Beruflich Dokumente
Kultur Dokumente
REVIEW
and analysis of composites. Finally, a detailed discussion of their eectiveness and perspectives in energy
DOI: 10.1039/c5nr08803h
storage and solar light harvesting is presented. In brief, a broad overview on the synthesis and possible
applications of conducting polymer nanostructures in energy domains such as fuel cells, photocatalysis,
www.rsc.org/nanoscale
1.
Introduction
a
CSIR - Central Glass and Ceramic Research Institute, 196, Raja S.C. Mullick Road,
Kolkata-700032, India. E-mail: ghosh.srabanti@gmail.com, rnbasu@cgcri.res.in
b
School of Chemistry, University of East Anglia, Norwich NR4 7TJ, UK
using microscopy and other techniques as well as their application in the fields of energy storage and conversion, and
electrocatalysis.
The initial work on CPs was instigated by three Nobel laureates (A. J. Heeger, H. Shirakawa, and A. G. MacDiarmid).15,16
They discovered an increase of nearly 10 orders of magnitude
in the electrical conductivity of polyacetylene (PA) when it was
doped with iodine or other acceptors.17 As shown in Fig. 1,
conducting polymers include polyacetylene (PA), polypyrrole
(PPy), polyaniline (PANI), poly(3,4-ethylenedioxythiophene)
(PEDOT) and poly( p-phenylenevinylene) (PPV) etc. Since then,
CPs have received increasing attention in both fundamental
research and various application fields in recent decades.
Compared to bulk polymers, CPNs displayed superior performances for energy storage and conversion which is associated with the nanoscale size giving a superior electrical
conductivity, high surface area, high carrier mobility, improved
electrochemical activity and good mechanical properties etc.
Numerous synthetic strategies have been developed to obtain
various conductive polymer nanostructures such as nanoparticles (NPs), nanowires, nanofibers, and nanotubes etc.,
and high-performance devices based on these nanostructured
polymers have been realized.1214
This review covers recent progress in the wet-chemical
development of conducting polymer nanostructures and
hybrid strategies based on the functional associations of semiconductors and metals via template synthesis routes, including soft and hard template methods. Controlling the
dimensions of each component permits engineering of the
Review
Fig. 1
Nanoscale
2. Synthesis
Conventionally, CPs have been synthesized via the chemical or
electrochemical oxidation of monomers, followed by coupling
of the charged monomers to produce the polymer chains,
which is the simplest system. However, CPNs have been fabricated with the help of templates during the polymerization
process. This section covers two main approaches for the controlled synthesis of CPNs and CP based hybrid nanocomposites as well as heterostructures, which are the template-based
synthesis and the template-free synthesis. The template-based
synthesis is the most commonly used for producing
morphology and size tunable nanostructures which are
Template-based synthesis
Nanoscale
Review
Fig. 2 (a) Image courtsey of Ran Lius personal webpage, Penn State Department of Chemistry. (b) Growth mechanisms of heterogeneous nanostructured MnO2/PEDOT by coelectrodeposition of MnO2 and PEDOT on ring-shaped and at-top electrodes. Reproduced, with permission, from
ref.36, American Chemical Society. (c) Schematic of the mechanism of the soft-template synthesis of dierent conducting polymer nanostructures:
(i) micelles acting as soft-templates in the formation of nanotubes. Micelles were formed by the self-assembly of dopants, and the polymerization
was carried out on the surface of the micelles; (ii) nanowires formed by protection of the dopants. The polymerizations were carried out inside the
micelles; (iii) monomer droplets acting as soft-templates in the formation of micro-spheres; and (iv) polymerization on the substrate producing
aligned nanowire arrays. Nanowires were protected by the dopants, and polymerization preferentially occurred on the tips of the nanowires. Reproduced, with permission, from ref. 48, Elsevier Ltd. (d) Schematic representation of the electrochemical polymerization of liquid crystalline EDOT
PDPPA. Reproduced, with permission, from ref. 64, American Chemical Society. (e) HAADF-STEM image of stepwise electropolymerization for the
fabrication of longitudinally integrated conducting polymer nanowires of PEDOTPPy segmented nanowires in the PEO114-b-PMA(Az)67 template.
Reproduced, with permission, from ref. 65, American Chemical Society. (f ) Depiction of peptide amphiphile (PA) self-assembly in the presence of
EDOT monomers. The self-assembly yields nanostructures with hydrophobic cores that sequester the organic monomer from aqueous solution.
Conned oxidative polymerization of EDOT once partitioned should occur predominately within these hydrophobic regions, resulting in encapsulated conductive polymers. Reproduced, with permission, from ref. 66, Wiley-VCH.
Review
by-layer self-assembly and block copolymer mediated fabrication etc.4247 The soft-template method based on the selfassembly of surfactants is typically employed for the synthesis
of shape-controlled CPNs as shown in Fig. 2c.4850 Wan et al.
discovered that PANI nanowires could be synthesized by in situ
doping polymerization in the presence of -naphthalene sulfonic acid (-NSA) as the dopant without the need of any membrane.51 Zhang et al. reported various PPy nanostructures in
the presence of various anionic, cationic, or non-ionic surfactants with various oxidizing agents.52 In the emulsion
polymerization route, the shape and dimensions of the CPNs
are highly dependent on their micellar state, either in the isolated or in the aggregated state. Jayakannan et al. obtained a
coral-like morphology of PPy nanospheres in the presence of
aggregated templates at a higher surfactant concentration,
whereas at a lower surfactant concentration the weakly aggregated micelles produced well-defined PPy nanospheres of
150800 nm.53
Shinkai et al. reported the preparation of a porphyrin-based
1D assembly by linking the porphyrin units using the polymerization of butadiyne in the gel state.54 Morin et al. recently
reported the synthesis of conjugated nanowires prepared by
the topochemical polymerization of butadiynes in the xerogel
state.55 Li et al. developed an in situ sacrificial oxidative template route for the bulk synthesis of two-dimensional nanorings and flat hollow capsules of PANI nanostructures.56
Manohar and co-workers reported the synthesis of clip-like
nanostructures of PPy, PANI, and PEDOT using an anionic
oxidant/cationic surfactant complex as a template.57 The judicious combination of the main parameters, such as the surfactants, oxidizing/doping agents, pH, temperature, and other
structure-directing agents, provides infinite possibilities for
fabricating nanostructures with desirable morphologies.
A self-organized template, lyotropic liquid crystal (LC) with
mesophases (hexagonal or lamellar phases) was utilized for the
synthesis of anisotropic conducting polymer nanostructures
which cannot be achieved using traditional bulk or solution
polymerizations.58,59 Hulvat et al. developed a new method for
the fabrication of hexagonally ordered fibrillar PEDOT nanostructures in hexagonal LC using the electropolymerization
technique.60,61 Remita and co-workers developed swollen hexagonal mesophases composed of oil-swollen tubes with tunable
diameters, which are stabilized by a monolayer of surfactant
and cosurfactant molecules, that have been used to eectively
control the morphology and the size of the nanostructures.62
Ghosh et al. reported a single-step preparation of PEDOT nanostructures with spindle-like or vesicle-like shapes in the hydrophobic domains of hexagonal mesophases via chemical
oxidative polymerization of EDOT monomers using FeCl3 as
the oxidizing agent.63 Ghosh et al. also reported the controlled
synthesis of micrometer long nanofibers of conducting poly
(diphenylbutadiyne) (PDPB) nanofibers that were synthesized
in the oil tubes of the hexagonal mesophases by photoinduced radical polymerization using a chemical initiator or
by gamma irradiation. The diameter of the nanofibers can be
varied from 5 to 25 nm in a controlled fashion, and is directly
Nanoscale
determined by the diameter of the oil tube of the doped mesophases, thus proving a direct templating eect of the mesophase. Moreover, controlling the liquid-crystalline phase,
depending on the composition which ranges from columnar
to lamellar or cubic phases, can direct the dimensionality and
the morphology of the nanoobjects grown in situ as shown in
Fig. 2d.64 Komiyama et al. also developed a block-copolymertemplated (a chemical anity template) electropolymerization
technique in order to form PPy and thiophene derivative based
CPNs (Fig. 2e).65 Stupp and coworkers described methods to
chemically and electrochemically synthesize CPs within bioactive aqueous gel matrices formed by a peptide amphiphile.66,67 Fig. 2f illustrates the formation of a hydrophobic
lipid environment due to the self-assembly of the peptide
amphiphile into cylindrical nanostructures, providing a reservoir for the uptake of the hydrophobic EDOT monomer, which
can consequently be utilized for polymerization in the confined region. Other syntheses through biomolecules are discussed by Kumar et al. and Niu et al.68,69 DNA molecules
provide attractive soft templates for the controlled fabrication
of CPNs.70 Hassanien et al. described the preparation of DNAtemplated polyindole nanowires, Moon et al. reported the formation of highly uniform conductive PPy nanowires with a
DNA template and Ma et al. discussed the preparation of PANI
nanowires on Si surfaces fabricated with DNA templates.7173
Richardson-Burns et al. developed a polymerization of PEDOT
around living cells and described a neural cell-templated CP
coating for microelectrodes and a hybrid conducting polymer
live neural cell electrode.74 Pomposo et al. also reported the
enzymatic synthesis of PEDOT nanostructures.75 Niu et al.
described the synthesis of one-dimensional composite nanofibers via the head-to-tail assembly of the tobacco mosaic virus
(TMV) as well as in situ polymerization of PANI on the surface
of the TMV.76 Other templates can serve as both the oxidant
and sacrificial template for the chemical oxidative polymerization, e.g., Pahovnik et al. described the synthesis of PANI
nanostructures using ionic liquids as soft templates and
Li et al. reported PANI nanorings and flat hollow capsules synthesized by in situ sacrificial oxidative templates using a V2O5/
H2O2/H3PO4 mixture.77,78 It is important to note that subtle
changes in the polymerization parameters often result in
drastic dierences in the morphology of the resulting CPNs.
Zhu et al. developed the synthesis of rambutan-like hollow
spheres of PANI by a self-assembly method in the presence of
perfluorooctane sulfonic acid (PFOSA), which served as the
dopant and soft template, and induced superhydrophobicity at
the same time.79 Park et al. developed a technique for the
anisotropic growth control of PANI nanostructures, specifically
nanospheres, nanorods, and nanofibers by employing a polymeric stabilizer, poly(N-vinylpyrrolidone). The polymerization
rate became slower in the presence of the stabilizer (the rate
constants calculated at the initial stage decreased with increasing concentration of the stabilizer), yielding PANI nanostructures with lower aspect ratios, and the stabilizer sterically
restricted the directional fiber growth mechanism governing
PANI chain growth in aqueous solution.80
Nanoscale
2.2.
Template-free synthesis
Review
Review
Nanoscale
Nanoscale
Review
Fig. 3 Emulsion-template strategy for the synthesis of conducting polymer aerogels: (a) digital photos of the EDOT-S stabilized EDOT emulsion,
(b) PEDOT-S/PEDOT hydrogel and (c) PEDOT-S/PEDOT aerogel and schematic diagrams of the (d) EDOT-S stabilized EDOT emulsion, (e) PEDOTS/PEDOT hydrogel and (f ) PEDOT-S/PEDOT aerogel. (g) SEM image of supercritical CO2 dried PEDOT-S/PEDOT aerogel. Panels (a)(g) are reproduced, with permission, from ref. 139, the Royal Society of Chemistry. (hj) Elasticity of PPy hydrogel. Macroscopic visualization, showing that the
PPy hydrogels recover their original shape after compression 70%. (k) versus curves for PPy hydrogels along the loading direction during
loadingunloading cycles at = 1070%. Digital photos showing the fast removal of (l and m) methyl orange, (n) victoria blue and (o) brilliant yellow
from wastewater with the elastic PPy hydrogels in syringes. Panels (h)(o) are reproduced, with permission, from ref. 140, Nature Publishers.
Review
Nanoscale
Fig. 4 TEM image of PPy/Pd composite nanorings. Schematic diagram of the fabrication of PPy/Pd composite nanorings. Reproduced, with permission, from ref. 146, Royal Society of Chemistry.
The probable mechanism of formation of composite nanorings is proposed as shown in Fig. 4. An insoluble complex of
(CTA)2PdBr4 formed between a noble metal compound,
sodium tetrachloropalladate, and a cationic surfactant, cetyltrimethylammonium bromide (CTAB), with lamellar mesostructures was used as a template and the composite nanorings
were synthesized via the redox reaction between PdBr42 and
the monomer. After complete polymerization, PPy/Pd composite nanorings were formed. Moreover, these nanocomposites
have shown a wide range of tailor-made applications. Platinum
NPs have been incorporated into a PANI matrix resulting in a
composite that is useful for the electrochemical process of
hydrogen evolution.155 An original second-order-template
method has been proposed for the fabrication of Ni and PANI
nanotube composite nanowires within the pores of an
alumina template, and then nickel nanowires were deposited
into these nanotubules.156 Drury et al. also studied the fabrication and characterization of silver/PANI composite nanowires
in porous anodic alumina.157 Gold NP based CP composites
can be used as substrates for surface enhanced Raman scattering.158,159 Palladium, gold and platinum NP based CP nanocomposites illustrated superior catalytic activity,160165 and
biosensing,166170 therapeutic,171,172 and water treatment
applications.173 Moreover, incorporating semiconductor nanocrystals into CPs can complement the visible light absorption
range of the polymers as well as allow sensitizing or immobilization of the semiconductor nanocrystals for renewable
energy applications such as heterojunction-type photovoltaics
and photocatalysis.174176 A significant eort has been devoted
to create heterojunction materials that contain a conducting
polymer layer as well as an inorganic layer. It is challenging
to design heterostructures with the appropriate morphologyrelated orientation and band position of each semiconductor
and polymer unit within the heterostructure. Appropriate band
gap alignment in combination with easy solution-processability makes this material a promising candidate for energy
harvesting applications. Here, we discuss the synthesis and
characterization of the unique heterojunction between conjugated polymers and semiconductor NPs. For example, PDPB
nanofibers were coupled with ZnO NPs and the photocurrent
response to visible light and photocatalysis applications along
with other conjugated polymer based heterojunctions has
been summarized.177180
3. Characterization
The characterization of CPNs is closely tied to the synthetic
technique. Electron microscopy, optical spectroscopy and
scattering techniques are widely used. Scanning electron
microscopy (SEM) continues to provide valuable information
about the morphology of polymer nanostructures and composite materials. A wide variety of complimentary methods are
also available, including atomic force microscopy (AFM), transmission electron microscopy (TEM) and cryo-TEM etc. As these
methods continue to improve, it will be possible to have a
more complete understanding of the relationship between the
polymer nanostructure and their macroscopic properties, for
example, through infrared absorption using a combined technique, namely, AFMIR. The use of cyclic voltammetry for
studying the electronic states of CPs is also promising and
electrochemical impedance spectroscopy can be used to study
the energy storage and dissipation properties of CPs, which is
reviewed in detail.181 The electrical conductivity of the polymer
films can be measured using a Kelvin four-point probe
technique. In this section, the latest advancements in the
characterization of CP-based functional nanomaterials for
sustainable development in energy conversion and storage are
reviewed.
3.1.
Atomic force microscopy has been extensively used to investigate the surface morphology, roughness, phase segregation,
packing of the polymer chains and conformation and
Nanoscale
mapping the distribution of the electric charges etc. of conducting polymers. Taranekar et al.182 studied the formation of
unique nanoscale morphologies due to phase-segregation of
polysiloxane domains and cross-linked PPy from the AFM
images. Pruneanu et al.183 studied the self-assembly of DNAtemplate PPy nanowires using the noncontact mode. Another
widely used application of dynamic modes using electrical
force microscopy (EFM) provides the possibility of probing the
localized charge distribution, surface potential, and doping
profiles at the surface.184,185 Takami et al. measured the conductivity of polydiacetylene thin films using double-tip scanning tunneling microscopy.186 Scanning Kelvin probe
microscopy (KPM), which identifies the local surface potential,
oers the possibility of distinguishing between regions with
dierent chemical natures or compositions.187 For example,
Semenikhin et al.188 studied the evidence of local structural
inhomogeneity and non-uniform dopant distribution in conducting polybithiophene (PBT) and the origin and characterization of the structural inhomogeneity and local potential
Review
Fig. 5 Simultaneous AFM and uorescence microscopy study: (a) two examples of simultaneously measured force curve (blue) and uorescence
intensity (black) traces on single MEH-PPV nanoparticles. (b) Fluorescence spectrum (black) of a MEH-PPV nanoparticle and transmission spectrum
(blue) of a dichroic mirror used to spectrally separate the emission into blue (Iblue) and red (Ired) components. (c) Scheme of the proposed model.
Panels (a)(c) are reproduced, with permission, from ref. 191, American Chemical Society. (d) Topographic image of PDPB nanobers by conventional AFM. AFMIR mappings of the photo-induced PDPB polymer nanostructures synthesized in the swollen hexagonal phase measured at dierent
xed wavenumbers: 1490 cm1 (e), 2146 cm1 (f ) and 3054 cm1 (g). (hj) NanoIR spectra recorded at three dierent spectral regions of the PDPB
polymer. Panels (d)( j) are reproduced, with permission, from ref. 192, the Royal Society of Chemistry.
Review
Nanoscale
Electrochemical characterization
Nanoscale
Review
Fig. 6 Bright eld TEM images of in situ electrochemical deposition of PEDOT: (a) early stage in the process (immediately after initial CV deposition
on the bench) showing the dark PEDOT depositing from an aqueous solution onto a 20 m wide glassy carbon working electrode (anode) supported
on a thin silicon nitride membrane; (b) later stage in the process (after subsequent constant voltage deposition), showing the increased thickness
and formation of rough protrusions at the edge of the PEDOT lm; (c) higher magnication view of the rough edge of the PEDOT lm after further
deposition. Inset: EDS elemental mapping after in situ electrochemical deposition of PEDOT: secondary electron image; sulfur (PEDOT); carbon
(PEDOT and glassy carbon working electrode); chlorine ( perchlorate dopant); oxygen (PEDOT and perchlorate dopant). Panels (a)(c) are reproduced, with permission, from ref. 193, Royal Society of Chemistry. (d) In situ solution 1H NMR spectra monitoring the temporal changes in the
nucleation of polyaniline in 0.10 M SDS at 298.3 K. (e) Schematic representation of the nucleation for polyaniline in SDS rod-like micelles. Panels (d)
and (e) are reproduced from ref. 198, American Chemical Society.
Review
Nanoscale
Fig. 7 (a) CV prole of nanostructured conducting polymers at a scan rate of 100 mV s1, bare iridium (squares), PPy lm (stars), PPy nanotubes (triangles), PEDOT lm (diamonds), and PEDOT nanotubes (circles). (b) Bode plot of electrochemical impedance spectroscopy over a frequency range
of 1105 Hz. (c) Phase plot of electrochemical impedance spectroscopy over a frequency range of 1105 Hz showing that both the uncoated and
coated electrodes were capacitive in the low-frequency range (<10 Hz). Panels (a)(c) are reproduced, with permission, from ref. 206, Wiley-VCH.
(d) Equivalent circuit model of electrodeCPelectrolyte interface. The circuit elements are: solution resistance (RS), coating capacitance (CC), pore
resistance (Rpore), double layer interface impedance ZCPE, charge transfer resistance Rt, and nite diusion impedance ZT. Panel (d) is reproduced,
with permission, from ref. 207, Elsevier Ltd.
across the frequency range due to the higher electrical conductivity of PEDOT compared to PPy (Fig. 7b). The phase plot of
the impedance spectroscopy (Fig. 7c) showed that both the
uncoated and coated electrodes were capacitive in the low frequency range (<10 Hz) and suggests that PEDOT nanotubes act
as a capacitive material for frequencies > 1 kHz and as a Faradaic (resistive) material for frequencies < 1 kHz. Fig. 7d shows
a detailed equivalent circuit model of PPy nanotubes comprising a solution resistance RS, a CP coating capacitance CC, a
pore resistance RPore, a double layer interface capacitance CPE,
a charge transfer resistance Rt, and a finite diusion impedance ZT.
4.
Applications
Nanoscale
Review
Fig. 8 (a) TEM image of nanobrillar PPy/Pt catalyst (inset: the size distribution histogram of the Pt nanoparticles), and (b) cyclic voltammetry (CV)
curves of nanobrillar PPy/Pt, nanobrillar CNx/Pt, and XC-72/Pt catalysts in 1.0 M H2SO4 aqueous solution with 1.0 M CH3OH (inset: the section
from 0.20.6 V vs. Ag/AgCl of the CV curves). Panels (a) and (b) are reproduced, with permission, from ref. 217, the Royal Society of Chemistry.
(c) TEM image of poly(3-methylthiophene) nanocones (without Pt). (d) Variation of current density with time in 1 M H2SO4/1 M CH3OH at +0.6 V
vs. Ag/AgCl. Panels (c) and (d) are reproduced, with permission, from ref. 220, Elsevier Ltd.
Review
Nanoscale
suciently stable and ecient for practical use have not yet
been realized. CPNs provided attractive advantages including
high conductivity, good electrochemical activity, large specific
surface area, and short and direct pathways for charge transport, which increases the energy conversion performance.
Recently, Ghosh et al. demonstrated that CPN based photocatalysts (visible light-activated catalysts) may become as
useful as inorganic semiconductor catalysts in ultraviolet light
and also oer intriguing opportunities for future research
because of their responses to visible light. PEDOT nanostructures, having a narrow band gap (E = 1.69 eV) and an
excellent ability to absorb light in the visible and near infrared
region, demonstrate unprecedented photocatalytic activities
for water treatment without the assistance of sacrificial
reagents or noble metal co-catalysts and have turned out to be
better than TiO2 as the benchmark catalyst.227 The first experimental evidence of a visible light responsive photocatalytic
activity of poly(diphenylbutadiyne) (PDPB) nanofibers by
photoirradiation for water depollution has been reported.228 It
has to be noted that the photocatalytic activity of PEDOT
nanospindles has been found to be even higher than PDPB
nanofibers under UV and visible light for phenol and MO
degradation (Fig. 9); 100% of phenol is degraded with PEDOT
nanospindles after 240 min irradiation under visible light,
while only 64% of phenol is degraded with PDPB. The novel
CPN based photocatalysts are very stable with cycling and can
be reused without an appreciable loss of activity. The key to
the success of ecient solar energy conversion is the development of high performance materials having a well matched
photoabsorption with the solar spectrum (visible light-harvesting capability), ecient photoexcited charge separation to
prevent electronhole recombination and an adequate energy
of charges that carry out the photodegradation of dyes and
other toxic molecules.
The integration of a semiconductor nanocrystal with a
narrow band gap at CP heterojunctions has been shown to be
an eective means of promoting charge carrier separation and
improving visible-light activity. However, the reported photoconversion eciency is small.229231 As the interfacial area is
critical in achieving a favorable charge separation, it is essential to incorporate nanoscale units in the heterojunctions.
Hence, designing heterostructures with the appropriate morphological orientation and band position of the semiconductor and the polymer unit is challenging. Very recently, Sardar
et al. reported the formation of a unique nanoheterojunction
using PDPB nanofibers with ZnO NPs to explore the eective
charge separation from the polymer to the semiconductor
nanocrystals.232 There is very limited direct experimental evidence to establish the photoinduced charge transfer mechanism at the heterostructure interface. By virtue of having the
intrinsic photoluminescence (PL) of ZnO from defect state
emission as well as CP from dierent oligomeric and polymeric chains, a deep understanding of the interfacial carrier
dynamics at the nanoheterojunction has been unraveled by
steady state and ultrafast spectroscopic studies, suggesting the
co-sensitization of ZnO NPs by multiple states of polymer
Nanoscale
Review
Fig. 9 Comparative photocatalytic activity of PEDOT vesicles, PEDOT nanospindles, PDPB nanobers, commercial P25 TiO2 and AgTiO2 for
photocatalytic degradation of (a and b) phenol and (c and d) methyl orange (MO) under UV (a and c) and visible light (>450 nm) (b and d) irradiation.
Panels (a)(d) are reproduced, with permission, from ref. 227, Nature Publishers. (e) Topographic image of photosynthesized PDPB nanobres by
conventional AFM after degradation of methyl orange. (f ) NanoIR mappings of the PDPB nanostructures after photocatalytic degradation of methyl
orange as measured at a xed wavenumber (3054 cm1) after ve cycles. The signal obtained at 3054 cm1 in the chemical mapping, which originates from the benzene ring in the PDPB polymer, does not change after degradation. (g) Recycling and stability of the PDPB nanobres after
photocatalytic degradation of MO and phenol up to ve cycles measured under visible light irradiation of 240 min duration. (h) Schematic representation of the photocatalytic mechanism and energy level calculation of polymer structures by density functional theory. Energy diagram representing
the evaluated HOMO and LUMO levels of the PDPB polymer and the photocatalysis mechanism with charge separation in nano-PDPB, with electron
reducing oxygen and hole oxidizing water; the holes and generated oxidative radicals can oxidize organic pollutants (noted as M); V. B. and
C. B. represent the valence band and the conduction band of PDPB polymer, respectively. Panels (e)(h) are reproduced, with permission, from ref.
228, Nature Publishers.
transfer process from the PDPB oligomers to the ZnO NPs. The
charge separation from the polymeric chain of PDPB to the
ZnO NPs is also monitored from steady state and time resolved
spectroscopy, as shown in Fig. 10b and d, respectively.
The steady state emission peak decreases and is red shifted
to 665 nm for the PDPBZnO LHNH upon excitation at
620 nm. As shown in Fig. 10d, the fluorescence decay curve for
PDPB upon excitation at 633 nm shows an intrinsic buildup
with a rise component of 290 ps (monitored at 660 nm due to
delocalization of electrons in the conjugated polymeric chain).
The emission decay curve of PDPB is fitted with a rise followed
Review
Nanoscale
Fig. 10 (a) Schematic presentation of the co-sensitization of dierent PDPB oligomers to ZnO NPs and the molecular structure of the PDPB
polymer; (b) the interfacial carrier dynamics at the heterojunction showing the photocatalytic degradation of methyl orange in aqueous solution.
Steady state and time resolved spectroscopy of PDPB nanobers and the PDPBZnO light harvesting nanoheterojunction. (c) Photoluminesence
spectra of PDPB and PDPBZnO at an excitation wavelength of 409 nm and (d) corresponding decay proles of PDPB and PDPBZnO at 520 nm
(excitation at 409 nm). (e) Photoluminesence spectra of PDPB and PDPBZnO at an excitation wavelength 633 nm and (e) corresponding decay
proles at 660 nm (excitation at 633 nm). The inset shows the excitation spectra monitored at 520 nm and 660 nm, respectively. Reproduced, with
permission, from ref. 232, Nature Publishers.
Nanoscale
Review
Fig. 11 (a) Operating principles and energy level diagram of a dye-sensitized solar cell with a polymer cathode. Reproduced, with permission, from
ref. 263, the Royal Society of Chemistry. (b) SEM images of a PEDOT NT counter electrode, top and cross section views. (c) JV curves of the analyzed dye sensitized cells using dierent counter electrodes and electrolytes. Reproduced, with permission, from ref. 244, the Royal Society of
Chemistry. (d) Schematic representation of a solar cell device with the conguration of ITO/PEDOT:PSS/P3HT nanowires/PCBM/Ca/Al. (e) AFM
image of a P3HT nanowire/PCBM blend lm. Reproduced, with permission, from ref. 262, Wiley VCH.
Review
Nanoscale
Fig. 12 SEM images of (a) PPy lm, (b) PPy nanowire network, and (c) PPy nanowire arrays. (d) Model describing ion transport pathways for lms,
nanowire networks and nanowire arrays. (e) Specic capacitances, and (f ) stability of PPy with dierent morphologies. Reproduced, with permission,
from ref. 271, the Royal Society of Chemistry.
Nanoscale
of CNTs and is responsible for the enhanced charge transfer.272 Meng et al.273 developed a flexible paper-like supercapacitor assembled from PANI-coated CNT networks. The specific
capacitance of this flexible supercapacitor is 332 F g1 at
1 A g1. The advantage of CPNs is that the density of the total
device is low (1.18 g cm3), resulting in a low weight for the
electrode with an outstanding flexibility, making it surpass the
current commercial supercapacitor. Wei, Han and colleagues
investigated a hierarchical nanocomposite of PANI nanowire
arrays on graphene oxide sheets which exhibited a high
specific capacitance of 227 F g1 at 2 A g1 and a long cycle life
with 92% capacitance retention after 2000 cycles compared
to pure PANI (74% capacitance retention).275 3D porous
reduced graphene oxide supported PANI nanowires display
better supercapacitive performances in terms of the specific
capacitance (1024 F g1 with good stability over 5000 cycles).
It is considered that this excellent supercapacitor performance
is mainly due to active PANI nanofibers with a large specific
surface area and the unique 3D structure of the graphene
backbone oering facile conducting pathways for charge
transportation.276
4.2.2. Lithium ion battery electrodes. Li-ion batteries are
particularly interesting due to their relatively high energy densities compared to other types of batteries, but a major constraint is the intrinsic diusivity of lithium ions. In this
regard, nanomaterials with shorter diusion paths are chosen
which would increase the rate of lithium insertion or
reduction and enhance electron transport as well as provide a
high surface area. Silicon is considered one of the most promising anode materials for high-performance Li-ion batteries.
However, a dramatic volume change (300%) during full
charge/discharge cycling, led to a severe capacity decay and
poor cycling stability for intimate contact with the electrolyte.
Liu et al. reported a new direction for fabricating robust, highperformance lithium-ion batteries using three-dimensional
(3D) ternary silicon NP/CP/carbon nanotube hybrid anode
materials for Li-ion batteries (Fig. 13a).277 Fig. 13a and b show
the discharge capacity of the ternary electrode and the first discharge capacity of the ternary electrode reached as high as
3600 mA h g1, approximately 10 times higher that of the
commercial graphite anode (372 mA h g1). The ternary electrode achieved a stable discharge capacity of 1600 mA h g1
over 1000 cycles with a capacity retention of 86% and the
Coulombic eciency increased to 99% and stabilized at
99.5% in the subsequent cycles. The improved cycling performance and life-span of the electrode could be attributed to
the stabilized Si NPs which were well confined within the 3D
conductive framework that was composed of both 3D PPy
hydrogels and SWCNTs. Fig. 13c shows the SEM image of the
cycled ternary electrode which suggests the polymeric coating
on the Si NP surface was well maintained after the cycling test
as confirmed in Fig. 13d. Overall, the cycling performance of
the ternary electrode is significantly improved compared to
previously reported Si anodes due to the enhanced electronic
conductivity, and shortened pathway length for ion transport
contributed from CP.
Review
5. Origin of exciting
multifunctionality in CP
nanostructures
The controlled synthesis of nanometer-scale conducting polymers is a fascinating objective in materials science. CP NPs are
formed by self-assembling the as-designed molecular building
blocks via the weaker intermolecular interactions between
adjacent molecules, such as hydrogen bonding, stacking
and hydrophobic interactions. This section highlights the fundamental understanding of the relationship between structural
properties and the electrochemical as well as optoelectronic
performances of CPs in the nano regime. A dramatic change
in various physicochemical properties, such as electrical,
thermal, mechanical, electrical and optical, has been realized
in nanoscale dimensions compared to the bulk counterparts.281 The performance of the CPN is expected to be better
in comparison to the bulk counterpart, since polymer nanostructures have light weights, high surface areas, unique optoelectronic properties, high conductivity, stability, flexibility
and processibility.1214 The CPNs show high electrical conductivity and high electrochemical activity, as compared to their
macrogranular structure or self-supporting films.282,283
For example, the electrical conductivity of the PDPB nanostructures obtained by gamma irradiation is 0.13 S cm1,
which is several orders of magnitude higher than the conductivity of bulk polyacetylene, 1011 S cm1.284 Morever, due to
the air sensitivity of bulk polyacetylene, the stability of the
bulk polymer films in air is limited. The conductivity of PDPB
nanofibers is found to increase slightly with the decrease of
the diameter of the nanofibers. The improved ordering of the
unidirectional polymer chains resulted in a greatly increased
conductivity. As another example, PANI NPs with a smaller
size of 4 nm and high crystallinity demonstrated a conductivity
of 85 S cm1 due to the highly compact and ordered structure
of the PANI chains.285 The star-shaped PANI showed higher
electrical conductivity than the corresponding homopolymers,
originating from the three-dimensional and nanostructured
morphologies of the star-shaped polymers, which allows
sucient overlapping of -orbitals.286 Several studies report a
Review
Nanoscale
Fig. 13 (a) Schematic illustration of the formation of a 3D Si/PPy/carbon nanotube (CNT) ternary electrode. Each Si nanoparticle is encapsulated
within a thin polymeric coating layer and closely incorporated within the conductive PPy framework. The CNTs act both as the wrapping layer and
conductive backbone, which further enhance the integration of the SiNP/conductive polymer framework and electrical conductivity of the electrode. The cycling performance and structural characterization of the hybrid electrodes after long-term cycling: (b) electrochemical cycling performance of three dierent electrodes, Si/PPy/CNT (red), Si/PPy (green), and Si/PVDF (black), and the Coulombic eciency of the Si/PPy/CNT
electrode (blue) under deep charge/discharge cycles from 1 V to 0.01 V versus Li/Li+ at a current rate of 3.3 A g1; (c) the discharge capacity and
Coulombic eciency versus cycle number for the Si/PPy/CNT ternary electrode were examined during the galvanostatic charge/discharge at a constant charge capacity limited to 1000 mA h g1 at a current rate of 8.6 A g1; (d) SEM image of the composite anode after cycling with the SEI layer
removed; (e) TEM image of the extensively cycled composite anode with the SEI layer removed and elemental mapping of the designated area
(marked in a rectangle). Panels (a)(e) are reproduced, with permission, from ref. 277, the Royal Society of Chemistry.
Nanoscale
Review
Abbreviations
CP
NPs
CPNs
PEDOT
PPy
PANI
PTh
P3HT
PDPB
PPV
PMT
AAO
PTM
AFM
LHNH
PSCs
DSSCs
TCO
ITO
CE
PEMFCs
CNx
DMFCs
Conducting polymer
Nanoparticles
Conducting polymer nanostructures
Poly(3,4-ethylenedioxythiophene)
Polypyrrole
Polyaniline
Polythiophene
Poly(3-hexylthiophene)
Poly diphenylbutadiyne
Poly( p-phenylenevinylene)
Poly(3-methylthiophene)
Anodic aluminum oxide
Particle track-etched membranes
Atomic force microscopy
Light harvesting nanoheterojunction
Polymer solar cells
Dye-sensitized solar cells
Conducting transparent oxides
Indium-tin oxide
Counter electrode
Polymer electrolyte membrane fuel cells
Carbon nitride
Direct methanol fuel cells
Review
DEFCs
LIBs
Nanoscale
Acknowledgements
The authors acknowledge Director, CSIR-CGCRI for his kind
permission to publish the work. One of the authors (SG) is
thankful to Council of Scientific & Industrial Research (CSIR),
India, for providing CSIR-Senior Research Associate (Scientists
Pool Scheme) award.
Nanoscale
Review
Review
Nanoscale
Nanoscale
Review
180 Y.-W. Su, W.-H. Lin, Y.-J. Hsu and K.-H. Wei, Small, 2014,
10, 44274442.
181 M. Ates, Prog. Org. Coat., 2011, 71, 110.
182 P. Taranekar, X. Fan and R. Advincula, Langmuir, 2002, 18,
79437952.
183 S. Pruneanu, S. A. F. Al-Said, L. Dong, T. A. Hollis,
M. A. Galindo, N. G. Wright, A. Houton and
B. R. Horrocks, Adv. Funct. Mater., 2008, 18, 24442454.
184 L. S. C. Pingree, O. G. Reid and D. S. Ginger, Adv. Mater.,
2009, 21, 1928.
185 J. N. Barisci, R. Stella, G. M. Spinks and G. G. Wallace,
Synth. Met., 2001, 124, 407414.
186 K. Takami, J. Mizuno, M. Akai-kasaya, A. Saito, M. Aono
and Y. Kuwahara, J. Phys. Chem. B, 2004, 108, 1635316356.
187 Y. Martin, D. W. Abraham and H. L. Wickramasinghe,
Appl. Phys. Lett., 1998, 52, 11031105.
188 O. A. Semenikhin, L. Jiang, T. Iyoda, K. Hashimoto and
A. Fujishima, J. Phys. Chem., 1996, 100, 1860318606.
189 K. D. ONeil, B. Shaw and O. A. Semenikhin, J. Phys.
Chem. B, 2007, 111, 92539269.
190 R. J. Tseng, J. Huang, J. Ouyang, R. B. Kaner and Y. Yang,
Nano Lett., 2005, 5, 10771080.
191 H. Kobayashi, S. Hirata and M. Vacha, J. Phys. Chem. Lett.,
2013, 4, 25912596.
192 S. Ghosh, L. Ramos, A. Dazzi, A. Deniset-Besseau,
S. Remita, P. Beaunier and H. Remita, New J. Chem., 2015,
39, 83118320.
193 J. Liu, B. Wei, J. D. Sloppy, L. Ouyang, C. Ni and
D. C. Martin, ACS Macro Lett., 2015, 4, 897900.
194 Y. Lattach, C. Coletta, S. Ghosh and S. Remita, ChemPhysChem, 2014, 15, 208218.
195 Z. Cui, C. Coletta, A. Dazzi, P. Lefrancois, M. Gervais,
S. Neron and S. Remita, Langmuir, 2014, 30, 1408614094.
196 Z. Cui, C. Coletta, R. Rebois, S. Baiz, M. Gervais,
F. Goubard, P.-H. Aubert, A. Dazzi and S. Remita, Radiat.
Phys. Chem., 2016, 119, 157166.
197 S. Admassie, O. Ingans, W. Mammob, E. Perzon and
M. R. Andersson, Synth. Met., 2006, 156, 614623.
198 X. Wu, K. Liu, L. Lu, Q. Han, F. Bei, X. Yang, X. Wang,
Q. Wu and W. Zhu, J. Phys. Chem. C, 2013, 117, 9477
9484.
199 S. J. Higgins, K. V. Lovell, R. M. Gamini Rajapaksea,
N. M. Walsby and M. Wals, J. Mater. Chem., 2003, 13,
24852489.
200 E. Barsoukov and J. R. Macdonald, Impedance Spectroscopy: Theory, Experiment, and Applications, Wiley Interscience, Hoboken, NJ, 2005.
201 M. D. Levi, Y. Gofer, D. Aurbach and A. Berlin, Electrochim. Acta, 2004, 49, 433444.
202 M. R. Abidian and D. C. Martin, Adv. Funct. Mater., 2009,
19, 573585.
203 B. W. Johnson, D. C. Read, P. Christensen, A. Mamnet and
R. D. Armstrong, J. Electroanal. Chem., 1994, 364, 103109.
204 J. R. Macdonald, Electrochim. Acta, 1990, 35, 14831492.
205 D. A. Harrington and B. E. Conway, Electrochim. Acta,
1987, 32, 17031721.
Review
Nanoscale
Nanoscale
Review