MWCNTs and synthesis of Pd NPs on HPW assembled PDDA-MWCNTs.
Reproduced with permission from ref. 186. r2010, The Royal Society of Chemistry.
Fig. 21 Illustration of the procedure for the assembly of MWCNT/IL/Au hybrids. Reproduced with permission from ref. 196. r2008, Elsevier.
Fig. 22 (A) The possible effect of charged functional groups of polyanions (PSS and PAA) and polycations (PDDA) and PAH) on the electron
donor–acceptor behavior of Pt NP; and (B) correlation between the adsorption energy of O and the d-band center of Pt slabs. Reproduced with
permission from ref. 201. r2010, Elsevier.
Fig. 23 TEM (a–c) and HRTEM (d, e) images of TP-BNGN at different magnifications. The circled parts in panel d denote Pd NPs. FFT pattern
(f) of the HRTEM image shown in panel e (circled part). Reproduced with permission from ref. 207. r2010, The American Chemical Society.
Cargnello et al.222 successfully prepared dispersible Pd@CeO2 showed significantly enhanced activity and high stability
core–shell nanostructures by exploiting the self-assembly between towards formic acid oxidation as compared with Pt NPs and
functionalized Pd nanoparticles and cerium(IV) alkoxides (Fig. 25). Au NPs.223 The high electrocatalytic activity of Pt-around-Au
The Pd@CeO2 core–shell nanostructures are effectively dispersible NPs indicates a significant synergistic effect of Au on the
in a range of organic solvents without any sign of agglomeration. activity of Pt NPs for the formic acid oxidation reaction.
They demonstrated that the size of the metal core and the thickness
of the oxide layer can be tuned and these nanostructures are
6 LbL self-assembly technique for supercapacitors
interesting precursors for the preparation of active hetero-
geneous catalysts. Supercapacitors, also known as ultracapacitors or electro-
Zhang et al.223 synthesized a novel Pt-around-Au nano- chemical capacitors, electrochemically store and deliver energy
composite by electrostatic self-assembly. PDDA and citrate at high charge–discharge rates and are a key emerging tech-
were used as polycation and polyanion. Pt-around-Au NPs nology for energy storage.224 Supercapacitors have attracted
Fig. 24 Illustration of the formation of hollow AuPd alloy nanoparticles and IL-CCG–hollow-AuPd nanocomposites. Reproduced with
permission from ref. 211. r2011, Royal Society of Chemistry.
much attention because of their pulse power supply, long cycle processes take place due to electro-active species. These two
life (4100 000 cycles), simple principle, and high dynamics of mechanisms can function simultaneously depending on the
charge propagation.225–227 They can complement or replace nature of the electrode materials. Progress towards super-
batteries in electric energy storage and harvesting applications capacitor technologies can benefit from the fundamental
when high power delivery or uptake is required. Currently, understanding of charging storage mechanism and the devel-
supercapacitors are widely used in consumer electronics, opment of advanced nanostructured materials.228
memory back-up systems and industrial power and energy Transition metal oxides such as ruthenium oxide,44 manga-
management. nese oxide,229 cobalt oxide,230,231 and tin oxide232 are the
Generally, on the basis of the energy storage mechanism, important materials for pseudocapacitors. However, several
supercapacitors can be classified into two categories. One problems such as high cost, low electrical conductivity and
is the electrical double layer capacitor (EDLC), where the poor stability limit the practical applications of metal oxides as
capacitance comes from the pure electrostatic charge accumu- supercapacitor electrodes. The LbL self-assembly technique
lated at the electrode/electrolyte interface, therefore it is offers an excellent opportunity for the interface engineering of
strongly dependent on the surface area of the electrode multilayer thin film structures or nanostructured building blocks,
materials that is accessible to the electrolyte ions. The other which can result in significantly improved electronic conductivity
is the pseudocapacitor, in which fast and reversible faradaic and high electrochemical performance of supercapacitors.
Table 2 Particle sizes and electrocatalytic activity of noble-metal NPs in representative noble-metal NPs/CNTs and noble-metal NPs/graphene
nanohybrids
Support material Metal NP dav/nm Functional material Current densitya Reactionb Ref.
2 1
CNTs Pt 1.47–2.6 PDDA 104.5 mA cm mgPt MOR 64, 182
2.8 PAH 32.4 mA mgPt 1(@0.9 V vs. RHE, 1600 rpm) ORR 189
4.1 1.5 PBI 480 mA mgPt 1 MOR 191
3.0 IS-IL 460 mA mgPt 1 MOR 197
Pd 2.0 HPW-PDDA 6 mA cm 2 mgPd 1 (@0.8 V vs. RHE, 2500 rpm)c ORR 186
Au 3.3 NH2-IL ORR 196
4.7 1.1 PDDA-PEI ORR 214
4.0–7.0 PEI ORR 215
1
PtRu 3.1 HPW-CS 178 mA mgmetal MOR 187
Graphene Pt 3.0 PDDA 500 mA mgPt 1 FAOR 204

Pd 6.0 PPy 359 mA mgPd 1 MOR 208
PtAu 3.3 0.2 PDDA 2310 mA mgPt 1 FAOR 205
PtRu 2.0 PMO12 2028 mA cm 2 mgPt 1
MOR 216
a
Current density under different reaction types and key parameters. b MOR: methanol oxidation reaction; ORR: oxygen reduction reaction:
FAOR: formic acid oxidation reaction. c Ik was normalized by the electrochemical surface area of the metal catalyst obtained from the CO
stripping.
Fig. 25 Schematic representation of the procedure to obtain dispersible Pd@CeO2 core–shell nanostructures. Reproduced with permission from
ref. 222. r2010, The American Chemical Society.
Inorganic nanosheets such as MnO2 nanosheets with thickness Zheng and co-workers fabricated sandwiched films of MONS
at nanoscale and conductive carbon materials such as CNTs and MWCNTs using the LbL self-assembly method.235 Sand-
and graphene can be used as building blocks for the fabrica- wiched films of MONS/MWCNT were assembled via electrostatic
tion of multilayer thin film structure based supercapacitors by interaction of positively-charged PDDA and negatively-charged
the LbL self-assembly technique. MONS and MWCNT. The fabrication of the multilayer thin
Table 3 lists selected literature reports where the self-assem- film was initiated by immersing an acid-treated ITO flat
bly technique has been utilized as main fabrication techniques substrate with a layer of positively charged PDDA to intro-
in the development of advanced supercapacitors. duce a uniform distribution of positive charges in the substrate
Zhang’s group234 fabricated multilayer thin films of MnO2 surface. Fig. 27 shows the fabrication procedures of sand-
nanosheets (MONS) with poly(ethylene imine) (PEI) poly- wiched films of MONS and MWCNT and the electrochemical
electrolyte by the LbL self-assembly technique. UV-Vis performance of sandwiched multilayer film electrodes of
absorption spectra showed that approximately equal amounts PDDA/MWCNT, PDDA/MONS and PDDA/MONS/
of manganese oxides were incorporated into the films for PDDA/MWCNT on ITO substrates. UV-Vis results show
each deposition cycle (see Fig. 26). The multilayer thin film the stepwise and regular film growth process. Electrochemical
showed a good electrochemical performance, which could be results revealed that the multilayer film had an excellent
attributed to the special microstructure of the film electrode. electrochemical capacitance because the CNT layers in the
The specific capacitance value of 288 F g 1 for (PEI/MONS)10 multilayer film not only provides a large surface area for the
film on ITO-coated substrate was obtained at a current density dispersion of MONS, but also improves the electronic con-
of 1.25 A g 1. The LbL self-assembly provides a simple and ductivity of the film. The CV curve of the (PDDA/MWCNT)4
effective method for preparing thin-film electrodes for electro- electrode (curve (1) in Fig. 27b) shows a typical double-layer
chemical capacitors. capacitive behavior with near-ideal rectangular profile. In the
As discussed earlier, the high chemical stability, good case of (PDDA/MONS)4 electrode, a broad peak around
mechanical property, excellent electronic conductivity and 0.62–0.84 V on the positive going sweep and a peak centre
high surface area of CNTs makes them particularly attractive at 0.68 V on the negative going sweep, which originates as
for electrochemical capacitors.243,244 Recent studies show pseudo-capacitance from the Mn4+/Mn3+ reversible redox
that electrode materials with a high supercapacity and rate process, can be observed. As seen in Fig. 27b, the capacitive
capability of the metal oxide can be achieved when MnO2 current of ITO/(PDDA/MWCNT/PDDA/MONS)2 electrode
nanostructures are loaded uniformly with CNTs.233,235,236 The was much larger than those of either ITO/(PDDA/MWCNT)4
addition of CNT to MnO2 materials is expected to not only or ITO/(PDDA/MONS)4 electrodes. This clearly indicates that
significantly improve the electronic conductivity but also CNT contributed significantly to the enhanced capacitance of
provide much better mechanical robustness for the composite. the composite electrode. The mechanism of CNT/MONS thin
Table 3 Specific capacitance of selected electrode materials for supercapacitors applications

1
Electrode material Specific capacitance/F g Electrolyte Ref.
CNT/PPy/MnO2 281 1.0 M Na2SO4 233
LbL-(PEI/MONS)10 288 2.0 M KCl 234
LbL-MWCNT/PDDA/MONS 581 0.1 M Na2SO4 235
LbL-MWCNT/MnO2 290 236
SAM-HNTS/PPy 522 0.5 M Na2SO4 237
LbL-(PEI-graphene/MWCNT-COOH)9 120 1.0 M Na2SO4 238
LbL-(PDDA/MWCNT)/PDDA/MONS 1.0 M Na2SO4 239
LbL-(CoOOHNW/MONS)2 856 0.1 M Na2SO4 240
Self-assembly carbon sphere/graphene 198 6.0 M KOH 44
LbL-MWCNT/rGO 157 18 0.5 M Na2SO4 241
LbL-(graphene/QP4VP-CO-PCN)9 49 1.0 M Na2SO4 242
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performances relative to those of pure FRGO-p and Na/MnO2

sheets, attributed to the contributions of the good electrical
conductivity of FRGO-p and the pesudocapacitance of the
MnO2 nanosheets. Additionally, over 89% of the original
capacitance was retained after 1000 cycles. This was attributed
to the fact that self-assembly of the MnO2 nanosheets on
FRGO-p effectively prevents the agglomeration of MnO2, thus

facilitating the ion transport in the electrode material and
improving the electric double-layer capacitance.
Recently, several attempts have been made to fabricate
hybridized carbon materials with good performance. For
example, Guo and Li employed the electrostatic self-assembly
method to fabricate a hierarchical nanostructure comprising
0-D carbon spheres and 2-D graphene nanosheets (see Fig. 30).44
The SEM image illustrates that functionalized carbon spheres
play a role as nanospacers to separate graphene nanosheets.
Moreover, the lateral dimension of the graphene sheets in the
Fig. 26 UV-Vis absorption spectra of multilayer films of (PEI/
MNS)n prepared on quartz glass substrates. The insert shows the nanostructure is continuous, which favors electron transport.
dependence of absorbance at 320 nm as a function of deposition The nanostructure significantly enhances the capacitance of the
cycles. Reproduced with permission from ref. 234. r2008, Elsevier. graphene supercapacitor by more than 70% (up to 198 F g 1),
while achieving a high power density of 15.4 kW kg 1 and long
film for electrochemical capacitance was further studied and cycle life.
the specific capacitance and energy density increased In supercapacitor applications, the combination of 1-D and
by increasing the number of MWCNT layers.239 Zheng et al. 2-D carbon materials can be applied to tune the pore structure
also developed a new type of multilayer films consisting of of hybrid films and enhance the structural stability. In hybrid
MWCNTs and cobalt oxyhydroxide nanoflakes (CoOOHNFs) films, as with the pure graphene structures described in the
by alternate electrostatic self-assembly and electrodeposition preceding section, CNTs can be used to physically separate the
technique; multilayer films of MWCNT/CoOOHNF on ITO graphene sheets to help preserve the high surface area. Using
glass reached a specific capacitance of 389 F g 1.231 The high LbL self-assembly techniques, graphene/CNT hybrid films
electrochemical performance is considered due to the effective have been prepared with an interconnected network of carbon
microporous structure, large specific surface-area and good structures.238 Supercapacitors prepared from such films show
electrical conductance. a specific capacitance of 120 F g 1 even at scan rate of 1 V s 1.
Lee et al. also synthesized LbL-assembled MWCNT/MnO2 Byon et al. developed a carbon-only electrode based on self-
in which the LbL-MWCNT films were created by alternating assembly of MWCNT-NH2 (amine-functionalized MWCNT)
adsorption of positively charged MWCNTs (MWCNTNH3+) and rGO, using hydrazine vapor treatment of the assembled
and negatively charged MWCNTs (MWCNT-COO ) (see MWCNT/rGO (see Fig. 31).241 In this multilayer structure,
Fig. 28).236 In this scheme, positively charged MWCNTs MWCNTs served as pillars to separate rGO layers, making the
(MWNT-NH3+) and negatively charged MWCNTs (MWNT- surfaces of graphene sheets electrochemically active. These
COO ) were prepared using surface functionalization processes. assembled MWCNT/rGO electrodes showed higher specific
The LbL-MWCNT films on ITO-coated glass slides were (up to 175 F g 1) and high volumetric (up to 160 F cm 3)
alternately dipped into a MWNT-NH3+ solution and capacitance.
MWNT-COO solution. The structure of the LbL-MWCNT/
MnO2 electrodes shows uniformly distributed MnO2 nano-
7 Concluding remarks
particles on interconnected MWCNTs in a random network.
The multilayer electrodes showed high volumetric capacitance LbL self-assembly technology is a fast growing field with
(the specific capacitance of MnO2 is 940 F g 1 as compared to a promising applications in electrochemical energy conversion
theoretical capacitance of MnO2 of 1370 F g 1) and remarkable and storage such as in fuel cells and supercapacitors. What
rate capability which were attributed to the electrode micro- makes the LbL self-assembly technique particularly attractive
structure, where nanoscale MnO2 particles were supported on a is that any multiply charged (or hydrogen-bonded) species
high-packing density, porous MWCNT network with good can be incorporated including electrocatalytic species such
access to electrons and ions in the electrolyte. as heteropolyacids, precious metal ionic species as well as
In addition to CNTs, graphene has also been proposed as an functional, structural and biomaterials such as colloidal nano-
attractive material for supercapacitor applications.245–248 particles, CNTs, graphene, purple membrane and chitosan.
Zhang et al. reported a synthesis of composites of FRGO-p The LbL self-assembly of oppositely charged polyelectrolytes
(PDDA functionalized reduced graphene oxide) and MnO2 on a Nafion membrane shows a significant effect on the
nanosheets (FRGO-p-MnO2) by anchoring negatively charged reduction in methanol crossover and on the enhancement of
manganese dioxide MnO2 nanosheets on positively charged the performance of DMFCs. The unique advantages and
FRGO-p via an electrostatic co-precipitation method (see versatility of the LbL self-assembly technique are also clearly
Fig. 29).249 FRGO-p-MnO2 exhibited enhanced capacitive demonstrated by the surface engineering and modification of
Fig. 27 (a) Scheme of fabrication of sandwiched film of MONS and MWCNT and (b) CV of sandwiched multilayer film electrodes of (1) ITO/
(PDDA/MWCNT)4; (2) ITO(PDDA/MONS)4 and (3) ITO/(PDDA/MONS/PDDA/MWCNT)2, measured in 0.1 M Na2SO4 electrolyte at a scan
rate of 1 mV s 1. Reproduced with permission from ref. 235. r2009, Elsevier.
Fig. 28 LbL self-assembly of MWNT (LbL-MWNT) film via alternate dipping of substrate into positively charged(MWNT-NH3+) and
negatively charged (MWNT-COO ) MWNTs, and preparation of LbL-MWNT/MnO2 electrodes through dipping of the LbL-MWNT film into
permanganate ion (MnO4 ) solution. Reproduced with permission from ref. 236. r2010, The American Chemical Society.
high-surface area carbon supports such as CNTs and Integration of polymeric or PE LbL self-assembly and inorganic
graphenes, the deposition and synthesis of new and highly and catalytically active nanomaterials such as HPAs would also
efficient Pt and Pt alloy electrocatalysts, and novel HPW- offer promising potential in the development of non-precious
functionalized mesoporous silica based HT-PEM for fuel cells. metal catalysts for fuel cells.
Fig. 29 Schematic representation of the assembling process of FRGO-p-MnO2. Reproduced with permission from ref. 249. r2011, The
American Chemical Society.
Fig. 30 (a) Schematic representation of the preparation of self-assembled hierarchical nanostructures comprised of graphene and carbon spheres
and (b) SEM image of the hierarchical nanostructure. Reproduced with permission from ref. 44. r2007, The Royal Society of Chemistry.
LbL self-assembly technique has also become one of the processes and interfaces, and by optimization of the multilayer
most promising new methods for the interface engineering of structures of building blocks of electrochemically active
multilayer thin film structures or nanostructured building materials as well as highly electronic conducting materials.
blocks for the development of advanced supercapacitors with Despite the considerable progress, many challenges still
significantly improved electronic conductivity and high electro- remain for the practical application and scale up of the
chemical performance. The tunable nature of the technique LbL self-assembly technique for electrocatalysts, electrode
allows for the incorporation and manipulation of electro- and membrane materials for fuel cells and supercapacitors:
chemically active species such as nanostructured transition- (1) although the LbL self-assembly requires only simple
metal oxides and highly conducting carbon materials including procedures, its assembling mechanism is still not fully under-
CNTs and graphenes. Further progress can be achieved stood. For instance, computational modeling could be an
by fundamental understanding of the LbL self-assembly effective tool to predict and explain how the LbL assembled
Fig. 31 Schematic illustration of (a) the LbL assembly of MWCNT/rGO and (b) hydrazine treatment process. Reproduced with permission from
ref. 241. r2011, Elsevier.
View Article Online
films could affect the methanol crossover and proton transfer NPs nanoparticles
under fuel cell operation conditions. Better understanding of OCP open-circuit potential
the structure–property relationship of the LbL self-assembled OCV open circuit voltage
structure/films would highly benefit this attractive research OPBI poly[2,20-(p-oxydiphenylene)-5,50-
area and significantly accelerate the development of advanced bibenzimidazole]
electrode catalysts and electrolyte materials for fuel cells and ORR oxygen reduction reaction
supercapacitors. (2) Tailoring of the nano-, micro- and surface P4VP poly(4-vinylpyridine)
structure and distribution of active sites is still difficult. As PAA poly(acrylic acid)
exemplified by Pt-based NPs, control of the size and shape can PAH poly(allylamine hydrochloride)
significantly promote the catalytic activity due to the fact that PAMAM poly(amidoamine)
open-structure surfaces with high-index planes have high PAMPS poly(2-acrylamido-2-methyl-1-propanesulfonic
density of atomic steps and kinks, which serve as active sites acid)
for breaking chemical bonds.250 Although there are many PANI polyaniline
studies on single crystals, it is important to synthesize PAZO poly(1-(4-(3-carboxy-4-hydroxyphenylazo)benzene
NPs or structures with preferential orientation. (3) Many sulfonaimdo)-1,2-ethanediyl, sodium salt)
LbL self-assembly syntheses processes will be hard to scale PDDA(PDAC)
up. Non-covalent functionalization of CNTs or graphenes by poly(diallydimethylammonium chloride)
PEs takes hours or even days to achieve. Multiscaled nano- PE polyelectrolyte
structured films take many repeated steps and such problem PEC polyelectrolyte complexes
could prevent the viable scale up of the synthesis of such PEI poly(ethylene imine)
materials. (4) Last but not least, cost needs to be reduced. PEO poly(ethylene oxide)
Most research on the synthesis of LbL self-assembled nano- PEM proton exchange membrane
structured materials emphasizes the structure and novelty with PEMFC proton exchange membrane fuel cell
little consideration of the expensive precursors used or the cost PFSA perfluorosulfonic acid
of processes to produce them. In the long run for future PM purple membrane
applications, cost is a critical issue. We believe that significant sPPO sulfonated poly(2,6-dimethyl-1,4-phenylene oxide)
efforts should be made to solve these challenges and problems PPy polypyrrole
for the LbL self-assembled nanostructured materials for use in PPyDEHS poly(pyrroledi(2-ethylhexyl) sulfosuccinate)
fuel cells and supercapacitors. PSS poly(sodium styrene sulfonate)
PVP poly(N-vinyl-2-pyrrolidone)
PVS poly(vinyl sulfate)
List of abbreviations
RH relative humidification
CCM catalyst coated membrane SEM scanning electron microscopy
CIM conventional impregnation method SPEEK sulfonated poly(ether ether ketone)
CNT carbon nanotube SPAEK-C sulfonated poly(aryl ether ketone) bearing
CoOOHNFs cobalt oxyhydroxide nanoflakes carboxyl groups
CS chitosan TEM transition electron microscopy
DCC dicyclohexylcarbodiimide TEOS tetraethoxysilane
DMFC direct methanol fuel cell VIM vacuum-assisted impregnation
EDLC electrical double layer capacitor
EDTA ethylenediamine tetraacetic acid
Acknowledgements
EG ethylene glycol
FAOR formic acid oxidation This research was financial supported by grants from the
FRGO-p PDDA functionalized reduced graphene oxide National Natural Science Foundation of China (21073010,
GO graphene oxide 21003007, 51108014, U1137602, U1134001), National Basic
rGO reduced graphene oxide Research Program (973 program) (2011CB935700), Beijing
HPAs heteropolyacids Novel Program (2008B12), Program for New Century Excellent
HPW (PWA) phosphotungstic acid Talents in University, Fundamental Research Funds for the
HT-PEMFC high-temperature proton-exchange membrane Central Universities, China and Australia Research Council
fuel cells (DP120102325, DP120104932), Australia. The contribution
IL ionic liquid and assistance from Mr Zhang Jin and Mr Lan Fei are deeply
IPCE incident photo-to-current efficiency appreciated.
IS-ILs imidazolium-salt-based ionic liquids
LbL layer-by-layer
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Cite this: Chem. Soc. Rev., 2012, 41, 7291–7321

www.rsc.org/csr CRITICAL REVIEW

Layer-by-layer self-assembly in the development of electrochemical

Prof. Yan Xiang received her Dr Shanfu Lu received his

conventional PEs and block polymers,13–15 various biomaterials,

and responsive materials for drug release.24 Charged inorganic

Low pH is beneﬁcial to the degree of ionization of the polar

in the subsequent dipping step. Furthermore, a higher pH

to the PE solutions has a positive eﬀect on reducing the

strong inﬂuence on the amount of PE adsorbed. Despite

HPW decreases the pH of the precursor, signiﬁcantly increasing

block copolymer, Pluronic P123, the tube-cumulated meso-

produced by in situ reduction on CNTs. Imidazolium-salt-based

energy and enhance the eletron transport pathway between

5.3 Metal NPs supported on graphene

Graphene Pt 3.0 PDDA 500 mA mgPt 1 FAOR 204

Table 3 Speciﬁc capacitance of selected electrode materials for supercapacitors applications

performances relative to those of pure FRGO-p and Na/MnO2

FRGO-p eﬀectively prevents the agglomeration of MnO2, thus

L. Zhang and G. Q. Lu, Carbon, 2009, 47, 1534–1542. 329, 1637–1639.

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