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polymers

Review
Recent Advances in Nanostructured Conducting
Polymers: from Synthesis to Practical Applications
Duong Nguyen Nguyen 1 and Hyeonseok Yoon 1,2, *
1 Department of Polymer Engineering, Graduate School, Chonnam National University, 77 Yongbong-ro,
Buk-gu, Gwangju 61186, Korea; nguyendun@gmail.com
2 School of Polymer Science and Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu,
Gwangju 61186, Korea
* Correspondence: hyoon@chonnam.ac.kr; Tel.: +82-62-530-1778; Fax: +82-62-530-1779

Academic Editor: Frank Wiesbrock
Received: 3 March 2016; Accepted: 25 March 2016; Published: 31 March 2016

Abstract: Conducting polymers (CPs) have been widely studied to realize advanced technologies in
various areas such as chemical and biosensors, catalysts, photovoltaic cells, batteries, supercapacitors,
and others. In particular, hybridization of CPs with inorganic species has allowed the production of
promising functional materials with improved performance in various applications. Consequently,
many important studies on CPs have been carried out over the last decade, and numerous researchers
remain attracted to CPs from a technological perspective. In this review, we provide a theoretical
classification of fabrication techniques and a brief summary of the most recent developments in
synthesis methods. We evaluate the efficacy and benefits of these methods for the preparation of
pure CP nanomaterials and nanohybrids, presenting the newest trends from around the world with
205 references, most of which are from the last three years. Furthermore, we also evaluate the
effects of various factors on the structures and properties of CP nanomaterials, citing a large variety
of publications.

Keywords: conducting polymers; nanomaterials; nanohybrids; synthesis methods; applications

1. Introduction
Over the past decade, there has been significant progress in fabricating nanostructured materials
with unique properties. In particular, the topic of intrinsically conducting polymers (CPs) has seen
an explosion in the number of published papers, which have been very useful for both fundamental
research and potential applications. CPs are polymeric materials that display high conductivities, good
electrochemical activity, unique optical properties, and biocompatibility. Because of these interesting
properties, CPs have received special attention as promising candidates in many areas of nanoscience
and nanotechnology.
CPs, also known as conjugated polymers or “synthetic metals,” are polymers with highly
π-conjugated polymeric chains. Alan MacDiarmid, Hideki Shirakawa, and Alan Heeger were awarded
the Nobel Prize in Chemistry in 2000 for the discovery of inherent CPs. Up to now, a variety of CPs
(e.g., polyaniline (PANI), polypyrrole (PPy), polythiophene (PT), poly(3,4-ethylenedioxythiophene)
(PEDOT), and other PT derivatives) have been developed (see Figure 1). While there has been
continuous progress in the development of CPs, there has also been increasing interest in CP
nanohybrids. Hybrid nanomaterials, the combination of CPs with different types of materials, such as
metals, carbonaceous materials, and inorganic compounds, have been studied most intensively. Such
nanohybrids have proven to be attractive for a wide variety of applications, from organic electronics to
energy storage, solar cells, and sensors. As can be seen in Figure 2, the number of studies regarding
CP nanomaterials has rapidly increased over the last decade.

Polymers 2016, 8, 118; doi:10.3390/polym8040118 www.mdpi.com/journal/polymers

Polymers 2016, 8, 118 2 of 38
Polymers 2016, 8, 118 2 of 36
Polymers 2016, 8, 118 2 of 36

Figure 1. Chemical structures of representative conducting polymers (CPs).
Figure 1. Chemical structures of representative conducting polymers (CPs).
Figure 1. Chemical structures of representative conducting polymers (CPs).

Figure
Figure 2.
2. The
The number
number of articles
of on
articles published
published on CP
CP nanomaterials
on over
nanomaterials over
over the last
last decade.
thefrom decade. Data
Data from
from the
the
Figure 2. The number of articles published CP nanomaterials the last decade. Data the
ISI Web
ISI Web of Knowledge database.
of Knowledge database.
ISI Web of Knowledge database.

From the very early years of studying CPs, there have been numerous efforts to hybridize CPs
From the very early From yearsthe of
very studying CPs, of
early years there have been
studying CPs, numerous
there haveefforts to hybridize
been numerous CPs to hybridize CPs
efforts
with inorganic species. Metals (Ag, Au, and Pd), metal oxides (NiO, Cu2O, CuO, TiO2, WO3, ZnO,
with inorganic species. Metals (Ag,
with inorganic species.Au, and
Metals Pd), metal
(Ag, Au,oxides (NiO,
and Pd), metal Cu2oxides
O, CuO, TiO2Cu
(NiO, , WO 3, ZnO,
2 O, CuO, TiO2 , WO3 , ZnO,
Fe2O3, Fe3O4, MnO2, SnO2, V2O5, and RuO2), and chalcogenides (Bi2S3, CdSe, CdS, and CdTe) have
Fe2O3, Fe3O4, MnO Fe2 O3 , Fe3 O4 , MnO2 , SnO2 , V2 O5 , and RuO2 ), and chalcogenides (Bi2 S3 , CdSe,have
2 , SnO 2 , V 2 O 5 , and RuO 2 ), and chalcogenides (Bi 2 S 3 , CdSe, CdS, and CdTe) CdS, and CdTe) have
been explored. Recently, carbon nanomaterials (graphene, graphene oxide, and nanotubes) have been
been explored. Recently, carbon nanomaterials
been explored. Recently, carbon (graphene, graphene(graphene,
nanomaterials oxide, andgraphene
nanotubes) have been
oxide, and nanotubes) have
frequently employed. This significant investment in development is due to the recognition that
frequently employed. This significant
been frequently employed. investment in development
This significant investment is due to the recognition
in development is due tothat the recognition that
nanostructured CPs can play a key role in applications such as Li-ion batteries and supercapacitors
nanostructured CPs can play a key role in applications such as Li-ion batteries
nanostructured CPs can play a key role in applications such as Li-ion batteries and supercapacitorsand supercapacitors
(fast electrolyte diffusion), solar cells (effective exciton dissociation), sensors (enhanced sensitivity),
(fast electrolyte diffusion),
(fast electrolyte solar cells (effective
diffusion), solar exciton dissociation),
cells (effective excitonsensors (enhanced
dissociation), sensitivity),
sensors (enhanced sensitivity),
and electrochromics (fast response times). In this review article, we first classify traditional synthesis
and electrochromics (fast response times). In this review article, we first classify traditional
and electrochromics (fast response times). In this review article, we first classify traditional synthesis synthesis
routes for CPs, as well as for hybrid nanomaterials, and present a new standard for classification.
routes for CPs, asroutes
well as forfor CPs,hybridas well nanomaterials,
as for hybridand present a new
nanomaterials, and standard
present for
a newclassification.
standard for classification.
From this point of view, we then discuss recent developments in synthesis approaches that have
From this point of view, we then discuss recent developments
From this point of view, we then discuss recent developments in synthesis in synthesis approaches that approaches
have that have
improved conventional methods. Finally, various selected applications have been reported in order
improved conventional methods. Finally, various selected applications have been
improved conventional methods. Finally, various selected applications have been reported in order reported in order
to demonstrate the merits of CPs. The key difference between our work and previously published
to demonstrate the merits of CPs.
to demonstrate theThe key difference
merits of CPs. The between our work
key difference and previously
between our workpublished
and previously published
studies [1–8] is that we provide a brief scheme of the synthesis processes for CP nanomaterials,
studies [1–8] is that we provide a brief scheme of the synthesis processes
studies [1–8] is that we provide a brief scheme of the synthesis processes for CP nanomaterials,for CP nanomaterials,
including the mechanism of polymerization, key rules of synthesis, and environments of reactions
including the mechanism
includingofthe polymerization,
mechanism of key rules of synthesis,
polymerization, key rulesandof environments
synthesis, and of environments
reactions of reactions
(e.g., solid, liquid, gas) instead of focusing on the details of one-dimensional (1D) nanostructures [2,3],
(e.g., solid, liquid,(e.g.,
gas)solid,
instead of focusing
liquid, on theof
gas) instead details
focusing of one-dimensional
on the details of (1D) nanostructures
one-dimensional (1D)[2,3],
nanostructures [2,3],
electrochemical synthesis [5], or sensor applications [1,4,6,8]. This approach creates a unified view of
electrochemical synthesis
electrochemical [5], or sensorsynthesisapplications
[5], or sensor[1,4,6,8]. This approach
applications creates
[1,4,6,8]. Thisa approach
unified view of a unified view
creates
the advantages and disadvantages of each method, thereby enabling the significant features to be
the advantages and disadvantages of each method, thereby enabling the significant
of the advantages and disadvantages of each method, thereby enabling the significant features to be features to be
better understood and, hopefully, to anticipate new synthesis routes for CP nanohybrids.
better understoodbetterand, understood
hopefully, toand, anticipate
hopefully, newtosynthesis
anticipate routes for CP nanohybrids.
new synthesis routes for CP nanohybrids.
As will be shown later, different synthesis approaches can be conveniently categorized based on
As will be shownAs later, different synthesis approaches can
will be shown later, different synthesis approaches can be conveniently categorized based on
be conveniently categorized based
three particular aspects: (i) the oxidizing agent or synthetic mechanism, (ii) the template used in the
three particular aspects:
on three(i)particular
the oxidizing agent
aspects: (i) or
thesynthetic
oxidizing mechanism,
agent or synthetic(ii) the template
mechanism, used(ii)in the
the template used in
synthesis reaction; and (iii) the order of addition of each component. In this review, we discuss
synthesis reaction; theand (iii) the
synthesis order of
reaction; andaddition
(iii) theof eachofcomponent.
order addition of In eachthis review, weIndiscuss
component. this review, we discuss
various procedures for fabricating CP-only nanomaterials, as well as CP-based nanohybrids (binary
various procedures for fabricating CP-only nanomaterials, as well
various procedures for fabricating CP-only nanomaterials, as well as CP-based as CP-based nanohybrids (binary
nanohybrids (binary
and ternary systems), which are the root of hybrid nanomaterials.
and ternary systems), which are
and ternary the root
systems), of hybrid
which are the nanomaterials.
root of hybrid nanomaterials.

Polymers 2016, 8, 118 3 of 38
Polymers 2016, 8, 118 3 of 36

2. Overview
2. Overviewand
and Classification
Classification of Synthesis Methods

2.1.
2.1. Polymerization Mechanism
Mechanism
CPs
CPs are
are usually
usually synthesized
synthesized via via oxidative
oxidative coupling
coupling of of monomers.
monomers. For For polymerization,
polymerization, the the first
first
step
step isis the
the oxidation
oxidation ofof the
the monomer,
monomer, which
which results
results in
in the
the formation
formation ofof aa radical
radical cation,
cation, which
which then
then
reacts
reactswith
withanother
anothermonomer
monomerororradical
radicalcation,
cation,forming
forming a dimer. Hence,
a dimer. an obvious
Hence, an obviousclassification is the
classification is
initiation process
the initiation of polymerization.
process The three The
of polymerization. general initiation
three routes
general are chemical,
initiation routeselectrochemical,
are chemical,
and photo-induced
electrochemical, andoxidation, each having
photo-induced its own
oxidation, eachadvantages
having its and
owndisadvantages
advantages and (Figure 3). In the
disadvantages
first route,
(Figure 3). chemical oxidants
In the first (such as ferric
route, chemical chloride
oxidants (suchorasammonium persulfate)
ferric chloride are applied
or ammonium to oxidize
persulfate) are
the monomer.
applied In thethe
to oxidize second route, In
monomer. thethe
monomers are oxidized
second route, electrochemically,
the monomers are oxidized andelectrochemically,
in the third route,
light
and in is required
the thirdtoroute,
oxidize the monomer
light is requiredwith a photoinitiator.
to oxidize the monomerA partial
withsummary of these techniques
a photoinitiator. A partial
is shown inofTable
summary these1.techniques is shown in Table 1.

Figure 3. Schematic comparing the chemical, electrochemical, and photopolymerization mechanisms.
Figure 3. Schematic comparing the chemical, electrochemical, and photopolymerization mechanisms.
Each method
Each method has
has been
been evaluated
evaluated in
in term
term of
of variables
variables (V),
(V), in
in which
which aa low
low value
value means
means there
there are
are many
many
key variables
key variables in
in the
thesynthesis
synthesisprocess;
process;cost effectiveness
cost effectiveness(C), in which
(C), in whicha low value
a low corresponds
value to high
corresponds to
high cost; morphology control (M); time of reaction (T); scalability (S); and the resulting purity of
cost; morphology control (M); time of reaction (T); scalability (S); and the resulting purity (P) (P)the
of
materials.
the materials.

Table 1. Polymerization routes employed to obtain conducting polymers (CPs).
Table 1. Polymerization routes employed to obtain conducting polymers (CPs).
Route Details Ref.
Route Requires an oxidizing agent to synthesizeDetails the polymer. The morphology of the Ref.
Chemical
polymer can be controlled
Requires by varying
an oxidizing the to
agent parameters
synthesizeofthe
thepolymer.
process, The
such as [9–14]
polymerization
monomer/oxidizing agent concentration, temperature, pH, and
morphology of the polymer can be controlled by varying the reaction time.
Chemical polymerization [9–14]
An oxidizing parameters
agent is notof the process,
required for thissuch as monomer/oxidizing
route, which is an efficientagent
approach
Electrochemical concentration, temperature, pH, and reaction
for depositing CPs on substrates. Some monomers are theoretically not time.
[13,15–19]
polymerization electropolymerizable. Furthermore,
An oxidizing agent is notit isrequired
difficultfor
to scale up this
this route, process.
which is an
A high oxidation potential
efficient may for
approach leaddepositing
to over oxidation of the polymer.
CPs on substrates. Some
Electrochemical polymerization monomers
Illumination is needed forarepolymerization.
theoretically not electropolymerizable.
This route was developed to solve the[13,15–19]
Photo-polymerization over oxidationFurthermore, it iselectrochemical
problem of the difficult to scalemethod.
up this process. A high
The process can be well [20–24]
oxidation
controlled simply potential
by turning the may
light lead
on ortooff.
over oxidation of the polymer.
Illumination is needed for polymerization. This route was
developed to solve the over oxidation problem of the
Chemical synthesis methods
Photo-polymerization involve method.
electrochemical eitherThecondensation
process can be well polymerization
controlled (step-growth
[20–24]
mechanism) or addition polymerization simply by(chain-growth
turning the light on mechanism).
or off. The main advantage of chemical
synthesis is that it not only provides various possible routes to synthesize different CPs, it also
permits the large-scale
Chemical synthesis production of these
methods involve materials,
either which is
condensation currently impossible
polymerization with
(step-growth
electrochemical synthesis. Furthermore, chemical synthesis methods have more options
mechanism) or addition polymerization (chain-growth mechanism). The main advantage of chemical in terms of
covalent modification
synthesis of the
is that it not only CP backbone.
provides various possible routes to synthesize different CPs, it also permits
the large-scale production of these materials,straightforward
Electrochemical synthesis is a relatively synthetic
which is currently method
impossible for electrochemical
with fabricating CPs.
The conductivity of CPs allows them to be electrochemically polymerized. In general, electrochemical
polymerization is employed using a three-electrode system (working, counter, and reference

the energy transfer from the light occurs via the photosensitizer in order to form the corresponding excited states. and mechanical properties. In photochemical polymerization. PEDOT) can be fabricated both chemically and electrochemically. PANI. However. Most CPs can be synthesized by chemical polymerization. photosensitizers can be used as photocatalysts (e. However. a general scheme for the electrochemical route cannot be provided.g.. Although chemical oxidative polymerization can also be applied. The significant differences between chemical and electrochemical methods have been investigated by many researchers.. Photopolymerization (or photoinitiation) is another approach by which monomers can be polymerized by exposure to ultraviolet (UV) light. Furthermore. including the electrolyte. the electrochemical route is still preferable for thin CP films because employing an appropriate electrical potential allows the production of high-quality films with the desired thickness [26]. an electrolyte. and at the moment. PPy. Another work by Gorey et al. whereas chemical growth can provide more homogeneous morphologies than the electrochemical route [29]. it should be noted that CPs cannot be achieved by direct photopolymerization because they have a more positive oxidation peak potential than the redox potential of the photosensitizers [21]. Direct photopolymerization proceeds by absorption of the energy of illumination and then decomposition of the monomers into radicals. A number of crucial factors must be considered. visible light.Polymers 2016. ruthenium complexes. One difference is that very thin CP films (approximately 20 nm in thickness) can be produced using electrochemical polymerization. chemical synthesis methods have more options in terms of covalent modification of the CP backbone. showed that the polymerization time for the electrochemical approach is more rapid than that using chemical methods (a few minutes versus a few hours). photochemical polymerization is more advantageous because the radical is formed through hydrogen abstraction by irradiation. The conductivity of CPs allows them to be electrochemically polymerized. this idea is being challenged. deposition time/method (continuous versus pulsed) and applied potential. which is generally more efficient than direct fragmentation via a thermal reaction. but electrochemical synthesis is limited to those designs in which the monomer can be oxidized via a potential to form reactive radical ion intermediates for polymerization. counter. and appropriate additives. which is the limitation of chemical polymerization. To date. which is similar to free radical polymerization. whereas powders or very thick films are typically produced using the chemical technique [25]. 8. or holes (photoelectrochemical reaction). conductivity.28]. owing to the chemical diversity of the studied monomers. PT. In addition. several standard CPs (i.e. the chemical route can generate thin CP films via modification of the type and concentration of the oxidizing agent. Common examples of photopolymerization can be divided into two main categories: (i) direct photopolymerization and (ii) photosensitizer-mediated polymerization. Much effort has been expended on experimental research to overcome this difference. this process provides better control over the shape. which interestingly show that the electrical conductivities of CPs produced electrochemically were higher than those of CPs produced via chemical polymerization. Each of these parameters has an effect on film morphology. in the photosensitizer-mediated polymerization. Several reports have made direct comparison of chemical and electrochemical polymerization methods for the same monomers [27. 118 4 of 38 synthesis. As a consequence. and reference electrodes) in a solution comprising a monomer. Some drawbacks of the electrochemical method are the relatively poor reproducibility of bulk CPs and the fact that it is quite difficult to remove the grown film from the electrode surface. . and ketones). camphorquinone. From a thermodynamic viewpoint. laser-generating radicals (photochemical reaction). On the other hand. which directly impact the utility of the material for many applications. size. In general. this approach can resolve the problem of large activation barriers for the reaction. electrochemical polymerization is employed using a three-electrode system (working. and physical properties of CP nanomaterials by tuning the source of the initiator. the initiation rate can be very fast and well controlled by simply turning the illumination source on or off. Electrochemical synthesis is a relatively straightforward synthetic method for fabricating CPs. silver nitrate. As compared to the conventional chemical route.

Each approach has its own merits and demerits. . CdSe. To the best of our knowledge. etc. not all CPs can be produced by photoelectrochemical polymerization. SnO. This classification is based on two aspects: the preparation step and the ability of the technique to achieve shape modification and stability. and optical properties. leaving holes in the solution.Polymers 2016. A primary aspect of photoelectrochemical polymerization is that the oxidation step is guided by the difference between the potential of the valence band edge of the inorganic species (e. First. and temperature.g. 118 5 of 38 light intensity. photoelectrochemical polymerization allows for the deposition of CPs into micro-templates [30].. metal oxides such as TiO2 . which we defined in a previous study [4]. Photoelectrochemical polymerization can overcome this issue because illumination of the semiconductor electrode employs band-gap irradiation and improves the electrical conductivity via photoconductivity. the electrochemical route provides for large-area synthesis. additives. the former is independent of the nature of the electrolyte in terms of both the generation and the electrical properties of the resulting CPs. however.g. 8. electrons from the valence band are stimulated to the conduction band. causing irreversible oxidation (an over-oxidative state) of the electrogenerated CP. we suggest a new standard for the classification. Furthermore. The mechanism of photoelectrochemical polymerization can be described as follows: when the semiconductor photosensitizer is illuminated. metal oxide) and the oxidation potential of the monomer.g. These various approaches are discussed in the following subsections. the shape of the CPs is mainly determined by the template. including microemulsion polymerization.. the solid template approach.e. Second. chalcogenides such as CdS. pH. there are no distinct definitions of the methods. the difference between hard and soft templates is sometimes ambiguous. some researchers consider the terms “template-free” and “self-assembly” as other names for “soft template” [1. Methods for Fabricating Conducting Polymer Nanomaterials Prior to discussing recent progress in the development of CP-based nanomaterials in detail.2. It should be noted that traditional classification is still not unified. TiO2 . oxidation begins and initiates polymerization.g. the solid template needs to be prepared before the synthesis of CPs (as-processed). the morphology of the CPs can be varied by changing key synthetic conditions. Therefore. One can see that in some cases. it is worth briefly categorizing and summarizing the template-based synthesis procedures employed to obtain various nanostructures.. namely. and WO3 . high potentials must be applied. This approach was developed in order to solve the problems of electrochemical polymerization. These electrons are drained into an external circuit. whereas this is not necessary with molecular templating. the photosensitizer is a dye-sensitized semiconductor (e. However. solid template techniques are more stable than molecular templating for various conditions of temperature. relatively short processing times. When the photogenerated holes react with a particular monomer. mechanical. For instance. such as in infiltration of CPs into oxides (e.. although chemical oxidative polymerization can produce CPs with controlled sizes and shapes. e. CPs with different nanostructures can be prepared by a number of methods. W2 O5 . whereas for molecular templates. For photoelectrochemical polymerization. and GaAs) or simply a dye. and lithographic techniques (Figure 4). the electrochemical route (i. whereas other studies arrange them into separate groups [3]. electrodeposition) is often hindered by the low conductivity of the inorganic matrix. 2. Photopolymerization remains a valuable method that needs further exploration. and good electrical.2]. and ZnO). Overall. Comparing photoelectrochemically produced CPs with those prepared either chemically or electrochemically. and the template-free approach (Table 2). the molecular template approach. Finally.. ZnO. template filling. Generally. Consequently. in solid templates.

g. 118 6 of 38 Polymers 2016. andmethod and porous molecules. it is crucial to . Synthesis methods of CP nanomaterials. time consumption (T). and (3) the short time for need thin-walled tubes to use of harsh and longer chemicals (e.. of oxidizing agent. Each Each mechanism mechanism has been has been evaluated in term of variables (V). the template. Hard to provide good For chemical uniformity of sizetemplate synthesis. structure-directing alumina membranes which are produced by an electrochemical approach have been widely used as commercial commonly made via self-assembly mechanisms using hydrogen bonding.1. products.1. Thetosolid be removed templateby post- method processing. electrostatic interactions.times foracids strong thick-walled and bases)tubes or fibers) in order and thethe to remove kind and concentration template. an electrode at the bottom of the membrane. fabricating template method is that the template Importantly.solid short time for thin-walled template method istubes and longer a feasible. For chemical template synthesis. Electrochemical Electrospinning Simpletemplate to producesynthesis continuous can be also accomplished by employing polymers CP nanofibers. a template synthesis is more controllable via changing membrane isthe applied usually potential required or current to grow density. and polymers. Polycarbonate simply be immersed membranes prepared in a solution of theby a ‘‘track-etching” desired monomer.The main disadvantage providing of the for complete solidoftemplate control method the size and shape is of that thethe template needs nanostructures. As a result. oxidant. Schematic Schematic ofof the synthesis methods the synthesis methods for for CP CP nanomaterials. The size and morphology of the final products are predominantly determined by the pre-assembled molecular templates. is relatively and interval. Only soluble and thermoplastic a metal film as are applicable.2.. van der Waals forces. large-scale production by the electrochemical template method is 2. pores at an appropriate applied potential. which act as a the membrane.2. occurs within the pores Limitedof to certain precursors. large-scale production the solid template method by the electrochemical gives template precise control method over the shapeisand impossible. because of limitations in the size and pore density of the solid template. In this method. polymerization is subsequently carried out within the pores at an 2. anddisadvantage versatile for of the solidnanostructures. providing for complete control of the size and shape of the nanostructures. the applied The potential or current main advantage of density. which act as a template. and polymers. Solid Template Approach Table 2. morphology control scalability (S). times forand powerful. membrane. An expensive micro-mold is required. cost aspect (C). the membrane possible canunder simply optimized conditions. method is attractive as Molecular template it can be Relatively used simple. The main inexpensive. as wellisasthat this approach the it deposition timesimple.prepared by a “track-etching” liquid crystalline phases. confined by the size of the The solid template template membrane. Therefore. Possible to inside pores or channels of the membrane. thick-walled controllable tubes or fibers) tool and the for preparing kind and concentration of oxidizing agent. Electrochemical template synthesis can be also accomplished by employing a metal film as an electrode at the bottom of the membrane. because of limitations in the size and pore density of the solidAlthough template. the desired monomer. as well nanostructures insideas pores the deposition or channels timeofand theinterval. The solid template method is a feasible. and and purity purity (P) (P) of of the the products. Many molecular templates have employed properties of the CP. Solid Template impossible. and controllable tool for preparing Synthesis methods Advantages Disadvantages nanostructures of inorganic semiconductors. Nanostructure quantity is precisely control the size and morphology. (M). a template A post-synthesis process is required to remove membrane is usually Applicable Solid template requiredtotoalmostgrowallnanostructures CPs. Figure 4. significant drawbacks such as (1) small quantity production.g. scalability (S). template. Although size of CPs. However. 8. 118 6 of 36 Figure 4. AlthoughApproach chemical polymerization can be controlled by adjusting the polymerization time The (e. Polycarbonate membranes surfactants. In this method. Template-free Simple process without monomer polymerization then templates. metals.2. stacking. 8. electrochemical template nanostructures of inorganic semiconductors. be immersed in a solutionandofmorphology.. Molecular appropriate Template applied Approach potential.2.method and and dopant. in which a low value corresponds to high cost. (2) expensive templates. oxidant. powerful. which often destroys or disorders the formed nanostructures or is attractive as it can be used either chemically or electrochemically. widely used as commercial templates. porous alumina membranes produced by an electrochemical approach have been monomer polymerization then occurs within the pores of the membrane. and dopant. it has chemical polymerization can be controlled by adjusting the polymerization time (e. π–π templates. in which a low value means there are many key variables in the synthesis process. However.Polymers 2016. needstemplate the molecular to be removed approachby has post-processing. surface micelles. degrades the major properties the membrane of the canCP. either and chemically thus scale-up is or electrochemically. 2. strong potential which for often destroys or disorders the formed nanostructures or degrades the major producing large quantities of CP nanomaterials. electrochemical template synthesis is more controllable via changing researchers have developed molecular templates as an alternative to the solid template method. metals. etc. polymerization is subsequently carried out within the Nanoimprinting High throughput and high resolution. nanomaterials.g.

Therefore. the length of the surfactant tail in the hydrophobic core and the volume and effective area of each surfactant head group) [1]. liquid crystalline phases. etc. and orientation of the CP nanostructures [6]. strong acids and bases) in order to remove the template.2. sometimes with the assistance of solvent vapors or temperature control [42].3.2. It should be noted that the use of a template increases the cost of the synthesis and may also either modify or damage the properties of the synthesized nanostructures. Template-Free Approach In order to circumvent the drawbacks of the template approach. the template-free route is attractive owing to its low cost. the development of synthesis methods without using templates has been studied. the surfactant-assisted approach is widely applied because surfactant meso-phases are versatile molecular templates that are arranged in regular structures through self-assembly. morphology. the disadvantage of such a method is the poor control of the size. soft lithography is a low-cost.or nanostructures that cannot be fabricated by the solid template approach due to the limitations imposed by the pore structure of the template used. sodium dodecylsulfonic acid (SDS) [36–38]. and (3) the need to use of harsh chemicals (e. In order to resolve the limitations of this method (the equilibrium shape and size of surfactant aggregates). numerous factors must be considered.g. high-resolution. it is crucial to maintain the microstructure of the molecular template during polymerization in order to obtain the desired product.2. Hence.40] are conventional surfactants that have been widely used to prepare CP nanomaterials with different morphologies in several polymerization systems. inexpensive. electrostatic interactions. 8. β-naphthalenesulfonic acid) as dopants [41]. the mechanisms of self-assembly are quite complicated and not clearly understood. researchers have developed molecular templates as an alternative to the solid template method. 118 7 of 38 2.Polymers 2016.4. Among the physical methods used to prepare CP nanomaterials without . Molecular Template Approach Although the solid template method gives precise control over the shape and size of CPs. Among the various molecular template routes. The size and morphology of the final products are predominantly determined by the pre-assembled molecular templates. surface micelles. 2. Other Methods Some publications have reported other methods for producing CP nanostructures. As a result. Indeed.g. In addition. Nevertheless. In general. For example. which are commonly made via self-assembly mechanisms using hydrogen bonding. and structure-directing molecules.. which has prevented wide utilization of molecular template synthesis. The template-free method limits precise control of the morphology and properties. and high-throughput approach to fabricating nanoscale patterns using a micro-mold. such as the geometry of the template molecules (for example. The main advantage of this approach is that it is relatively simple.35].. simplicity. sodium dodecylbenzenesulfonate (SDBS) [23] and non-ionic isooctylphenyl ether (Triton™ X-100) [39. 2. (2) expensive templates. anionic sodium 4-[4-(dimethylamino) phenyldiazenyl]benzenesulfonate (MO) [34. van der Waals forces. in the case of micelles. and flexibility for thin-film device fabrication. a drawback that is similar to that of the molecular template approach [3]. Importantly. and versatile for fabricating nanostructures. One of the frequently cited methods is in situ polymerization using protonic acids (e. The main feature of this method is that the micelle-like structures formed by the monomer and dopant act as “molecular templates” during polymerization. it has significant drawbacks such as (1) small quantity production. Many molecular templates have employed surfactants. the molecular template approach has strong potential for producing large quantities of CP nanomaterials. Cationic cetyltrimethylammonium bromide (CTAB) [31–33]. the directed electrochemical nanowire assembly technique has been used to grow CP nanowires [43]. a template-free method is highly attractive because a template is not required for either the synthesis or the stabilization of the nanostructures. The template-free approach has great potential for preparing unique micro.2. π–π stacking.

ranging from very simple methods such as mechanical mixing of the two components. which limit the application of electrospinning. chemical or electrochemical In situ synthesis parameters need to Electrodeposition. Main Group Advantage Disadvantage Example Ref.g.5% have been obtained. 8. 2. heterogeneous components can be incorporated into CPs grown in the form of a film on the electrode surface [56]. [50–52] route. Preparation methods for synthesizing CP nanohybrids. (ii) in situ (sequential) synthesis. this process is not straightforward because the polymeric guest materials may be prevented from infiltrating the pores of the nanostructured host due to high interfacial tension as a result of physical limitations such as the hydrodynamic radius of the polymer. Furthermore. and the hybridization is achieved during a subsequent step by simple or more complex blending of two or more components in which interfacial tension between the different components determines the major properties of the resulting nanohybrids. These procedures are simple and usually highly suitable for solution-based processing. the electrospinning process seems to be the only method that can produce continuous long nanofibers. However. Finally. pore-filling ratios as low as 0. Facile control of be considered In situ reduction many variables Limited control over Redox reaction One-pot synthesis Simple Short processing time structure and morphology [53–55] Co-deposition of the products In the second category of methods (in situ synthesis).3. Limited applications Poor Mechanical mixing [45] Ex situ synthesis Simple Solution-processable control of the contact Layer-by-layer between each component [46] deposition Variable methods based on Higher complexity as many In situ polymerization. Synthesis Methods for CP Nanohybrids Based on the mechanism and procedure for the fabrication of CP nanohybrids. It is apparent that nanohybrids obtained by in situ methods may have several advantages over their ex situ-prepared counterparts because the organic/inorganic interface can be better controlled at the molecular level. leading to incomplete pore filling. first.. to achieve good fiber formation. in the case of the electrochemical in situ route.Polymers 2016. The main characteristic of all the methods in the first category is that the CPs and inorganic species are synthesized separately. there are various valuable strategies available. polyethylene oxide (PEO)) are usually added for the purpose of tailoring the viscosity of the mixture [44]. Table 3. to more sophisticated methods such as ligand exchange or layer-by-layer fabrication procedures [45–47]. Specifically. electrospinning is one of the most popular methods because it is easy and effective for generating long CP nanofibers using strong electrostatic forces. differences in the hydrophobic/hydrophilic nature of the two components can further limit the application of such procedures. One benefit of such an approach is that the structure and properties of the hybridized material can be controlled by changing the critical variables such as deposition time and . These techniques can be further classified on the basis of the component formed in situ. some non-conducting polymers (e. resulting in highly ordered nanoarchitectures [48. the methodologies may be classified into three main categories: (i) ex situ (sequestered) synthesis. However. Finally. and (iii) one-pot (concurrent) synthesis [5]. which is a milestone for enabling mass production and processing via roll-to-roll printing. Another benefit of these methods is the well-established synthesis procedures because each component is manufactured separately using a known process. the nanofibers may exhibit a substantial concentration of defects and a large size distribution. As for the hybridization process. 118 8 of 38 templates. at least one component of the nanohybrid is generated in the presence of its counterpart.49]. As compared to other synthesis routes. physical infiltration of CPs into inorganic nanostructures can also be achieved. as represented in Table 3 and Figure 5.

These techniques can be further method. The poly(styrene sulfonate) (PSS) chains on the silica core surfaces not only facilitate uniform deposition of the conducting copolymer poly(aniline-co-pyrrole) through electrostatic interaction. time time required required (T). The general interface can be better controlled at the molecular level. in which a low value corresponds to high cost. disadvantage of these methods is the poor control of the size and morphology first. 4 3 Figure 5. The highlights of this route can be summarized as follows: (i) the symmetrical spherical structure of the ASPB can guarantee a spherical morphology with enhanced conductivity. Recent Advances in the Synthesis of CP Nanomaterials The most significant trials in liquid-phase polymerization have relied on the utilization of templates for controlling the morphology of CPs on a nanometer scale. where solid templates are an excellent candidate for many applications. For Higher chemicalcomplexity in situ as In syntheses. many parameters need to Electrodeposition. category the third category. differences in the hydrophobic/hydrophilic nature of the two components can further limit the application of such procedures. and the polymer mayVariable be methods based insufficiently on compact. they also serve as anionic dopants for the copolymer. and (ii) charged polymer chains can still be included on the periphery of the nanocomposites via control of the length of the brushes and the thickness of the CP shells to improve the stability of the suspension of the nanoparticles. process.ofnamely methods (in situ one-pot synthesis). synthesis Most methods focus on Facile control of many variables strategies where the CPs be considered are formed in the presence In situ reduction [52] of the inorganic species. Schematic Figure 5. [51] is rather straightforward. form of a film on the electrode surface [56]. resulting of the products in hybridized structures [57]. methods. Then. Limited applications Mechanical mixing [45] Ex situ Simple Poor control of the contact synthesis Solution-processable Layer-by-layer deposition [46] current density.5% have been obtained. control over namely. 118 Main Group Advantage Disadvantage Example 9 of 38 Ref.as 0. The advantages of using TiO2 -PSS are similar to those of using ASPB because it too exhibits the ability to capture and control the ions within the layer of PSS chains via electrostatic interaction. however. (M). Zhang et al. Similarly. formation of the [50] nanohybrid In situ chemical or electrochemical route. In the second Lastly. a high concentration of monomers is mainly distributed close to the cores of the ASPB. Specifically. Schematic of of nanohybrid nanohybrid synthesis synthesis methods. exbut situ-prepared counterparts co-electrodeposition because is more the organic/inorganic attractive [55]. situ polymerization. the inorganic component is One-pot Simple Redox reaction [53] synthesized in situ within the CP. These “one-pot” synthesis methods are fundamentally based on in situ reactions classified on the basis that of the component formed in situ.1. For example. . Although a higher current density between eachtocomponent leads faster growth. (V). heterogeneous components can be incorporated into CPs grown in the hybridized materials. Huang´s group proposed a strategy using anion spherical polyelectrolyte brushes (ASPB) with silica cores as templates and dopants for the synthesis of conductive copolymer nanocomposites [58]. Wet-chemical co-precipitation structure and morphologyis an approach for synthesis of CPs synthesis Short processing time Co-deposition [54. Each Each mechanism mechanism has has been been evaluated evaluated in in terms terms of of variables variables (V). It is apparent that nanohybrids obtained by in form organic/inorganic phases simultaneously in a single stage. pyrrole monomers are oxidized by ferric ions in the shell of the PSS to generate PPy. (T). it is not easy to control. [59] used TiO2 nanotube-PSS as a template and dopant for the synthesis of PPy.55] with an oxidant such as KMnO or FeCl . scalability (S). in in which which aa low low value value means means there there are are many many key key variables variables in in the the synthesis synthesis process. Table 3. Finally. Both chemical and electrochemicalsitu methods may have several processes can advantages be applied toover this their group. morphology morphology control control (M). Thus. and purity (P) of products. in the case of the of the resultant electrochemical in situ route. Progress in CP Nanomaterial Synthesis 3. cost (C). Preparation methods for synthesizing CP nanohybrids. syntheses at least one is probably component the simplest (butofleast the controllable) nanohybrid is generated in the presence of its counterpart. Polymers 2016. One benefit of such an approach is that the structure and 3. 8. the opposite is also Limited possible.

. stepwise polymerization created PPy-PEDOT or PEDOT-PPy nanowire heterojunctions (Figure 6).63]. A recent pentadecylphenyl phosphoric acid. permission from with [60]. which have become expensive owing to increased demand and depletion containing brine. Copyright permission 2015. [60] reported electropolymerization of pyrrole and bithiophene (BiTh) using PEO-filled cylindrical domains of a microphase-separated PEOm -b-PMA(Az)n as a template. Importantly. which determines the electrical properties [67]. from [60]. with the acid group as a notable example of such a formation mechanism is outlined in Figure 7. have a unique amphiphilic design. Note that molecular based surfactants. Polymers 2016. the main constituent of cashew nut shell extract. In particular. which determines the electrical properties [67].Polymers 2016. templates with demonstrated an efficient method to fabricate large-area two-dimensional (2D) colloidal crystals as a high-aspect-ratio nanopores suffer from poor monomer diffusion in liquid-phase polymerization. Other surfactants that have been investigated a hydrophilic head group and a long alkyl chain as a hydrophobic tail. Although the nanostructural fabrication of CPs has been achieved with nanoporous solid Molecular templating has also continued to play a key role in CP synthesis. properties of supercritical fluids are intermediate between those of liquids and gases. Komiyama et al. namely.g. This approach might be a good alternative to traditional petroleum- Molecular templating has also continued to play a key role in CP synthesis.6. Supercritical fluids are characterized by lower viscosities on the size.g.4- with different diameters were prepared by surfactant templating and their electrical properties ethylenedioxythiophene (EDOT) formed liquid crystalline templates of various shapes with the acid depended on the size.69] explored liquid crystalline templates with an inexpensive and and large diffusivities as compared to conventional liquids because the physicochemical properties of abundantly available industrial by-product. The results were very impressive: while one-pot polymerization gave lateral-composition-modulated copolymer structures. Choi et al. where CPs are generally synthesized in a microphase-separated domain. which has a relatively high solubility and dielectric constant without the crystals at the air-water interface. and cyclohexane oil.. In addition. the main constituent of cashew nut shell extract. with the acid group as compound and a cationic surfactant such as CTAB [70]. Supercritical fluids are characterized by lower as nanosphere lithography-mediated electrodeposition [62. Although the nanostructural fabrication of CPs has been achieved with nanoporous solid As a possible milestone for industrial fabrication of colloidal crystal templates. PPy hollow nanoparticles with (scCHF3 ). Much effort has been invested in finding the best composition for use as a molecular template. [36] fabricated swollen liquid crystalline templates with a quaternary mixture petroleum-based surfactants. cardanol(3-pentadecylphenol). polar solvents) [64. Note that molecular templates via electropolymerization. In particular. Dutt et al. supercritical fluids are intermediate between those of liquids and gases.65]. [61] templates via electropolymerization. this method involves the electrophoretic deposition of negatively solution for this problem might be the use of supercritical fluids such as supercritical charged polystyrene colloidal particles and the assembly of the colloidal particles to 2D colloidal trifluoromethane (scCHF3). polar solvents) [64. such need for additives (e. Importantly. cardanol(3-pentadecylphenol). PEOm -b-PMA(Az)n (polymethacrylate with azobenzene-mesogen in side chain )block copolymer Reprinted withReprinted as a template. Copyright Chemical Society. it also resources. [68. 118 10 of 36 Figure Figure 6. the monomer include indigo carmine [71] and Pluronic® F127 [72]. gyroids. Devaki et al. columns.69] explored liquid crystalline templates with an inexpensive derivative of cardanol. where the PMA(Az) indicates polymethacrylate with azobenzene-mesogen in side chain. American2015. templates with templating is not only used to control the morphology of the resultant nanoparticles [66].65]. such as discs. of resources. Devaki et al. and abundantly available industrial by-product. Acid derivatives of cardanol. A affects the doping state of the CPs. Acid derivatives of cardanol. 118 10 of 38 Block copolymers can also be used as templates. including 3-pentadecyl phenol-4-sulfonic acid and insoluble complex templates with lamellar mesostructures were formed with a noble metal 3-pentadecylphenyl phosphoric acid. the monomer 3. this process is still challenging. A template for nanopatterning of CPs. 8. 8. this process is still challenging. which has a relatively high solubility and dielectric constant without the need for different diameters were prepared by surfactant templating and their electrical properties depended additives (e. it also high-aspect-ratio nanopores suffer from poor monomer diffusion in liquid-phase polymerization. [68. Similarly. which have become expensive owing to increased demand and depletion of templating is not only used to control the morphology of the resultant nanoparticles [66]. in which Langmuir-Blodgett deposition viscosities and large diffusivities as compared to conventional liquids because the physicochemical and drop casting were used to fabricate nanosphere templates. American Chemical Society. other solid template methods have been developed. For example. have a unique amphiphilic design. and lamella. PPy hollow nanoparticles hydrophilic head group and a long alkyl chain as a hydrophobic tail. A recent notable solution for this problem might be the use of supercritical fluids such as supercritical trifluoromethane example of such a formation mechanism is outlined in Figure 7.. SDS as a surfactant. namely. This approach might be a good alternative to traditional For instance. including 3-pentadecyl phenol-4-sulfonic acid and 3- affects the doping state of the CPs. 1-pentanol as a co-surfactant.Comparison of stepwise Comparison (above) of stepwise and one-pot (above) (below)(below) and one-pot electropolymerization using PEO electropolymerization m-b- using PMA(Az) n (polymethacrylate with azobenzene-mesogen in side chain )block copolymer as a template.

4-ethylenedioxythiophene (EDOT) formed liquid crystalline templates of various shapes with the acid derivative Polymers of cardanol. mechanism. and (iii) SDBS not only acts as a surfactant but also a dopant for PPy to trap cations present been reported. However. 1-pentanol as a co-surfactant. (a) Schematic of (a) Schematic of the the formation formation mechanism. effect of the time when the anionic surfactant SDS was added during the template polymerization of These differences determined the final morphology of the PPy nanostructure. respectively. such as discs. Liao et al. Copyright 2015. (ii) the inverse opal PPy presented a growth with parallel channels approximately 2–3 nm in width. due to their complexity. Various impressive approaches have also been developed. Interestingly. Rivero et al. such as direct growth by chemical Using a method based on template-free electrochemical polymerization. β-naphthalenesulfonic acid used as a dopant led to of the as-prepared film appeared only after the surfactant molecules were removed [75]. Other surfactants that have been investigated include treatment to remove them. [74] designed a new approach using mesostructured SiO2 as a solid as a surfactant for fabricating 3D macroporous PPy inverse opals. 8. in the CTAB-free higher surface area (19. columns. the differences in the self-assembly behavior of further growing PPy chains at different redox states. the CPs was also investigated [76]. SDS as a surfactant. 2016. they can be easily dissolved by common solvents. many interesting results have Much effort has been invested in finding the best composition for use as a molecular template. (c. Sharma and co-workers [73] employed monodispersed poly(methyl methacrylate) For instance. Table 4 lists representative examples of synthesis methods for CP nanomaterials developed over the last three years. Copyright 2015. (ii) the inverse opal PPy indigo carmine [71] and Pluronic® F127 2[72].2 m ·g−1) as compared to conventional non-porous PPy films (4. Moreover. Preparation Figure Preparation of of PPy PPy hollow hollow nanoparticles. Group. nanoparticles. enzymatic polymerization using sodium bis(2- fabricated PPy nanostructures of several different morphologies on a prenucleated PPy thin film and ethylhexyl) sulfosuccinate (AOT) as a template [81]. Other new developments for combining templating methods have also been [75]. the silica template showed well-ordered remove them. precursor solution. bipolar electrochemistry [79. It should be noted that the redox current response electron microscopy (FE-SEM). Reprinted with permission from [67]. [77] successfully micropatterning [78]. been reported. On the other hand. Dutt et al. including solid and molecular templates.8 By combining templates. It should be noted that the redox and (iii) SDBS not only acts as a surfactant but also a dopant for PPy to trap cations present in the current response of the as-prepared film appeared only after the surfactant molecules were removed surrounding solution.d) Transmission electron electron microscopy (TEM) images of the hollow PPy nanoparticles with diameters of microscopy (TEM) images of the hollow PPy nanoparticles with diameters of 100 and 200 nm. . they can be easily dissolved by common solvents. and edge nanoimprint lithography [82]. Rivero et al. the silica template showed well-ordered growth with successfully fabricated PPy nanostructures of several different morphologies on a prenucleated PPy parallel channels approximately 2–3 nm in width. When CTAB was added to the synthesis medium. presented a higher surface area (19.7.Polymers 2016. Sharma and co-workers [73] employed monodispersed poly(methyl methacrylate) in the surrounding solution. [36] fabricated swollen liquid crystalline templates with a quaternary mixture (PMMA) colloids ~430 nm in diameter as three-dimensional (3D) colloidal crystal templates and containing brine. There are three main advantages template to synthesize self-doping copolymer poly(aniline-co-aminobenzoic acid) in the presence of to this method: (i) although PMMA colloids are solid templates and require chemical treatment to CTAB. When Using a method based on template-free electrochemical polymerization. gyroids. a microporous silica deposit was obtained.80].100 and 200 nm. [77] CTAB was added to the synthesis medium.2 m2 ¨ g´1 ) as compared to conventional non-porous PPy films (4. such methods are not popular for the synthesis of CP nanomaterials for applications. SDBS as a surfactant for fabricating 3D macroporous PPy inverse opals. and cyclohexane oil. By combining templates. and they will require significant time for improvement. [74] designed a new approach using mesostructured SiO2 as a solid template to polymerization of the CPs was also investigated [76]. Moreover.8 m2 ¨ g´1 ). There are three main insoluble complex templates with lamellar mesostructures were formed with a noble metal compound advantages to this method: (i) although PMMA colloids are solid templates and require chemical and a cationic surfactant such as CTAB [70]. including solid and molecular templates. On the other hand. Other new developments for combining templating methods have also (PMMA) colloids ~430 nm in diameter as three-dimensional (3D) colloidal crystal templates and SDBS been reported. (c. 118 11 of 38 3. Reprinted with permission from [67]. in the CTAB-free precursor thin film and examined their growth mechanism using 3D AFM imaging and field-emission scanning solution. Liao et al. a microporous silica deposit was obtained. synthesize self-doping copolymer poly(aniline-co-aminobenzoic acid) in the presence of CTAB. 118 11 of 36 Figure 7. In addition. and lamella. many interesting results have m2·g−1). Nature Publishing respectively. the effect of the time when the anionic surfactant SDS was added during the template reported.d) Transmission (b) UV-vis absorption spectra of aminopyrene in different solvents. 8. Nature Publishing Group. (b) UV-vis absorption spectra of aminopyrene in different solvents.

and they will require significant time for improvement. These differences determined the final morphology of the PPy nanostructure.14]. Table 4. For the chemical route. and edge nanoimprint lithography [82]. CP Polymerization method Details Refs. effects of the dopant (D-tartaric acid [11]. was investigated for a combination of chemical and electrochemical polymerization [13. β-naphthalenesulfonic acid used as a dopant led to differences in the self-assembly behavior of further growing PPy chains at different redox states. sulfanilic acid azochromotrop [18]. Interestingly.Polymers 2016. due to their complexity. bipolar electrochemistry [79. However. aromatic and amphiphilic sulfonate [17]). these include oxidant/monomer ratio and washing post-treatment [9].95]. the investigation of various crucial processing factors has been undertaken. such as direct growth by chemical micropatterning [78]. enzymatic polymerization using sodium bis(2-ethylhexyl) sulfosuccinate (AOT) as a template [81]. investigations of the deposition potential and temperature [96] and chloroform as the environment [97] have been undertaken. 118 12 of 38 examined their growth mechanism using 3D AFM imaging and field-emission scanning electron microscopy (FE-SEM). Amyloid nanofibers were successfully used as Amyloid nanofiber template templates for the formation of conductive [83] polymerization core-shell nanowires Production of CPs with controlled shapes on Planar DNA template 2D polyelectrolyte templates was investigated [84] for the first time Electrospinning using poly(amic acid) Hollow nanofibers with controllable wall [85] fiber as a template thicknesses were successfully obtained PANI Water-dispersed CP nanofibers with high Dedoped chemical polymerization [12] capacitance were achieved by double doping The mechanism for self-assembly in crystalline Biphase interfacial polymerization [86] 1D nanostructures was investigated A new approach for multimodal core-shell Surface-initiated polymerization nanoparticles with a stable doping state was [87] reported A novel hollow PANI nanocapsule with holes Interfacial polymerization [88] in the wall was synthesized A new synthesis approach for the precise Time-dependent template-assisted control of wall morphologies of colloidal [89] polymerization microparticles was studied PPy A good method to control the shape of micelles Modified pulse potentiostatic method at the substrate/electrolyte interface and [90] control the morphology of CPs was proposed Good result combining a carboxylated polystyrene template made by nanosphere Galvanostatic electrodeposition [91] lithography with SDS as a molecular template was achieved PEDOT A novel method using colloidal chemistry to Non-spontaneous emulsification [92] fabricate multifunctional CPs was developed Electron pulse-enabled in situ The mechanism of CP growth was investigated [93] polymerization experimentally and via modeling In addition to the development of templating techniques to synthesize CP nanomaterials. Representative examples of fabrication methods for CP nanomaterials developed over the last three years. Based on the electrochemical route. a new anionic dopant. the electrophoretic force was successfully . the chemical effects of the solvent (solvent-free versus solvent-limited syntheses) [10]. 8. Finally. For the electrochemical approach.80]. such methods are not popular for the synthesis of CP nanomaterials for applications. Table 4 lists representative examples of synthesis methods for CP nanomaterials developed over the last three years. Various impressive approaches have also been developed. and the polymerization kinetics [94.

whereas with dielectrophoretic assembly. It was found that co-vapors such as alcohols and water can affect (i) the vaporization of the monomer. 118 13 of 38 exploited for the deposition and assembly of CP nanomaterials.Polymers 2016. however. factors that are essential for industrial manufacturing. to date. The initiator and monomer must be in a vapor phase in the CVD process. the “particles” are subjected to a non-uniform electric field and thus need not be charged. Shen et al. and (v) the diffusion of the monomer into the substrate. In order to solve this problem. For non-liquid phase polymerization. and large-area processing. the two methods for synthesizing CPs in a vapor phase are quite efficient. by applying a uniform electric field. namely vapor-phase polymerization (VPP. Hairy CP nanowires were obtained via mechanochemical polymerization using PANI [99] citric acid as a dopant Solid phase The role of temperature in the solid-state synthesis was studied [102] PEDOT A low-cost. whereas only the monomer needs to be in the vapor phase for VPP. all of which lead to significant changes in the characteristics of the resultant CP. Phase CP Details Refs. high deposition rate. The distinction between these methods is in how the initiator is applied during polymerization. The latest work reported that co-vapors can be introduced into the VPP process to modulate the morphology and properties of the resulting CP product (Figure 8) [82]. charged “particles” are deposited onto electrodes in a solution. often called vapor deposition polymerization. The morphology of CPs using the VPP method is highly affected by the synthesis conditions. Representative reports for the solid/vapor-phase polymerization of CP nanomaterials. Meanwhile. [98] made PANI directly assembled onto multiscale sub-micron templates using a dielectrophoretic technique. vapor-phase synthesis has provided unique possibilities in terms of tuning the synthesis process of CPs. Consequently. The dielectrophoresis approach has advantages over electrophoresis. the dimensions of the assembled CPs were limited to the micron scale. as well as by the substrate curvature [100]. VDP) and chemical vapor deposition (CVD). Solid-phase polymerization is rarely used for CP synthesis. As compared to other approaches. low-temperature method to fabricate high-performance CPs was [103] successfully developed PANI The effect of microwave radiation was studied [104] The role of co-vapor in the vapor-phase polymerization (VPP) method [105] was studied PPy An application for drug storage was carried out by depositing PPy using the [106] chemical vapor deposition (CVD) method Vapor phase The dependence of electrical conductivity on VPP temperature was discussed [107] Single-crystal CP nanowires were developed using VPP with [108] PEDOT liquid-bridge-mediated nanotransfer printing A one-step fabrication of 2D nanoparticles was investigated [109] The advantages of directly depositing CP nanofibers was demonstrated [110] . meaning that the template can be reused and the materials can be assembled without charging. the two main routes are solid phase and vapor phase (Table 5). although it is very simple. the advantages of such a method are not clear. (ii) the orientation of forming polymer chains. Bhandari et al. Table 5. 8. In electrophoretic assembly. electrophoresis offers advantages such as additional controllable synthetic parameters. As compared to liquid-phase polymerization. [99] presented the first study of PANI nanowires prepared using a mechanochemical route. even multi-dimensional CP nanostructures can be fabricated via this route [101]. CVD and VPP can produce thinner films with better reproducibility and higher crystallinity and conductivity. Although good results have been achieved for doped CPs patterned onto microscale templates by electrophoresis. PANI was successfully deposited uniformly onto 100-nm-wide electrodes with multiple length scales. (iv) the swelling of the substrate. such as avoiding oxidation of the template surface. To date. (iii) the rate and efficiency of oxidative polymerization.

111. (b–h) Scanning electron microscopy (SEM) images of papers papers prepared with co-vapors: (b) methanol. Nature high magnification). (left: low magnification.112]. Interestingly. (d) water. nanohybrids have fascinated many researchers because of their usefulness in many The formation mechanism of Au-PANI was Au Interfacial polymerization applications. 8. Reprinted with permission from [105].115]. Characteristics of the preparation methods can be recognized by comparing the synthesis examples of MnO2 /PANI using adsorption templates [113] and reactive templates [114.67. benzene. It has been noted that the Chemical oxidative Aqueous diethylene glycol solution medium properties of hybridCdO nanomaterials may vary significantly depending [119] polymerization was used for the first on timethe preparation methods even for the same materials.Polymers 2016. Nature Publishing Group. Reprinted with and (h) no vapors. (a) Vapor-phase polymerization (VPP) of pyrrole with co-vapors on a cellulose substrate Figure 8. (c) ethanol. (a) Vapor-phase polymerization (VPP) of pyrrole with co-vapors on a cellulose substrate and and a typical photograph of as-prepared paper. and (h) no vapors. (f) toluene. (b–h) Scanning electron microscopy (SEM) images of a typical photograph of as-prepared paper. The resulting Combination nanohybrids of with an optimized A multicolor ratiofilm electrochromic of MnO was x /CP showed the TiO following merits: (i) the 2 hydrothermal coated CP providedand fabricated conductive based onfor pathways hybrid core-shell better [118] . species Recently. (g) prepared with co-vapors: (b) methanol. (f) toluene. in electrochemical capacitor applications. 3. and utilization of MnO x electropolymerization nanorod arrays (ii) both MnOx and CP exhibited synergistic electrochemical properties. (e) hexane. Representative examples of the incorporation of inorganic species into CPs. the results using the adsorption template method showed higher specific capacitances than their counterparts using the reactive template . 118 14 of 38 Polymers 2016. Novel Trends Inorganic for Synthesis of CP Nanohybrids CP Preparation method Details Refs.wasdirect CP nanocoating has been[46] first reported made on the surface of MnOx .2. 118 14 of 36 Figure 8. The structure A notable of a Cu/PANI hybridexample was is manganese [117] studied oxide (MnOx )/CP nanohybrids [51. permission from(left: [105]. Publishing Group. right: high magnification). Table 6. (g) benzene. Copyright right: 2015. (c) ethanol.low magnification. 8. (d) water. as discussed synthesis above. (e) hexane. Copyright 2015. Because MnOx can act as a reactive template in an A Pd/PANI/Pd sandwich-structure nanotube acidic medium PANI forPd Layer-by-layer the chemical technique polymerization ofarray CP. The fabrication of these hybrids can bepresented commonly achieved via the combination [116] of CPs and inorganic speciesCu in theConcurrent nanometer regime.

Table 6 shows several representative examples for nanohybrid synthesis using CPs and metal. As a partial summary. 118 15 of 38 method. The formation mechanism of Au Interfacial polymerization [116] Au-PANI was presented The structure of a Cu/PANI hybrid Cu Concurrent synthesis [117] was studied A Pd/PANI/Pd sandwich-structure Pd Layer-by-layer technique [46] nanotube array was first reported A multicolor electrochromic film was Combination of hydrothermal and TiO2 fabricated based on hybrid core-shell [118] PANI electropolymerization nanorod arrays Aqueous diethylene glycol solution CdO Chemical oxidative polymerization [119] medium was used for the first time Vertically aligned chemical A good example of hybrid 3D tubular MoS2 [120] polymerization structures was discussed A mesoporous dual-layer film was Se0. CdSe RAFT polymerization [134] was emphasized * Commercially available chemical. the exact composition is given in the reference. no mention of any specific CPs. an [123] Ag technology “aero-sponge. Au. CP Inorganic species Preparation method Details Refs.Polymers 2016. Table 6.or metal oxide-based species. ** a general term. namely.5 Te0.” was proposed Highly stable sensing activity of the Cathodic co-deposition [124] hybrid was studied MnO2 Electropolymerization Effect of deposition time was reported [51] Ultrasound-assisted chemical Well-controlled granular and layered ZnO [125] polymerization nanocomposite was formed The previous method was extended to CuO Wire template technique [126] study polymerization time PPy Modified hydrothermal and 3D growth of well-aligned nanowire CoO [127] post-annealing process array was developed A facile strategy for intercalation of MoS2 In situ intercalative polymerization PPy into MoS2 nanosheets was [128] proposed Pulsed-light and pulsed-potential Good control of the deposition rate TiO2 [129] method was demonstrated Low-temperature in situ A new anode material for rechargeable LiV3 O8 [130] polymerization lithium batteries was reported A facile method for fabricating Reflux method and chemical ZnCo2 O4 mesoporous ZnCo2 O4 -coated PPy was [131] polymerization developed Interfacial bonding and morphology PT ZnO Electropolymerization growth [16] control was described First method for fabricating layered “Cocoon-to-silk” fiber reeling V2 O5 V2 O5 /PEDOT nanowires was [132] method reported PEDOT A new simple. 8.5 Lyotropic liquid crystalline template [121] synthesized using Brij56 surfactant Dual nature of hybrid (cathode MnFe2 O4 Incorporative polymerization catalyst and anode modifier) was first [122] demonstrated Incipient network conformal growth A new porous material. . Representative examples of the incorporation of inorganic species into CPs. fast. and inexpensive Spin-coated-assisted deposition Iron oxide * technique for the fabrication of a [133] with “supporting layer technique” free-standing hybrid was reported Role of the direct covalent attachment CP ** Ag.

Polymers 2016. the electrochemical growth of PEDOT starts to take place predominantly on the surfaces of the nanoparticles. One-pot UV-induced Effect of concentration ratio of composite in cellulose [135] photopolymerization fabric was studied PPy/Ag One-step interfacial Thin. Ansari et al. which can result in irreversible oxidation of the CPs. Mazzotta et al. In addition. Using photoelectrochemical polymerization. such infiltration is often hindered due to the high interfacial tension between the host and the guest. resulting in excellent electrochemical activity due to the synergistic properties between the nanoparticles and CPs. graphene. [32] synthesized graphene/PANI nanocomposites using an in situ oxidative polymerization in the presence of CTAB as a surfactant. flexible nanofilms were synthesized at the [136] photopolymerization water–air interface Photo-assisted electrodeposition Effect of LiClO4 in the presence of SDBS was investigated [23] PPy/TiO2 Photoelectrochemical Properties of nanohybrid in the presence of SDS [22] polymerization was studied PPy/WO3 In situ photopolymerization A room-temperature H2 S gas sensor was fabricated [24] A good example of one-step photopolymerization PPy/ceria Photo-induced polymerization [137] was shown UV and visible light The mechanism of photopolymerization with iodonium PPy/methacrylate [138] photopolymerization salt was presented Microemulsion Effect of different concentrations of cationic surfactant PPy/AgBr/Ag [31] photopolymerization CTAB was studied A novel methodology for fabricating a network film PT/epoxy One-pot photoinduced synthesis [20] was given The silanization of clay on a PPy/Ag surface was Clay/PPy/Ag In situ photopolymerization [139] discussed Role of donor-π-acceptor sensitizers was described [140] A new method using aqueous micellar solutions Photoelectrochemical [141] PEDOT/TiO2 was shown polymerization The effect of light intensity on the oxidation level of [142] PEDOT was studied Carbon and carbon derivatives such as carbon nanotubes (CNTs). Using simple thermal treatments and chemical VPP. 8. A summary of recent photosynthesis studies for CP nanohybrids reported in the literature is given in Table 7. [75] overcame this problem. proper control of the corresponding morphology (such as pore size and specific surface area) is critical. Next. Samu et al. [30] also successfully demonstrated that highly flexible CP microstructures can be achieved from a silicon template via light-activated electrochemical processes. Representative examples for photosynthesis of CP nanohybrids. an EDOT monomer is oxidized by photogenerated holes on the surface of a metal oxide. however. Therefore. a high-surface-area composite with high conductivity is desired to achieve superior performance for applications of CPs. Table 7. One of the most well-known routes for in situ synthesis of CPs within a nanostructured host metal oxide is the infiltration method. even though the electrical conductivity decreased with increasing nanoparticle content. Graphene nanosheets were uniformly distributed in the PANI matrix with the aid of CTAB. [111] successfully synthesized MnO2 nanoparticles/PEDOT porous hybrids. leading to high conductivity and thermal stability . The highlight of this porous hybrid is an “open” porosity. graphene oxide (GO). in addition to the optimization of the main properties such as electrical conductivity. and reduced graphene oxide (rGO) are other potential components for the synthesis of nanohybrids (Table 8). The polymerization is initiated by sensitizer nanoparticles. As a first step. the combination of the physical infiltration approach and electrochemical polymerization requires positive potentials. Material Preparation method Details Refs. The simplest approach is physical infiltration. 118 16 of 38 In general. Yang et al.

Table 8. Exfoliation of graphite by CPs may be an efficient strategy for functionalization of graphene with CPs [147]. they also exhibited high dispersion stability in N-methyl-2-pyrrolidone Polymers 2016. This method is more beneficial than the conventional approach due to the high electrical conductivity of pure graphene layers. 2015. The resulting nanohybrids not only showed excellent electrochemical performance. 1. glue. John John Wiley Wiley& &Sons. (b) Photographs (GPMNs) by direct physical exfoliation of graphite with PANI glue. p-toluenesulfonic acid used as a dopant also contributed the enhanced electrical and thermal properties. amaranth. Many studies have focused on the use of GO or rGO with CPs. 118 (NMP) and water for more than three months at room temperature. Similarly. Carbon CP Preparation method Details Refs. 8. Copyright Copyright 2015. the promotion of the coupling of the EDOT monomer in the 2-. Representative examples of studies where carbon nanomaterials were incorporated into CPs. Wang et al. [45]. 118 17 of 38 via the π–π interactions between graphene and PANI.5-naphthalene disulfonate. (b) Photographs showing showing the the long-term colloidal stability of the GPMN dispersion solution in the absence (left) and long-term colloidal stability of the GPMN dispersion solution in the absence (left) and the presence the presence (right) of (right) of PANI PANI glue. For instance. Figure 9. 5-positions of the thiophene unit reduced undesirable coupling. water. it is noteworthy that several dopants. [146] synthesized nanohybrid electrode materials through in situ polymerization of thiophene-grafted GO in the presence of an EDOT monomer and investigated the covalent linking of GO with PEDOT chains. (a) (a) Schematic Schematic illustration illustration of of the theformation formationof ofgraphene/PANI graphene/PANI multilayered multilayered nanostructures nanostructures (GPMNs) by direct physical exfoliation of graphite with PANI glue. and pyrocatechol violet [145]. 8. Via the covalent coupling of GO with the 3-position of the thiophene unit. A microspherical and porous structure In situ polymerization [50] was fabricated Complex of PANI and GN for enhancing Reflux technique [148] charge-transfer ability was reported PANI Sandwiched GN–mesoporous A novel approach to fabricate [149] silica as template mesoporous PANI film coating on GN GN * Low-temperature in situ PANI nanorods were coated on graphene [150] polymerization nanomesh Double-doping A good example for anchoring double- PPy [144] electropolymerization doped CP on GN sheet was given The role of SDS surfactant in the PEDOT Electrochemical codeposition incorporation of GN into PEDOT was [38] studied In situ reduction A high-surface-area hybrid was reported [52] PANI Electrostatic adsorption The thickness was well-controlled by pH [151] synthesis modification . Sons. such as citric acid [143].Polymers 2016. influence the main structure and properties of nanohybrids. Notably. GPMNs GPMNs showed showed outstanding outstanding colloidal colloidal stability stability in in both both N-methyl-2-pyrrolidone N-methyl-2-pyrrolidone (NMP) and (NMP) and water. As can be seen in Figure 9. Reprinted Reprinted with with permission permission from from [45]. 2-naphthalene sulfonate [144].17 of 36 Figure 9. a notable recent work reported the fabrication of free-standing flexible graphene/PANI multilayered nanostructure (GPMN) films via simple physical intercalation of CP into graphite [45].

instead of crystalline Ni(OH)2 . where an effective and simple route for fabricating a ternary nanohybrid via the combination in situ polymerization and electrodeposition method was presented. emphasizing the strength of interfacial [154] polymerization A new simple. wrapping the MWCNT/Ni(OH)2 with PEDOT:PSS significantly reduced the contact resistance among the metal oxide/hydroxide-deposited MWCNTs. large specific surface areas. or CPs) is introduced to . MWCNTs with relatively low cost. A microspherical and porous structure was In situ polymerization [50] fabricated Complex of PANI and GN for enhancing Reflux technique [148] charge-transfer ability was reported Sandwiched PANI A novel approach to fabricate mesoporous PANI film GN–mesoporous silica as [149] GN * coating on GN template Low-temperature in situ PANI nanorods were coated on graphene nanomesh [150] polymerization Double-doping A good example for anchoring double-doped CP on PPy [144] electropolymerization GN sheet was given Electrochemical The role of SDS surfactant in the incorporation of GN PEDOT [38] codeposition into PEDOT was studied In situ reduction A high-surface-area hybrid was reported [52] PANI Electrostatic adsorption The thickness was well-controlled by pH [151] synthesis modification The improvement of cycling stability was Vacuum filtration method [152] demonstrated via the addition of rGO Hydrogen bubble dynamic A general method for fabrication of 3D macroporous [153] template hybrid was studied rGO The comparison of two different methods was PPy Interfacial polymerization shown. such that aqueous dispersions of PEDOT:PSS are commercially available. a nano-carbon. First. [162]. which is commonly used as a pseudocapacitive material. PEDOT:PSS is a mixture of PEDOT and PSS polymers that provides good processability.and cost-efficient was developed One-step synthesis A good example of a cathode material was shown [156] Interfacial polymerization A novel electrode material was developed [157] Fast thermal treatment with A good example of a hybrid CP for gas sensing was PEDOT [158] in situ deposition studied Liquid–liquid interfacial The synthesis and characterization of hybrid thin PANI [159] polymerization films in liquid–liquid interface was first studied SWCNT A facile covalent strategy was developed to address P3HT ** Diels-Alder ligation [160] the bundling issue of CNTs Electrochemical A facile and effective approach for electrode MWCNT PEDOT:PSS [54] co-deposition preparation was reported * GN—Graphene. Second. Representative examples of studies where carbon nanomaterials were incorporated into CPs. Finally. and excellent conductivity serve as an ideal conductive template for Ni(OH)2 deposition. 118 18 of 38 Table 8. These examples share similar attributes in the sense that an external component (either a metal-based semiconductor. environmentally benign method that Bioreduction technique [155] was time. various synergistic effects were observed in their application as the electrode material for supercapacitors. ** P3HT—poly(3-hexylthiophene). amorphous Ni(OH)2 was chosen because structural disorders in Ni(OH)2 can greatly improve the electrochemical efficiency. Carbon CP Preparation method Details Refs. In this ternary architecture design. 8.Polymers 2016. Another interesting result of this ternary system was proposed by Ramasamy et al. The coupling of PEDOT:PSS with nickel hydroxide Ni(OH)2 and multi-walled carbon nanotubes (MWCNTs) has also been examined [161].

There . and electrochemical [180] polymerization Water-in-oil emulsion of TiO2 microspheres PT Pd/TiO2 [181] Loading Pd species and coating PT Mechanical stirring and sonochemical treatment of PEDOT:PSS in rGO RuO2 PSS-coated rGO solution [182] PEDOT:PSS Chemical interaction between RuO2 and hybrid GO/CNT Self-assembled interfacial coupling method [123] * CNF—carbon nanofiber.097 [171] In situ electropolymerization of PANI Hydrothermal reaction to disperse MnFe2 O4 well on the rGO surface rGO MnFe2 O4 [172] In situ polymerization of PANI One-step electrodeposition of PANI and rGO Vertical rGO Pd [173] Spontaneous redox reaction of PANI with Pd salt In situ chemical polymerization of PANI in the presence of AgNO3 CNT Ag [174] and MWCNTs Sequential coating of C and PANI on the surface of TiN C TiN [175] nanowire array In situ polymerization of aniline on the pore surface of mesoporous C C S [176] which served as a reservoir for S Reduction of GO in the presence of CNT rGO/CNT [177] In situ chemical polymerization of PPy in the presence of rGO/CNT powders PPy In situ polymerization of PPy in the presence of GN GN [178] Suspension mixture of PPy/GN with nano-S Chemical preparation of complex of TiO2 /CNT CNT TiO2 [179] In situ polymerization using MO as template Series of processes: high-temperature reflux technique. there are a wealth of examples illustrating the fabrication of ternary hybrids. providing a unique solution to the residue problem of the PMMA-assisted method in graphene substrate transfer (Figure 10). For example. Interestingly. [183] developed the so-called “doping transfer” approach. CP Carbon Inorganic species Intercalation of CNT between GN sheets GN/CNT [163] In situ deposition of PANI on GN/CNT paper Graphite Electropolymerization of PANI in the presence of graphite felt [164] felt/CNT Electrophoretic immobilization of CNT on the hybrid Production of G/CNF by electrospinning GN/CNF * [165] In situ polymerization of PANI Layer-by-layer synthesis of PANI layer on GO-S composite GO S [166] with heating PANI vertically grown on GO sheet rGO MnO2 [167] Reduction of GO and follow by the deposition of MnO2 onto PANI Combination of chemical foaming. thermal PPy/PEDOT CNT compression. thermal reduction. Representative examples of ternary CP nanohybrids.Polymers 2016. oxygen plasma etching. 118 19 of 38 assist the fabrication of the ternary CP nanohybrids. Ternary system Details Refs. Table 9. A partial summary of recent research is shown in Table 9. and KOH rGO/CNT activation to prepare rGO [168] PANI Interfacial polymerization N-doped NiFe2 O4 simultaneously grown with reduction and doping of GO NiFe2 O4 [169] rGO In situ chemical polymerization of PANI CNT Fe Reduction of FeCl3 in the mixing solution of aniline and CNTs [170] Hydrothermal synthesis of CNT/CoS1. Lee et al. 8.097 CNT CoS1. PEDOT:PSS has been employed as a dopant for graphene films.

the enhanced purity. PMMA and PEDOT:PSS were used as the support films transfer and (b) “doping transfer” methods. 2016.8. PMMA and PEDOT:PSS were used as the support films in in both methods. CPs have provided further in the electrical properties. John Wiley & Sons Inc. [186] designed a develop many competitive applications in various fields. which allowed for enhanced response time and accuracy. First. CPs were deposited into the void spaces devices. Sensors 4. Another critical issue in CP sensors is that it is very difficult for CP sensors to achieve high selectivity for specific target species. both electrical and optical signals were successfully monitored using the conductive photonic crystal film.Polymers 2016. John Wiley & Sons Inc. Zhong et al. of silica colloidal crystal templates. Upon exposure to ammonia gas. the doping effect of PEDOT:PSS on graphene can be accomplished via the following three mechanisms: (i) the attraction of electrons from the graphene to the PSS chains. 118 20 of 38 were two interesting points reported. Schematic illustrations and representative conductive AFM analysis for (a) conventional Figure 10. PPy/cellulose papers with different .1. the addition of a PEDOT:PSS layer decreased the optical transmittance value by only 1%. and flexibility. and drug carriers. 4. the benefits of the simplified process. both methods. Reprinted with permission from [183]. Commonly. such as easy synthesis and 186].6. Finally. Recently. doping stability was also achieved through the environmental stability of PEDOT:PSS and the chemical robustness of graphene. energy conversion/storage gas sensor based on conductive opal photonic crystal films. chemical and structural diversity. The signal transduction mechanism of CPs for sensor applications has mostly relied on changes processing. many data are collected from a sensor array. (ii) charge-transfer doping due to electron transfer from graphene to PEDOT:PSS by a difference in the work function. This approach was well demonstrated by a recent study using PPy- coated cellulose papers as the sensing material (Figure 11) [187]. Selected Applications of CP Nanomaterials A great deal of effort has been made to develop various types of CP-based sensors [4. 8. Reprinted with permission from [183]. which bypasses the charge through the conductive film across resistive grain boundaries in the graphene. Schematic illustrations and representative conductive AFM analysis for (a) conventional transfer and (b) “doping transfer” methods. Copyright 2014. The subsequent silica etching resulted in an inverse opal structure.101. such as sensors. and the stable doping Polymers effect made it possible to generate reliable and versatile graphene/CP nanohybrids. Second. This was attributed to the following effects: (i) the strong cohesion between PEDOT:PSS and the graphene film due to the strong attraction between the sulfonic acid group of PSS and graphene. low weight. Furthermore. 118 20 of 36 Figure 10. Copyright 2014. and (iii) percolation doping. which has made it possible to mechanisms to obtain more accurate information on the target species.184– Polymers have advantages over metals or inorganic semiconductors. 8. and (ii) the increased cohesion within the PEDOT:PSS layer. and then statistical tools such as principal component analysis for data processing are utilized to evaluate the selectivity of the sensor. there has been an effort to use multiple signal transduction advantages arising from the inherent π-electron-conjugated system. which was ascribed to the cross-linking effect of the PSS chains during processing.

The signal transduction mechanism of CPs for sensor applications has mostly relied on changes in the electrical properties. which support the potential for using the PPy/cellulose paper as a high-selectivity sensor for detecting the three metal ions. Zhong et al. This approach was well demonstrated by a recent study using PPy-coated cellulose papers as the sensing material (Figure 11) [187]. The subsequent silica etching resulted in an inverse opal structure. The lowest detection level was as low as 10 pM. and hormones [193]. and large-area processing techniques for fabricating nanostructured sensor devices. and their ability to electrochemically recognize metal ions was systematically investigated. and induced-charge electrokinetic flow. [186] designed a gas sensor based on conductive opal photonic crystal films. Ag(I). odorants [190]. With this operating mechanism.184–186]. CPs were deposited into the void spaces of silica colloidal crystal templates. Consequently. Another critical issue in CP sensors is that it is very difficult for CP sensors to achieve high selectivity for specific target species. For example. the gate potential being applied on the channel changes.8. Commonly. proteins [191. speeded up the assembly process. A significant benefit is the short assembly time (approximate 5–10 s). alternate current electro-osmotic flow. Upon exposure to ammonia gas. Unique signal patterns were observed for Hg(II).Polymers 2016. Remarkably. . many data are collected from a sensor array. even after storage in air. When the receptor recognizes a target species. the nanostructured PANI-based sensors exhibited excellent reversibility to low concentrations (a few ppm) of ammonia gas at room temperature. many different types of FET sensors have been developed to detect glucose [189]. both electrical and optical signals were successfully monitored using the conductive photonic crystal film. The combination of forces such as dielectrophoresis. and then statistical tools such as principal component analysis for data processing are utilized to evaluate the selectivity of the sensor.1. inexpensive. and Cr(III) through principal component analysis of the response dataset.101. Ferrala et al. Recently. the field-effect transistor (FET) configuration has been used to achieve enhanced sensitivity. 118 21 of 38 4. Receptor-modified CP nanomaterials are deposited as a channel bridging the source and drain electrodes. a high-performance dopamine FET sensor was successfully demonstrated using human dopamine receptor-containing nanovesicles as the gate-potential modulator on a PEDOT nanotube channel (Figure 12) [184]. 8. despite the fact that electrode gaps are micrometer-sized. Sensors A great deal of effort has been made to develop various types of CP-based sensors [4.192].6. PPy/cellulose papers with different oxidation levels were prepared at different applied potentials. there has been an effort to use multiple signal transduction mechanisms to obtain more accurate information on the target species. as well as high sensitivity. Recently. It is also challenging to develop simple. which was 10 times more sensitive than that of previously reported CP-based dopamine sensors. [188] achieved the rapid electrophoretic assembly of nanostructured PANI on a gap between microelectrodes by applying an alternating current electric field. which allowed for enhanced response time and accuracy. Electrodeposition can be a good candidate technique to satisfy those requirements. which in turn modulates the source-drain current.

which in turn modulates the source-drain current. sensors were linearly proportional to the acetone concentration in the range from a few to a few tens alternate current electro-osmotic flow.f) Calculation of Hg(II) concentration in groundwater. large-area. Copyright RoyalRoyal Society of Chemistry.[187]. and large-area processing techniques for Surface acoustic wave (SAW)-based sensors are also an interesting approach for gas detection fabricating nanostructured sensor devices. 8. Consequently. 118 21 of 36 Figure11.2014. high sensitivity.d) component Principal analysis component plotsplots analysis of theof responses the responses of PPy/cellulose papers of PPy/cellulose withwith papers datadata fromfrom real samples. 118 22 of 38 Polymers 2016. even after storage in air. 200 nm). The combination of forces such as dielectrophoresis. (c.f) Calculation of Hg(II) concentration in groundwater. Remarkably. (e.freestanding freestandingPPy/cellulose PPy/cellulosepaper. as well as high sensitivity. from Copyright 2014. the nanostructured PANI-based sensors exhibited excellent reversibility to low concentrations (a few ppm) of ammonia gas at room temperature. Figure 11. speeded up the of ppm. the gate potential being applied on the channel changes. Reprinted with real samples. Reprinted with permissionpermission from [187]. When the receptor recognizes a target species. the scale bar is (b) SEM images of a PPy/cellulose paper (inset: high-magnification image. Additionally. despite and excellent sensitivity resulting from low gas-diffusion resistance. assembly process. Society of Chemistry. inexpensive. SEM images of a PPy/cellulose paper (inset: high-magnification image. A significant benefit is the short assembly time (approximate 5–10 s). (b) paper. the responses of the the fact that electrode gaps are micrometer-sized.d) Principal (c. the field-effect transistor (FET) configuration has been used to achieve enhanced sensitivity. and fast and reliable response. With this operating . (e. Photograph Photograph showing showing (a) (a)the theflexibility flexibilityofofa alarge-area. Receptor-modified CP nanomaterials are deposited as a channel bridging the source and drain electrodes. 8.Polymers 2016. Ferrala et al. The assembly of nanostructured PANI on a gap between microelectrodes by applying an alternating nanoparticle layer coated onto the ZnO intermediate layer showed rapid response/recovery times current electric field. the scale bar is 200 nm). It is also challenging to develop simple. Electrodeposition can be a good candidate technique to due to their many benefits. and induced-charge electrokinetic flow. [188] achieved the rapid electrophoretic and coworker [40] spin-coated PPy nanoparticles onto SAW transducers to trace acetone gas. For example. such as small size. Li satisfy those requirements.

the sensors were linearly proportional to the acetone concentration in the range from a few to a few tens 4. providing enhanced capacitances. As a result. 8.g. application of nanostructured PANIs as sensing materials has been widely due to their many benefits.mechanism. NatureGroup. The partial negative hydroxyl group of alcohol. thus flexible. Publishing Publishing Group. A variety of capacitances. PPy hollow nanoparticles were simply prepared using surfactant templates and was observed via electrostatic interaction between the partial positive amine group of PANI and the their performance as the electrode for electrochemical capacitors was examined (Figure 13) [67]. including CP nanomaterials. of ppm. [194] prepared a colorimetric alcohol sensor using PANI-coated glass microfibers coworker [40] spin-coated PPy nanoparticles onto SAW transducers to trace acetone gas. IMA. application of nanostructured PANIs as sensing materials has been widely There is an increasing demand for high-performance energy storage devices. PDL.g. respectively. and DRNCN note interdigitated microelectrode array. electrode for electrochemical kinds of materials havecapacitors was examined been hybridized to obtain(Figure 13)synergistic desirable [67]. As a recent microfibers with laser light source with a wavelength of 1550 nm. many different types of FET sensors have been developed to detect glucose [189]. Chiam et al. such as small size. A redshift in the output spectrum remarkable example. and fast and reliable response.nanoparticles served as a nanohybrid Typically. Very recently. graphene/CP nanocage to electrodes prevent metal ionused can be leaching during high-performance.where whereIMA. the responses of hydroxyl group of alcohol. and dopamine receptor-containing receptor-containing nanovesicles-immobilized nanovesicles-immobilized CPEDOT CPEDOT NTs.CPEDOT CPEDOT NTs. geometry. In addition. The graphene/PANI nanostructure-based electrode . PPy nanospheres species allowing excellent capacitance retention. as thedifferent Therefore. Copyrights Copyrights Nature2014. anddopamine -lysine.and Ni-related species) were readily deposited on the inner and outer surfaces of the hollow nanoparticles. poly- poly-DD-lysine. respectively. Chiam et al. high sensitivity. the nanohybrids had high capacitance.12. carboxylated PEDOT NTs. Li and explored.. odorants [190]. and hormones [193]. importantly. and DRNCN note interdigitated microelectrode array. carboxylated PEDOT nanotubes. including microstructure CP nanomaterials. The lowest detection level was as low as 10 pM.. The physically exfoliated graphene provided much better electrical properties than GO and rGO. Similarly. solid-state electrochemical capacitors. pseudocapacitive metal (e. Mn. There enhanced providing is an increasing demand for high-performance energy storage devices. Reprinted with Reprinted withfrom permission permission from [184]. A redshift in the output spectrum was observed nanoparticle layer coated onto the ZnO intermediate layer showed rapid response/recovery times via electrostatic interaction between the partial positive amine group of PANI and the partial negative and excellent sensitivity resulting from low gas-diffusion resistance. The with laser light source with a wavelength of 1550 nm.192]. electrolyte diffusion [147]. in which graphite was physically exfoliated by PANI glue (Figure 14).2014. the packing density of the nanohybrids varied with the nanosphere content. [194] prepared a colorimetric alcohol sensor using PANI-coated glass electrode materials have been designed and tested so far. as well as good long-term cycling stability. to fabricate charge/discharge. In addition. stacked graphene were readily deposited which resulted in aonunique the inner and outer 3D opened surfaces structure thatof the hollow allowed facile nanoparticles. Storage Devices In addition. indicating the potential for high volumetric capacitance. PDL. [184]. Recently.2. hollow nanoparticles served as a nanocage to prevent metal ion leaching during charge/discharge. the fabrication of graphene/PANI multilayered nanostructures has been reported [45]. a high-performance dopamine FET sensor was successfully demonstrated using human dopamine receptor-containing nanovesicles as the gate-potential modulator on a PEDOT nanotube channel (Figure 12) [184]. and properties As does of a material a recent not remarkable example. nanotubes. proteins [191. Electrochemical Energy Storage Devices Among various CPs. A variety of explored. Additionally. which was 10 times more sensitive than that of previously reported Polymers 2016. Mn- were intercalated and into Ni-related species)layers. NTs. Surface acoustic wave (SAW)-based sensors are also an interesting approach for gas detection Among various CPs. The hollow effects.2. PPy hollow nanoparticles were simply prepared using surfactant templates guarantee improvement in the material’s performance because each material has an intrinsically limited and their performance capacitance. pseudocapacitive metal species (e. electrode materials It should have that be noted beencontrol designed overand thetested so far. thus allowing 4. Figure Figure12. excellentEnergy Electrochemical capacitance retention. 118 CP- 23 of 38 based dopamine sensors.Schematic Schematicillustrations illustrationsofofconstruction constructionsteps stepsfor forreceptor receptorgeometry.

electrolytes. a cycling stability with capacitance retention of ~80% after 5000 Polymers charge/discharge 2016. in namely. 8. Flexible. as well as symmetric/asymmetric electrode configuration and the weight ratio of two electrodes is also a key as good long-term cycling stability. In addition. Copyright 2015. flexible. MnO2 /PEDOT nanotubes and rGO/CNFs [196]. the fabrication of graphene/PANI multilayered nanostructures has been reported [45]. electrode systems such as symmetric/asymmetric electrode configuration and the weight ratio of two electrodes is also a key factor affecting the performance of the capacitor. 118 cycles. Our group well demonstrated the importance of the electrode system in electrochemical capacitors using two different nanohybrid electrode materials. Figure 13. the nanohybrids had high capacitance. . other components such as additives. Nature Publishing efficiencies. redox-active electrolytes have shown significant improvements in the specific capacitance of pseudocapacitors using various CPs such as PANI. The graphene/PANI nanostructure-based electrode showed a high specific capacitance of 200 F·g−1. (d)(d)calculated calculated coulombic coulombic efficiencies. Employing redox-active electrolytes can be a limited capacitance. other components such as additives. 23 of 36 Figure 13. Therefore. As a result. the latest review article addresses major issues in electrochemical capacitor application using nanostructured electrode materials [197]. 118 24 of 38 showed a high specific capacitance of 200 F¨ g´1 . different kinds of materials have been hybridized to obtain desirable good approach toward enhancement of the pseudocapacitive performance of CPs [195]. In addition. Copyright 2015. Lastly. (c)capacitances measured specific capacitances at different measured current at different densities. the packing density of the nanohybrids factor affecting the performance of the capacitor. solid-state electrochemical capacitors. namely. current andand densities. (a) (a) Pictorial Pictorial representation of an all-solid-state flexible electrochemical capacitor cell. Typically. and PEDOT as compared to conventional electrolytes. MnO2/PEDOT nanotubes and rGO/CNFs [196]. electrode systems such allowed facile electrolyte diffusion [147]. the latest review article addresses which graphite was physically exfoliated by PANI glue (Figure 14). Very recently. and excellent flexibility. Reprinted with permission from [67]. Prepared by simply adding a redox mediator to the conventional electrolyte.1 specific g´1 . In addition.1 A·gof density −1. which resulted in a unique 3D opened structure that PANI. Reprinted with permission from [67]. graphene provided much better electrical properties than GO and rGO. Lastly. importantly. and excellent flexibility. graphene/CP nanohybrid electrodes can be used to fabricate high- simply adding a redox mediator to the conventional electrolyte. all-solid-state cells based based on on Mn/PPy Mn/PPy hollow hollow nanoparticle nanoparticle electrodes. all-solid-state cells Flexible. Prepared by synergistic effects. Nature Publishing Group. 8. Similarly. Group. indicating the potential for high volumetric capacitance. electrode system in electrochemical capacitors using two different nanohybrid electrode materials. electrolytes. (c) A¨ 0. and separators can be tailored to provide better device performance. a cycling stability with capacitance retention of ~80% after 5000 charge/discharge cycles. PPy. (b) typical galvanostatic representation of an all-solid-state flexible electrochemical capacitor cell. In addition to electrode materials. It should be noted that control over the microstructure and properties of a material does not In addition to electrode materials. (b) typical galvanostatic charge/discharge curves charge/discharge curvesof of metal/PPy metal/PPyhollow nanoparticles hollow measured nanoparticles at a current measured at a density current of 0. and separators guarantee improvement in the material’s performance because each material has an intrinsically can be tailored to provide better device performance. Our group well demonstrated the importance of the varied with the nanosphere content. electrodes. PPy nanospheres were significant improvements in the specific capacitance of pseudocapacitors using various CPs such as intercalated into stacked graphene layers. PPy. The physically exfoliated major issues in electrochemical capacitor application using nanostructured electrode materials [197]. redox-active electrolytes have shown performance. and PEDOT as compared to conventional electrolytes. Employing redox-active electrolytes can be a good approach toward enhancement of the pseudocapacitive performance of CPs [195].Polymers 2016.

198–200].201].198–200]. (e) coulombic efficiency as a function of current density. Photovoltaic Cells Cells Dye-sensitized solar Dye-sensitized solar cells cells (DSSCs) (DSSCs) havehave become become popular popular for for various various energy energy conversion conversion applications.37.3.142. Copyright & Sons Inc.142. high electrical conductivity. The hollowPEDOT hollow microflower microflower arrays to arrays contributed contributed a high power to aconversion high powerefficiency conversion of 7. 8.180. cycling and (h)oflong-term stability cycling the cell with stability an acidic of the cellReprinted electrolyte. John Wiley & Sons Inc. aa redox redox couple. much attention beenbeenpaidpaid to to CPs CPs as as a relatively a relatively low-cost low-cost devicedevice for photovoltaic for photovoltaic application application due to due to their their excellent excellent electrocatalytic electrocatalytic activity. 118 25 of 38 Polymers 2016. high electrical conductivity. which was comparable to that of a cell with a sputtered Pt film (7.180. A typical DSSC consists of a transparent photo-anode with a dye-sensitized mesoporous dye-sensitized mesoporous thin film.61%). and and aa counter counter electrode electrode withwith aa catalytic catalytic layer layer deposited deposited on on aa fluorine-doped fluorine-doped tin-oxide (FTO) substrate [17. Kung et al. 118 24 of 36 Figure 14.162.201].162. Consequently.3. The lower the the electrolyte region. John [45]. Considering (7.20%. [180] reported the effect of PEDOT coating on the of PEDOT coating on the electrocatalytic activity of CNT/polypropylene plates. reported the effect Lin et al. from permission Reprinted with permission [45]. [198] examined a PEDOT hollow microflower array film as the catalytic examined a PEDOT hollow microflower array film as the catalytic material on the counter electrode of material on the counter aelectrode DSSC.Polymers 2016. For example. (b) typicalofphotograph photograph of cell cell performance performance measurement under mechanical deformation. the higher the fill of Warburg diffusion resistance the factor DSSC. The lower the Warburg diffusion resistance of the DSSC. electrocatalytic activity of it was CNT/polypropylene plates. and good film-forming ability [198. A typical DSSC consists of a transparent photo-anode with a applications. 4. Interestingly.14. . thin film. efficiency of 7.of the cell [180] performance). it was believed it was that the believed unique that the microflower unique microflower structure would facilitatestructure a kindwould facilitate adiffusion of hemispherical kind of of hemispherical diffusion of ions ions for the electrocatalytic for the reaction in electrocatalytic reaction in the electrolyte region. it was found that the PEDOT-coated found that the PEDOT-coated CNT/polypropylene plate showed a Pt-like electrocatalytic activity for CNT/polypropylene plate showed a Pt-like electrocatalytic activity for I3− reduction. Lin et al.capacitor (b) typicalcell. Recently. For example. resistance of the DSSC.1density A¨ g´1 forof 0. even after the bending test.77%. activity. and function of bend long-term radii. of the(ahigher the cell criticalthe fill factorfor parameter of evaluation the cell (a critical parameter of the cell for evaluation performance). Kung et [198] al. (f) Ragone plots. and good film-forming ability [198. (f) Ragone (e) coulombic efficiency as a function of current density. electrolytes.1 different for different(d) A·g−1 electrolytes. Photovoltaic 4.61%). which was comparable to that of a cell with a sputtered Pt film the low Considering value the low value of the Warburg of the diffusion Warburgofdiffusion resistance the DSSC. much attention hashas tin-oxide (FTO) substrate [17.20%. (c) galvanostatic charge–discharge curves at a current curves at a current density of 0. Recently.37.2015. couple. Copyright fromWiley 2015. (g)bend of capacitance as a(h) radii. (c) galvanostatic charge–discharge measurement under mechanical deformation.48. all-solid-state all-solid-state graphene/PANI-glue graphene/PANI-glue multilayered multilayered nanostructure nanostructure cells: cells: (a) schematic (a)an of schematic of an all-solid-state all-solid-state flexible electrochemical flexible electrochemical capacitor cell. (d) specificascapacitances specific capacitances a function ofas a function current of density. The of aPEDOT DSSC. 8. Figure Flexible. with an acidic with electrolyte. current density. (g) capacitance as a function plots.48. Interestingly. Flexible. a DSC with the PEDOT-coated CNT/polypropylene counter electrode showed a high power conversion efficiency of 6.

CPs can immobilize anionic drugs during oxidation (doping). a DSC with the PEDOT-coated CNT/polypropylene counter electrode showed a high power conversion efficiency of 6. Nevertheless. with the aim of unraveling the complex mechanisms governing cancer biology. Interestingly. These charges attract ions of the opposite charge in the polymeric matrix. .Polymers 2016. CPs exhibit reversible electrostatic immobilization. on-demand release. [202] fabricated a robust and low-cost nanocomposite based on PEDOT and oleanolic acid. Drug Carriers Recently. It is anticipated that the use of nanostructured CPs will open a new avenue for industrial fabrication of DSSCs due to their low cost and reasonable performance as compared to Pt electrodes [199]. a limited range of drugs and relatively low drug-loading capacities are two main drawbacks for the practical application of CP-based drug delivery systems. [203] proposed an integrated strategy with conductive disulfide–biotin-doped PPy nanowires for cell capture.or micro-sized inter-nanowire pores of a PPy nanowire network can serve as reservoirs to store drugs. The materials exhibited competitive characteristics such as good biological activity of the embedded drug and well-controlled release. the types of drugs that can be used are limited to charged and small molecules. Consequently. 8. Jiang et al. there has been substantial effort to fabricate drug delivery systems based on smart materials [73]. In addition. Hence. In a trial of a drug delivery solution for anticancer treatment. it can be confirmed that the application of CP nanomaterials as potential substitutes for Pt counter electrodes in DSSCs is a recent trend. the enzymatic reduction of hydrogen peroxide on PPy resulted in a greatly increased amperometric response with a wide range and low limit of detection. even after the bending test. In contrast to physical entrapment. making it a potential candidate for further development and a promising commercial application. Krukiewicz et al. In order to partly solve those problems. Therefore. which strongly depend on their oxidation state. 118 26 of 38 I3 ´ reduction. In addition.4. and release the drug via the process of reduction (dedoping). both the range of loaded drugs and the drug-loading capacity can be effectively improved. Although the mechanisms of CP-based drug carriers are very attractive due to the inherent doping–dedoping and stimulus–responsive properties of CPs (where drugs can be incorporated into polymer chains as doping agents and then released through electrical stimulation). CPs that possess ion-exchange properties are being studied as promising materials for drug reservoirs for this purpose. The mechanism of this process relies on the fact that CPs undergo a charging-discharging process and adopt positive/negative charges. The PPy nanowire platform showed very high sensitivity and specificity. From a survey of numerous studies. [106] found that nano. Herein.77%. this helps us to achieve a better understanding of circulating tumor cells. Furthermore. Consequently. move to a target site. a clear mechanism to describe the function of CP nanomaterials as counter electrode materials still needs to be clarified. a PPy film was further deposited on top of a PPy nanowire network by chemical vapor deposition to inhibit leaking of the stored drugs (Figure 15). 4. the capacity of drug loading is usually low because it is strongly dependent on the doping level. and in situ quantification of captured cells within the same platform. Hong et al. it is not necessary to consider the volume and the charge of the loaded drugs because the space for drug storage has been changed from the backbones of the CPs to the vacancies among the nanowires. linking them via coulombic interactions.

118 26 of 36 application of nanoscale devices. Reprinted with permission from [106]. In fact. a generalized and tripleMore solution. numerous researchers water-solubility. critical have challenges in achieving also been developed to further provideadvances desirableinproperties CP research: and(i)functions metallic conductivity. thevalue harderof itCPis nanomaterials is obvious. the doping is suggested the harder by it theis Drude to controlmodel: and charge predictcarriers the major hopcharacteristics between ordered metallic of the domains resulting instead of unordered CP nanomaterials. FeClmethod 3. Inspired including by theconductivity metal-like Nobel Prize and in 2000.β-coupling APS and metal salts (e.CPs such as dual with doping. [26.interesting there properties not observed are no effective in thetoindividual methods characterizecomponents and control and theirthe bulk counterparts. to control and predict we believe the major that their characteristics offull potential the resulting is yet CP to be realized. presence it has been believed of undesired α. has been an easy. 8. of CPsThis on amight nanoscale be theoffers reason a very why broad and promising most studies have not“toolbox” focused onfor theresearch. CPs are domains insoluble[26. (b) addition network coated by a PPy film: (a) electropolymerized PPy nanowire network. Conclusions and Outlook further advances in CP research: (i) metallic conductivity. solubility. application there are noAs of CPs. such as reproducibility. doubt that the hybridization particularly in hybrid systems. a high degree CPofnanohybrids structural order are would also promising lead to high candidates electrical because they show conductivity. enormous common number of approaches explanation have been developed of the conductive mechanism to of fabricate CPs is CP nanomaterials. CPs acids with suchdesirable as HClsizes.107. more Althoughthe complex the tremendous doping step. (c) preparation of the PPy film by CVD. 118 and 27 of 38 control of individual nanostructures. PSS. Furthermore. have efforts also been should developed be aimed to provide at designing desirable properties and synthesizing new monomersand functions to CPs. contribute improvement stability of the properties in the solubility of CPs. double properties. More sophisticated doping Specifically.crystalline/amorphous many researchers have ratio usedof CPs. However. doping. doping. backbone acids [205]. with stableMoreproperties. in hybrid Another systems. This andabout story some PEDOT:PSS anionic surfactants may bearea not goodonly molecular model templates for developing but also doping processable CPsagents. in terms of the major properties. 8. (b) addition of the drug. anthe First. last decade. to CPs. range of However. Elsevier. in commonThus. amorphous In general. Polymers 2016. (d) application of electrical stimulation to release drug. and and anionic some control of individualare surfactants nanostructures. is that the It coupling is highly anticipated of PEDOT with PSS enhances the environmental stability of PEDOT’s properties. stability of the properties of CPs. including (ii) processability.within Fe2 (SOthe ) 4 3 ) are polymerthe best oxidants. there are several and triple doping.β. although in which sulfonic acids such as dodecylbenzenesulfonic acid and camphorsulfonic it fortunately showed stability and high conductivity. and (iii) environmental metal-like conductivity and water- stability.g. such in asterms of the major dual doping. was initially Doping is an essential developed to provide stepa for the preparation soluble conducting of CPs. sulfonic acids suchthere are still limitations inacid as dodecylbenzenesulfonic the application of nanoscaleacid and camphorsulfonic devices. itHowever.Polymers 2016. drug. applications.to be aAnother key topic in variousissue important applications. not only molecular templates but also doping agents.g. of thiophene FeCl rings3 . whichlead hastoprevented high electricala wideconductivity. such astoreproducibility. techniques. There crystalline/amorphous ratiois of noCPs. of CPs. Specifically. H2SO4 are the common and properties is still in doping agents.107.204]. Schematic process showing the fabrication and drug release of the drug-loaded PPy Figure 15.204]. as HCl the and resultingH 2 SO PEDOT 4 are the was common still doping insoluble. stability. During thenanosystems. Schematic process showing the fabrication and drug release of the drug-loaded PPy nanowire nanowire network coated by a PPy film: (a) electropolymerized PPy nanowire network. ithave should been be devoted also noted tothat CP theresearch. such However. thea numerous representative advantages of CPs soluble commercialized with other CP. and dopants. agents. of the drug. is an essential step for butthealso to achieveofmultifunctional preparation CPs. particularly PEDOT:PSS. techniques. effective methods tocommercialized a representative characterize and soluble control the CP. Fe2(SO4for nanostructured )3) are the best oxidants. PEDOT became soluble in water when blended acid contribute to improvement in the solubility with a polyelectrolyte of CPs. and microstructures. Elsevier. nanomaterials. issue important This might is thatbe the the reason coupling whyof mostPEDOTstudieswith havePSS not focused enhances on the the crystalline environmental properties of CPs stability for achieving of PEDOT’s metal-like properties. sophisticated dopingcombining Of course. During polymer the last that lacked thedecade. for whichCP nanomaterials. (ii) processability.be PSS cannot double doping. PEDOT was initially . Copyright 2013. that believed efficient. the common However. inwhich demand. electrical In fact. has prevented aand widethe rangeintelligent integration of application of As of CPs.andthatβ. a high solvents anddegree of structural are not order would thermoplastic. (d) application of electrical stimulation to release (c) preparation of the PPy film by CVD. Figure 15. notproperties crystalline only to solve the for of CPs abovementioned achieving metal-like challenges and electrical enhance properties. materials many has beenhave researchers and willusedcontinue PEDOT:PSS.. APS and andmetalscalable saltssynthesis (e.First. CPs interdisciplinary are insoluble in common researchsolvents will provide and arenew not opportunities thermoplastic. suggested by the The Drude goalmodel: of this charge review carriers article washopto between better illustrate orderedthemetallic recent advances domains in the synthesis instead of unordered of CP nanomaterials amorphous domains and their potentialThus. However. Facilitating In general. Copyright 2013. it should explanation be also noted of the thatconductive the more complexmechanism of CPs step. Reprinted with permission from [106]. there are several critical challenges in achieving 5.. theDoping corresponding properties. PEDOT properties. and (iii) environmental To date.

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