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Nanoparticles meet electrospinning: recent

advances and future prospects
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Cite this: DOI: 10.1039/c3cs60426h

Chuan-Ling Zhang and Shu-Hong Yu*

Received 25th November 2013
DOI: 10.1039/c3cs60426h
www.rsc.org/csr
Nanofibres can be fabricated by various methods and perhaps electrospinning is the most facile route.
In past years, electrospinning has been used as a synthesis technique and the fibres have been prepared
from a variety of starting materials and show various properties. Recently, incorporating functional
nanoparticles (NPs) with electrospun fibres has emerged as one of most exciting research topics in the
field of electrospinning. When NPs are incorporated, on the one hand the NPs endow the electrospun
fibres/mats novel or better performance, on the other hand the electrospun fibres/mats could preserve
the NPs from corrosion and/or oxidation, especially for NPs with anisotropic structures. More importantly,
electrospinning shows potential applications in self-assembly of nanoscale building blocks for generating
new functions, and has some obvious advantages that are not available by other self-assembly methods,
i.e., the obtained free-standing hybrid mats are usually flexible and with large area, which is favourable for
their commercial applications. In this critical review, we will focus on the fabrication and applications of
NPs–electrospun fibre composites and give an overview on this emerging field combining nanoparticles
and electrospinning. Firstly, two main strategies for producing NPs–electrospun fibres will be discussed,
i.e., one is preparing the NPs–electrospun fibres after electrospinning process that is usually combined
with other post-processing methods, and the other is fabricating the composite nanofibres during the
electrospinning process. In particular, the NPs in the latter method will be classified and introduced to
show the assembling effect of electrospinning on NPs with different anisotropic structures. The subsequent
section describes the applications of these NPs–electrospun fibre mats and nanocomposites, and finally a
conclusion and perspectives of the future research in this emerging field is given.

1. Introduction spontaneously connected and integrated through direct inter-

Nanoscience and nanotechnology have been a highly inno-
vative area in the recent decades and constitutes two major
branches: one is the synthesis of different materials with various
morphologies, and the other is the construction/assembly of
these as-synthesized nanostructures.1–6 A huge variety of nano-
components with different structures and dimensionalities
(i.e., zero dimensional (0D), one dimensional (1D) and two
dimensional (2D)) have been synthesized and their broad
applications in physical, chemical and biological fields have
been widely investigated.7 Construction of the synthesized
nanostructures is necessary with the increasing requirements
in energy, material and biomedical fields and the resulting
assemblies generally show novel or better performance.8 Self-
assembly technique has been demonstrated to be the most
effective way, in which the constituent components are
Division of Nanomaterials and Chemistry, Hefei National Laboratory for Physical
Sciences at Microscale, Collaborative Innovation Center of Suzhou Nano Science
and Technology, University of Science and Technology of China, Hefei 230026,
P. R. China. E-mail: shyu@ustc.edu.cn; Fax: +86 551 63603040
actions (e.g., van der Waals interaction, electrostatic inter-
action, molecular surface forces) or indirectly using template
or external fields (e.g., carbon nanotubes (CNTs), magnetic,
electronic, flow field, and liquid interfaces).9–11
1D nanomaterials have been intensively investigated due to
their unique properties and fascinating applications in many
areas. Various methods have been developed to fabricate and
assemble 1D nanostructures in the form of wires, belts, rods,
tubes and rings from many materials.7,12 Among the methods,
the electrospinning technique has been rapidly developed in
the last decade for the facile preparation of continuous fibres
from submicron down to nanometer diameter. Although there
are other methods for preparing 1D fibres with high aspect
ratio, such as template synthesis, few methods could match
electrospinning in terms of its flexibility, versatility and ease of
fibre production. Electrospinning was invented at the beginning of
the last century (1902), but it was not until the mid-1990s that
investigators started to realize the huge capability of the procedure
for/of fibre preparation. It is notable that the amount of publica-
tions in this field (Fig. 1) is continuously increasing at breakneck
speed in the past few years, benefitting from the remarkable

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Fig. 1 Schematic representation of the number of publications per year
on electrospinning over the last 14 years following the SciFinder Scholar.
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low cost, flexibility, simplicity and potential applications of this
technique. So far, electrospinning has been used to fabricate a
huge range of nanofibres, such as polymers, metals, ceramics
and composites.
By simply electrospinning the polymers with no important
performance, the obtained fibres/films have no other applica-
tions except for using as scaffolds. In order to give full play to
the advantages of electrospinning and fabricate functional
materials, many functional materials or their precursors have
been electrospun. Among the various fibres prepared by electro-
spinning, NPs–electrospun fibres exhibit huge potential appli-
cations, as the composite fibrous mats show flexibility, are
free-standing and have applications determined by the polymer
and NPs. It is notable that when electrospinning NPs with
anisotropic structures such as nanorods (NRs) and nanowires
(NWs), the NPs would be aligned within the fibres to a certain
extent to reduce Gibbs free energy.13,14 Thus the electrospinning
technique is not only a fabrication method, but also could be
used as a simple and effective self-assembly method. Because of
the weak interactions of self-assembly, it is sensitive to environ-
mental variation, and the assembled structure is usually solution
Chuan-Ling Zhang received her
PhD in Inorganic Chemistry in
2013 from the University of
Science and Technology of China
(USTC) under the supervision of
Prof. Shu-Hong Yu. Currently, she
holds a post-doctoral scholarship
at the Hefei National Laboratory
for Physical Sciences at Microscale
in Prof. Shu-Hong Yu’s group.
Her research interests centre on
combining and assembling nano-
Chuan-Ling Zhang scale building blocks with fibres
via electrospinning technique,
and investigating the properties
of the composites.
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or template based. While for electrospinning, as the NPs are
stabilized on the surfaces or within the electrospun fibres,
it overcomes the disadvantages of the traditional self-assembly
methods as described above. Moreover, electrospinning generally
does not need any surface functionalization process with high
output: it simply requires a suitable solvent in which the NPs
can be uniformly dispersed and one kind of polymer that can
be dissolved in the solvent.
Many excellent review articles on the preparation, alignment
and applications of electrospun fibres have been published.
Most of them mainly summarized the exciting works emerging in
a period of time, the preparation and applications of a specific
kind of material, or discussed around particular applications.15–18
However, review articles focused on NPs–electrospun fibres,
especially about directly fabricating NPs–electrospun fibres
during electrospinning process, are as yet not fully realized.
Most review articles just generally introduce this area, which,
however, is of high importance and more articles are needed to
further promote electrospinning-related research. Recently, the
Popa group well summarized the important results and dis-
cussed the perspectives of electrospinning of organic or/and
inorganic dispersions for the synthesis and characterization of
multicompartment fibres.19 However, up to now, electrospinning
of NPs with different anisotropic structures has been relatively
neglected, though of great significance because electrospinning
shows potential applications in self-assembly of anisotropic NPs
for generating new functions. Besides, the applications of the
produced various fibre composites are little mentioned in litera-
ture. In this critical review, we will focus on the fabrication and
applications of NPs–electrospun fibre composites. First, two
main strategies for producing NPs–electrospun fibres will be
Shu-Hong Yu received his PhD in
Inorganic Chemistry in 1998 from
the University of Science and
Technology of China (USTC).
From 1999 to 2001, he worked in
Tokyo Institute of Technology as
a Postdoctoral Research Fellow.
From 2001 to 2002, he was as
an Alexander von Humboldt
Research Fellow in the Max
Planck Institute of Colloids and
Interfaces, Potsdam, Germany.
Shu-Hong Yu He was appointed as a full
professor in 2002 and the
Cheung Kong Professorship in 2006 by the Ministry of Education in
the Department of Chemistry, USTC. His research interests include
bio-inspired synthesis and self-assembly of new nanostructured
materials and nanocomposites, and their related properties. He
serves as an editorial advisory board member of several journals.
His recent awards include Chem. Soc. Rev. Emerging Investigator
Award (2010) and Roy-Somiya Medal of the International
Solvothermal and Hydrothermal Association (ISHA) (2010).
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Chem Soc Rev
discussed: one is preparing NPs–electrospun fibres after electro-
spinning that is usually combined with some other post-processing
methods, and the other is fabricating the composite nanofibres
during the electrospinning process. Specifically, the NPs in the
latter method will be classified and introduced to show the
assembly effect of electrospinning on NPs with anisotropic
structures. Then, we will overview the applications of these
hybrid fibres/mats, and finally give our conclusions and pers-
pectives of this emerging research field on the fabrication and
applications of NPs–electrospun fibres.
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2. Fabrication of nanoparticles–
electrospun fibres
2.1 Basic setup and principles
Electrospinning is a simple and versatile technique that utilizes
high electrostatic forces for fibre production. Four major com-
ponents are required for electrospinning: a direct current
power supply, a metallic needle with blunt-tip, a syringe for
containing the electrospun solution, and a grounded conduc-
tive collector (Fig. 2). Although the setup for electrospinning is
very simple, there are several influencing factors during the
fibres preparing process, such as polymer concentration, solution
viscosity and flow rate, electric field intensity, the work distance
(distance between collector and tip of the needle), air humidity,
etc.15,17–22 Generally, increasing the polymer concentration or
adding a pinch of surfactant to the electrospun solution could
decrease the number of beads, which is a common problem in
electrospun fibres.22
The reservoir containing the electrospun solution can be
placed horizontal or vertical: the solution flow rate is controlled
by a syringe pump in the former set-up, while mainly through
the gravity of the solution itself for the latter mode to supply the
liquid at the tip. When the electrospun solution is hosted in a
syringe and is ejected at a controlled rate by a syringe pump,
the solution will emerge from the spinneret connected to the
syringe, and a droplet would form due to the confinement of
Fig. 2 Schematic representation of the laboratory setup for electrospinning.
The inset is a sketch of the electrified Taylor cone.
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surface tension. When a high voltage is supplied to the spinneret,
charges are built on the surfaces of the droplet, and a Taylor
cone will be formed once the repulsion among the charges is
sufficiently strong to overcome the surface tension, followed by
a liquid jet directed towards the grounded collector. Before
reaching the collector, the jet is stretched by electrostatic
repulsion, and the solvent is evaporated rapidly at the same
time. Finally, the jet will be solidified and fibres will be formed
and deposited on the collector.
In general, nearly all soluble polymers can be processed into
fibres by electrospinning, provided that a large set of para-
meters that influence electrospinning are correctly adjusted.
For example, the properties of the polymer itself (such as
molecular weight, molecular-weight distribution, solubility,
melting point, glass-transition temperature and solubility), the
properties of the polymer solution (such as viscosity, concen-
tration, surface tension, temperature), and the parameters of
electrospinning process (substrate, electric field, feed rate and
relative humidity) play a major role in fiber formation. Different
electrospinning parameters can lead to fibers with very different
shapes and dimensions.17,22
The viscosity of polymer solution is very important as it
determines whether fibers can be electrospun or not, which is
affected by the molecular weight and concentration of polymer,
temperature and relative humidity of the surroundings.
In principle, high molecular weight is in favor of increasing
the viscosity of the solution. If the molecular weight of the
polymer is too low, the viscosity of the polymer solution still be
very low even with a large concentration, the surface tension
will make the polymer break up into droplets before reaching the
collector. Conversely, if excess polymer with high molecule
weight is added, the viscosity of solution is so high that it is
impossible to spin, and so unable to form fibres. All polymers
therefore have an optimal molecular weight/concentration range
in which they can be electrospun. Within this optimal range,
higher molecular weight leads to increased fiber diameters. It is
not possible to make a general recommendation for particular
molecular weights/concentrations and the resulting viscosities
and surface tensions, because the ideal values of these parameters
vary considerably with the polymer–solvent system.
Although electrospinning can be used to fabricate a huge
range of polymer fibres, not all polymers can be electrospun
into fibres easily, such as alginate. Because the gelation of
alginate solution starts to occur at very low polymer concentra-
tions (about 2 wt% polymer solution in deionized water), this
leads to solution containing insufficient material to form fibre
structures or just sprayed droplets, while at higher concentration,
the solution becomes so viscous that it can not be injected.
In this case, the way to solve the problem is to incorporate a
fraction of copolymer, and to apply surfactant or/and cosolvents
into the polymer solution.23,24
In some cases, for example, when used for catalysis and
sensors, materials with high specific surface areas are needed.
The solid electrospun nanofibres have high surface to volume
areas, and this can be further enhanced by coaxial electrospinning
(co-electrospinning), adding appropriate amounts of other materials
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that could be subsequently removed, or electrospinning into a
cryogenic liquid. So far, electrospun fibres with hollow,22,25
multichannel,26–28 porous29 and thin-wall assembled structures30
have been successfully prepared, as shown in Fig. 3. In particular,
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Fig. 3 (a) Schematic illustration of the hollow fibre fabrication system. The
spinneret consists of two coaxial capillaries, through which the immiscible
inner (mineral oil) and outer fluids (an ethanol solution containing poly(vinyl
pyrrolidone) (PVP) and titanium tetraisopropoxide) were ejected into the
individual capillaries. (b) TEM image of TiO2 hollow fibres, which were
fabricated by calcining the as-spun fibres at 500 1C after the oil cores were
extracted with octane. Reprinted with permission from ref. 22. Copyright 2004
Wiley. (c) Schematic illustration for the fabrication of a three-channel tube. The
inner and outer fluids (red for mineral oil and blue for titanium tetraiso-
propoxide solution) were separately injected to the individual syringe needles.
(d) SEM image of the three-channel tubes in which the channels were divided
into three independent parallel parts. Reprinted with permission from ref. 26.
Copyright 2007 American Chemical Society. (e) A modified electrospinning
setup with liquid nitrogen as collector. (f) TEM images of the porous polymer
fibres with insets at higher magnification. Reprinted with permission from
ref. 29. Copyright 2006 American Chemical Society. (g) Schematic illustration
of fabrication of as-spun and calcined SnO2 fibres prepared at a flow rate of
25 mL min1. (h) Magnified SEM image of fibrous thin-wall assembled SnO2
fibres. Reprinted with permission from ref. 30. Copyright 2012 Wiley.
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a variety of functional composite materials could be prepared
by co-electrospinning technique, which is derived from electro-
spinning. Co-electrospinning is based on a spinneret con-
sisting of two coaxial capillaries with different diameters. By
co-electrospinning two different fluids with this spinneret,
fibres with hollow or core–sheath structures could be fabri-
cated. For example, the curing agent of poly(dimethylsiloxane)
(PDMS) could be fixed within poly(vinyl pyrrolidone) (PVP)
electrospun fibres, and the composite film immersed in a
PDMS template. When the PDMS template is destroyed, the
curing agent could outflow from the polymer fibres and cross-
link the PDMS across the incision, thus the material could self-
heal.31 Inspired by feathers of many birds, Jiang and co-workers
fabricated multichannel fibres by a multifluidic compound-jet
electrospinning technique for the first time (Fig. 3c and d).26
Furthermore, emulsion electrospinning technique has been
developed because it can encapsulate functional materials
within fibres to form porous or core–shell structures without
the need of a complex spinneret.27
Besides the controllable morphology for the fibres, electro-
spun fibres could also be aligned by either rotating collectors or
patterned electrodes (Fig. 4).32–37 The ability to control the
arrangement of fibres is critical to achieve the desirable func-
tions, particularly for mechanical enhancement and tissue
engineering. By changing the grounded collector to two pieces
of conductive (silicon or Au) strips separated by a void gap, the
electrospun fibres could be aligned across the gap (Fig. 4a
and b). It has been reported that arrayed crossbar junctions
could be readily obtained by transferring uniaxially aligned
nanofibres onto the same substrate in a layer-by-layer fashion.
With this similar method, Xia’s group successfully stacked
aligned nanofibres into multilayered films with controllable
hierarchical structures (Fig. 4c and d).35 In addition to using
an electric field, magnetic fibres could also be aligned by
producing an external magnetic field at the collector region.
In 2010, Yang et al. demonstrated that polymer nanofibres
without magnetic NPs also could be well-ordered over a large
area and thick fibrous mats could be obtained (Fig. 4e and f).36
Furthermore, if collected by a rotating drum, the fibres
also could be aligned through use of a mechanical field
(Fig. 4g and h).37
Therefore, electrospinning technique is not only a facile
method for preparing ultralong fibres with specific structures,
but also a convenient technique to assemble nanofibres at
large-scale, while for other methods this is difficult. However,
if just electrospinning the polymers with no important perfor-
mance, the obtained fibres/films have no other applications
except using as scaffolds. In order to give full play to the
advantages of electrospinning and fabricate functional materials,
many functional materials or their precursors have been electro-
spun. Among the various fibres prepared by electrospinning, the
NPs–electrospun fibres exhibit a huge variety of potential appli-
cations, as the composite fibrous mats show flexibility, are free-
standing and will show applications determined by the polymer
and NPs. Until now, two major ways have been used to fabricate
NPs–electrospun fibres.
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2.2.1 NPs formed on the surfaces of electrospun fibres

2.2.1.1 Surface treatment. Surface treatment of the electro-
spun fibres is the simplest way to prepare NPs–electrospun
composite fibres by just immersing the surface-treated electro-
spun fibres/films into the colloidal solution, through which the
as-prepared NPs could be adsorbed on the surfaces of fibres
by electrostatic force, hydrogen bonding or the interactions
among functional groups. Many kinds of NPs, such as metal,
metal oxide, carbon, polymer, fluorescent NPs, and even cells,
have been successfully combined with electrospun fibres and
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form composite fibres.38–41 For example, our group fabricated

AuNPs–poly(vinyl alcohol) (PVA) water-stable nanofibrous mats,
as shown in Fig. 5a, in which the surfaces of the fibres were pre-
treated with 3-mercaptopropyltrimethoxysilane (MPTES), and
AuNPs were adsorbed on the surfaces via Au–S bonds (Fig. 5b).42
Kim and co-workers found a novel method for applying reduced
graphene oxide (RGO) directly to prepare electronic textiles from
yarns to fabrics.43 First, the electrospun Nylon-6 fibres were
functionalized with bovine serum albumin (BSA) molecules via
a simple dipping process to make the surface of fibres positive
charged, and then a uniform GO coating was formed on the
surfaces of the fibres via electrostatic self-assembly, finally con-
ductive RGO/nanoyarns were obtained after a low-temperature

Fig. 4 (a) Schematic illustration of a pattern that used to align electrospin

fibres. The collector was composed two gold electrodes separated by a void
gap. (b) Dark-field optical micrographs of aligned PVP nanofibres collected
between the two gold electrodes patterned on a quartz wafer. (c) Schematic
illustration of the patterns composed of six electrodes deposited on quartz
wafers. (d) Optical micrograph of a trilayer mesh of PVP fibres collected in
the center area of the electrodes shown in (c). Alternating layers with their
fibres rotated by B601 were collected by the electrode pairs (1–4, 2–5, 3–6)
sequentially grounded for 5 s. Reprinted with permission from ref. 35.
Copyright 2004 Wiley. (e) Schematic illustration of the setup using for the
magnetic-field-assisted electrospinning (MFAES) to align polymer fibres.
(f) SEM image of the aligned poly(lactic-co-glycolic) acid (PLGA) fibres
fabricated by the MFAES. Reprinted with permission from ref. 36. Copyright
2010 Wiley. (g) Schematic diagram of modified collector to align electro-
spun fibres. The collector was an insulated roller fixed with parallel sticks.
(h) Fibres collected by a roller with parallel sticks and a baffle. Reprinted with
permission from ref. 36. Copyright 2007 Wiley. Fig. 5 (a) Schematic illustration of water-stable functional AuNPs-PVA/
GA electrospun fibres, which is also a universal route for preparing hybrid
fibres by surface treatment. (b) High magnification SEM image of RGO/
Nylon-6 fibres. Numerous rumples were observed, indicating that RGO
2.2 Indirect fabrication of NPs–electrospun fibres after was well wrapped around the fibres. Reprinted with permission from
electrospinning process ref. 42. Copyright 2012 American Chemical Society. (c) TEM image of
AuNPs assembled on Nylon-6 fibres at pH 5. Reprinted with permission
If the NPs are not well dispersed within the electrospun solution, from ref. 43. Copyright 2013 Wiley. (d) SEM image of TiO2 hollow fibres
or can not be fabricated on a large scale, NPs–electrospun fibres whose inner and outer surfaces were derivatized with CH3– and NH2–
can be directly fabricated by handling the fibres with some terminated silanes, respectively, followed by incubation with Au colloids,
and found that AuNPs were only adsorbed on to the outer surfaces.
other methods, such as surface treatment, hydrothermal, sput-
(e) SEM image of hollow fibres whose inner and outer surfaces were both
tering etching, or gas–solid reaction. Based on different post- treated with an NH2-terminated silane, and then immersed in Au colloids.
treatment methods, NPs can be formed on the surfaces or In this case, the AuNPs were adsorbed on both surfaces. Reprinted with
within the fibres. permission from ref. 44. Copyright 2005 Wiley.

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vapour reduction process using hydriodic acid as reducing
agent (Fig. 5c). Interestingly, the RGO/nanoyarns show a high
electrical conductivity (41000 S m1) even under real-world
conditions, such as washing, low and high temperatures, and a
large number of repetitive bending cycles. Besides solid fibres,
the NPs also could be adsorbed on the inner or outer surfaces
of hollow fibres, such as Au–TiO2 hybrid fibres (Fig. 5d and e).44
2.2.1.2 In situ reduction. Sometimes, the surfaces of fibres are
stable and do not readily adsorb NPs. In such instances, NPs may
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attach on the surfaces by an in situ reduction method. Upon
immersion of the electrospun mats into the precursor solution,
then NPs can be formed on the surfaces by a reducing agent: the
as-prepared electrospun fibres are first immersed into an aqueous
solution containing the precursor metal ion complex to coordinate
with the groups on the fibres and then the NPs are synthesized by
reducing the complex by photoreduction or a reducing agent. For
the case of preparing metal NPs (Au, Ag, etc.), a vacuum drying
process at room temperature is often needed to prevent reoxida-
tion. For example, Xia and co-workers demonstrated that Au–TiO2
composite nanofibres could be synthesized by UV photoreduction
of HAuCl4 in the presence of TiO2 nanofibres and organic stabi-
lizers. Depending on the type and concentrations of organic
stabilizers, different shapes of Au NPs, such as nanospheres, fractal
nanosheets or nanowires, could be synthesized on the surfaces of
TiO2 nanofibres. Such a technique could also be applied in the
formation of other metal nanostructures on TiO2 nanofibres, which
might be used for chemical or biological sensing.45 This method is
a compact way to fabricate NPs–polymer hybrid fibres, and many
NPs have been synthesized on the electrospun fibres, such as Au,
Ag, Pd, Pt, TiO2, WO3, SnO2.46–51 A requirement is the electrospun
polymer fibres does not dissolve in the colloidal solution.
2.2.1.3 Hydrothermal-assisted process. Novel hierarchical
heterostructures, in which the major 1D cores and branches
consist of different materials, are more attractive in many
nanoscale photonic and electron-optical device applications.
The hydrothermal process is a well-known method for prepar-
ing nanomaterials,52–55 and when it is combined with electro-
spinning, many kinds of NPs with different morphologies (e.g.,
sphere, plate and rod) can be synthesized on the surfaces of
electrospun fibres. This strategy for preparing NPs–electrospun
fibres has several favorable merits including: (i) both the
electrospinning and hydrothermal method have been proven
to be a comparatively versatile, low cost, applicable and environ-
mentally friendly technique; (ii) this method could be extended
to the fabrication of various metal oxides (MOs) (e.g., TiO2, WO3,
CuO, Co3O4, Fe2O3, Fe3O4, etc.) on electrospun nanofibres to
form MOs–electrospun hierarchical heterostructures; (iii) the
synergistic effects of nanoscale building blocks as well as
the unique hierarchical heterostructures may contribute to the
improved performances. With this strategy, ZnONWs–polystyrene
(PS) hybrid nanofibres with ‘‘nanobrush’’ structure were fabri-
cated by immersing the PS electrospun fibres into ZnO NPs
solution to lead to the NPs adsorbing on the fibre surfaces,
and then ZnO nanowires were grown from the seeds through a
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simple hydrothermal process. The fabricated composite fibres
with special heterostructures showed high performance for strain
sensing.56 Zhang and co-workers also controlled synthesized metal
oxide–TiO2 hierarchical heterostructures with improved lithium-
ion battery performances by using this method.57 Other composite
fibres, such as SnO–C, In2O3–C, hydroxyapatite–C, TiO2–WO3 and
WO3–TiO2, also have been successfully fabricated.58–61 With this
similar method, TiO2–Pt nanocomposite fibres can be prepared
by a combination of microwave irradiation and electrospinning
technique, and show improved electrical catalytic activity.62
In addition to the commonly used methods, ultrasonication
and sputtering etching are also applied to fabricate NPs on the
surfaces of electrospun fibres.39,40,63
2.2.2 NPs formed within electrospun fibres. Besides on the
surfaces, NPs could also be synthesized within the fibres by first
electrospinning a solution containing metallic or ceramic acetate
precursor, and then applying other treatments such as gas–solid
reaction, calcination or laser ablation.
2.2.2.1 Gas–solid reaction. Doped NPs within electrospun
fibres through gas–solid reaction was first reported by Wang
et al.,64 and a series of composite fibres have been fabricated.
For this method, precursor nanofibres with metallic or ceramic
acetate dissolved in polymer are electrospun, and then exposed to a
special gas atmosphere, such as H2S, to form NPs. Especially,
semiconductor NPs with diameters below 10 nm can be readily
synthesized with this method. Wang and co-workers successfully
fabricated PbS–PVP and CdS–PVP composite fibres by using lead
acetate and cadmium acetate as precursors, respectively, and finally
exposed the fibres to H2S gas.64 Similarly, Yang and co-workers
fabricated AgCl–poly(acrylonitrile) (PAN) composite nanofibres by
exposing AgNO3–PAN electrospun fibres to HCl atmosphere, by
which AgCl NPs both on the surfaces and interior of the fibres can
be synthesized.65 In addition to the metallic compounds, purely
metallic nanofibres have also been fabricated with this method. For
example, Greiner and co-workers fabricated Cu NWs by electro-
spinning copper nitrate within poly(vinyl butyral) (PVB) nanofibres,
and then heating the fibres in an air atmosphere to 450 1C for 2 h
to remove PVB; further heating in a hydrogen atmosphere at 300 1C
for 1 h was then applied and resulted in copper fibres.66 Recently,
the Cui group electrospun PVA nanofibres containing copper
acetate onto a glass substrate, then the fibres were calcined at
500 1C in air for 2 h to remove PVA and transformed the composite
nanofibres to CuO nanofibres. Finally, the CuO nanofibres were
reduced into red Cu nanofibres after annealing in an H2 atmo-
sphere at 300 1C for 1 h. The copper nanofibres showed great
flexibility and stretchability, and glass substrates coated with Cu
nanofibres showed high transmittance at low sheet resistance.67
2.2.2.2 Calcination. Calcination of the electrospun fibres
containing metallic or metal/ceramic acetate precursors is
another method to prepare NPs–electrospun composite materials,
and the NPs are usually well dispersed within the electrospun
fibres. Its basic principle is combining electrospinning technique
with the traditional sol–gel method to prepare precursor fibres,
and then calcining the as-prepared composite fibres to prepare NPs
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within the fibres. With this method, different kinds of metal, metal
oxide and their carbon composite fibres have been prepared. The
use of water-based polymer and metallic precursor for fabricating
metallic fibres sometimes limits the measurements in terms of
magnetic and electrical properties owing to low loading of metal
precursors, while the metal/ceramic acetate precursors could over-
come the above shortcomings and have been widely used. Joo and
co-workers electrospun acetates of Cu, Ni, Fe and Co within PVA
fibres, calcined the fibres at 400 1C in an Ar atmosphere, and the
synthesized NPs were uniformly distributed within the fibres.68
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Wang and co-workers fabricated Sb–C fibres via electrospinning
SbCl3 with PAN. After a calcination process, SbNPs (B30 nm) were
uniformly distributed within the fibres and the fibrous mat can be
used as a stable and fast sodium-ion battery anode.69 Similarly,
Li3N–C composite fibres were fabricated and show advanced
hydrogen storage performance.70 If different precursors were added
into the electrospun solution, sometimes composite fibres with two
or three kinds of metal oxide could be synthesized, such as ZnO–
SnO2,71 TiO2–V2O572 and Al2O3–ZnO.73 Interestingly, the V2O5 NPs
were not uniformly distributed within the fibres with TiO2, but
found on the surfaces of the fibres in rod form.72
Besides spherical structure, NPs with other special structures
could also be fabricated. For example, Co3O4 hollow NPs were
fabricated within carbon nanofibres (CNFs), and the formation
of hollow NPs can be easily understood and explained by the
well-known Kirkendall effect during the transformation from Co
NPs into Co3O4 hollow NPs.74 The Marier group reported on
Sn–C nanofibres fabricated by forming Sn NPs encapsulated in
porous multichannel carbon microtubes via electrospinning and
subsequent calcination (Fig. 6).75 In this way, an appropriate
Fig. 6 (a) Schematic diagram of the electrospinning process of a poly-
(methyl methacrylate) (PMMA) PAN–tin octoate mixture in dimethylformamide
(DMF). The inset shows a magnified view of the solution in the needle.
(b) SEM image of the as-synthesized core–shell nanofibres obtained via
electrospinning. (c) Proposed synthetic scheme for Sn NPs encapsulated in
porous multichannel carbon microtubes. (d) High-magnification cross-
sectional image of PMMA–PAN–tin octoate nanofibres after carbonization
that reveals the multichannel tubular structure of the fibres. Reprinted with
permission from ref. 75. Copyright 2009 American Chemical Society.
This journal is © The Royal Society of Chemistry 2014
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cooperation between a high filler density of Sb NPs and
sufficient space to buffer the volume change can be realized.
In 2011, the same group reported single-crystalline carbon-
coated LiFePO4 nanowires synthesized by a similar method.
The obtained nanowires not only differ from reported analogues
in crystallinity, but they were also substantially thinner.76
2.3 Direct fabrication of NPs–electrospun fibres during
electrospinning process
The as-prepared NPs can be directly added into the polymer
solution, by which the composite fibres could be synthesized in
one-pot by electrospinning the above solution. This is the most
straightforward strategy to fabricate composite electrospun fibres
and has been widely used. Until now, various NPs have been
successfully synthesized, and the NPs–polymer electrospun fibres
could be easily prepared as long as the NPs are uniformly
distributed within the polymer solution. By varying the amount
of NPs added into the electrospun solution, the density of NPs
within the polymer fibres can be easily controlled, and thus the
properties of the composites could be tuned. Especially for
anisotropic NPs, such as polymer chains, NRs and NWs, electro-
spinning exhibits its assembling effect with several advantages,
i.e., the NPs can be readily assembled on a large scale and a free-
standing film can be fabricated. With years of development of
electrospinning, different kinds of NPs have been directly electro-
spun. Here, we divide these NPs into four main classifications, i.e.,
0D NPs, 1D NPs, 2D NPs, and other organic or biomolecules.
2.3.1 0D NPs–electrospun fibres. Inorganic NPs have higher
electronic density than the polymers, as a result of which the NPs
could be encapsulated within the polymer fibres by electrospinning
technique. Compared to the film composed of spherical NPs, the
morphology of the electrospun fibres do not have a regular
hexagonal structure, which is caused by the different time scale:
the film formation is measured in hours, whereas the electrospun
fibre is formed within milliseconds. Up to now, a variety of 0D
nanomaterials, such as metal, metal oxide, quantum dots and
polymer spheres, have been prepared and show advanced pro-
perties in various areas. When these materials are electrospun,
the NPs are usually randomly dispersed within the polymer
fibres and functionalize the fibres. Sometimes, the NPs can not
be well dispersed in the electrospun solution, and cluster like
structures form in the obtained composite electrospun fibres.
In such cases, some surface treatments of the particles are
needed to make the NPs uniformly distributed.
2.3.1.1 Metal and metal oxide NPs. Zero-valent NPs have
great potential applications in material engineering. NPs with
different diameters have been successfully electrospun within
polymers, such as water-soluble polymers (poly(ethylene oxide)
(PEO), PVA, PVP) and non-water-soluble polymers (PAN, poly-
(L-lactide) (PLLA), etc.). This is the simplest method for preparing
composite fibres: just adding the NPs into the electrospun
solution with appropriate polymer concentration, stirring it to
make the NPs uniformly distributed, and finally electrospinning
the above solution. If both NPs and polymer dissolve in the
solvent, the NPs are generally randomly distributed within the
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electrospun fibres. Sometimes we need to combine the perfor-

mances of both NPs and functional polymers together even if
the two components can not be dissolved in the same solvent.
In that case, two strategies can be used, the first one is
dissolving the NPs and polymers separately in different solvents,
then mixing the two solutions, the premise of this method is the
solvents are miscible; the other strategy is modifying the surfaces
of the NPs using surfactants, such as PVP and thionaphthol, to
make the NPs evenly dispersed.
Gold NPs have special plasmonic properties and have been
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widely electrospun.77,78 After electrospinning, the AuNPs–polymer

composite fibres have better conductivity than the pure polymer
fibres, and could be used as scaffolds for tissue engineering.
Based on the plasmonic property of AuNPs, the electrospun fibres
Fig. 7 (a) Photograph of AgNPs/PVA fibrous mat by electrospinning for
can also be used for SERS and photothermal applications. For the 1 h, the molar ratio of PVA/Ag is 530 : 3. (b) Schematic illustration of
latter application, the fibres are not only used for cancer therapy formation of Ag NP aggregates with chain-like structures within PVA
but also used as localized sources for surface plasmon resonance- fibres. (c–f) TEM images of AgNPs/PVA fibres with different PVA/Ag molar
mediated heating, which could lead to the melting of polymers or ratios of 530 : 1, 530 : 2, 530 : 3 and 530 : 4. Reprinted with permission from
ref. 82. Copyright 2009 American Chemical Society.
altering their nanostructures.79 Recently, a novel flexible non-
volatile flash transistor memory device based on poly(ethylene
naphthalate) (PEN) substrate using 1D electrospun nanofibres of within the fibres (Fig. 8A),86 while when over 140 nm, the NPs
poly(3-hexylthiophene) (P3HT):AuNPs hybrid as the channel was tend to aggregate,87 and are aligned within the polymer fibres
presented. In this device, AuNPs were employed as localized with necklace-like structure once increasing to over 260 nm
charge traps across the nanofibre channel and could program/ (Fig. 8B).88 If Rhodamine B is electrospun with SiO2 NPs at the
erase the device towards low conductance (OFF)/high conduc- same time, the SiO2–PMMA composite fibres could be used for
tance (ON) states under an applied electrical field.80 The electro- white light emission.89 Cai and co-workers found that the
spinning process was also successfully used to fabricate polymer position of SiO2 NPs within the polymers is also related to the
nanofibres containing one-dimensional arrays of AuNPs. The mixed solvent used for dissolving the polymers. When decreas-
intrinsic nature of semicrystalline PEO was used as a template ing the vapor pressure of tetrahydrofuran/dimethylformamide
to arrange the AuNPs within the fibres during electrospinning. (THF/DMF), the SiO2 NPs transferred from the middle of the
The TEM image revealed that AuNPs form quite long and one
dimensionally arranged chainlike arrays within the electrospun
fibres.81
Silver NPs are another important metallic material for their
plasmonic and antimicrobial properties. Different diameters of
AgNPs have been widely electrospun. Interestingly, AgNPs tend
to aggregate and form chain-like structures after vigorous
stirring of AgNPs–PVA solution in a shaker at 40 1C for 5 h, as
shown in Fig. 7. The number of NPs in the chain is determined
by the concentration of AgNPs. After electrospinning, the NP
chains were confined and aligned within PVA fibres. The
obtained free-standing electrospun mat could be used as a SERS
substrate with high sensitivity and reproducibility.82
Some other zero-valent NPs, such as nanodiamond, Si, Zn,
Co, Ti and Cu, have also been successfully electrospun.83–85
Especially for electrospinning CuNPs, the NPs were fixed within
PVA fibres, and form cable-like structures, which may be related
Fig. 8 (A) SEM image of Ag2S–PVP composite fibres fabricated by electro-
to the polarization of the NPs.
spinning PVP solution containing Ag2S colloid. Reprinted with permission
Different kinds of ceramic NPs, such as SiO2, TiO2, MgO, from ref. 86. Copyright 2009 Wiley. (B) PVA/SiO2 (910 nm) electrospun fibres
ZnO and ZrO2, have been electrospun. The NPs with dimensions with necklace-like structure. PVA : SiO2 = 300 : 700, PVA 12 wt%, voltage
ranging from nanometers to micrometers have been electrospun 15 kV. Reprinted with permission from ref. 88. Copyright 2010 American
into hydrophobic or hydrophilic polymers. For example, when Chemical Society. (C) HRTEM image of MRF–PET composite fibres fabri-
cated by co-electrospinning. The mass ratio of solution was 1.5 : 1, the flow
SiO2 NPs were electrospun, the obtained film was usually super-
rate of both core and sheath was 5 mL min1. Reprinted with permission from
hydrophobic with mesoporous structure. The state of the NPs in ref. 98. Copyright 2012 Elsevier. (D) HRTEM image of a self-assembled array
the polymer fibres is diameter-related: when the diameter of NPs of FePt NPs encapsulated within PCL nanofibres by co-electrospinning.
is far below the fibres, the NPs could be randomly dispersed Reprinted with permission from ref. 99. Copyright 2005 Elsevier.

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Chem Soc Rev
fibres to the surfaces slowly.90 Also for the case of TiO2 NPs,
TiO2–polymer electrospun fibres showed better photocatalytic
performance than TiO2 NPs, the authors explained that the
photocatalytic superiority of TiO2 nanofibres is attributed to
effects of mesoporosity and nanoparticle alignment, which
could cause efficient charge separation through interparticle
charge transfer along the nanofibre framework.91
Another important species in metal oxide NPs is magnetic
NPs. Magnetic composite nanofibres, in which magnetic NPs are
embedded, are expected to exhibit interesting magnetic field-
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dependent mechanical behavior with potential applications in a
range of areas. For example, the composite nanofibres could be
used as ‘‘intelligent’’ fibres or fabrics for defensive clothing for
military use, and in health care. Due to their high surface-to-
volume ratio, magnetic NPs tend to agglomerate with each other
to reduce energy. To overcome this problem, the use of stabilizer,
electrostatic surfactant, and steric polymers have been
proposed.92–95 Rutledge and co-workers first prepared super-
paramagnetic nanofibres containing stably-dispersed super-
paramagnetic NPs via electrospinning. The NPs were synthe-
sized in the presence of a polymer that attached to the particle
surfaces and conferred steric stabilization to the nanoparticle
dispersion in the polymer solution. The NPs were observed to
line up within the fibres in columns parallel to the fibre axis
direction, apparently induced by the electrospinning process.96
Ferrofluids are a colloidal suspension of magnetic particles,
and magnetic NPs in ferrofluids are coated with an organic
material, thus they are free from agglomeration to some extent.
It is well known that fibres with core–shell or hollow structures
could be fabricated by coaxial electrospinning. Similarly, by
adding mineral oil into a ferrofluid and coaxial electrospinning
the composite solution, magnetic NPs could be uniformly aligned
on the inner wall of hollow fibres, and the obtained mats/fibres
possess magnetic properties.97 For example, Fe3O4–poly(ethylene
terephthalate) (PET) magnetic composite nanofibres have been
fabricated by coaxial electrospinning. Interestingly, the NPs could
align in the middle of the fibres and form cable-like structures
(Fig. 8C).98 The magnetic properties as well as mechanical
properties with applied magnetic field were distinctly increased
due to the dipole–dipole interaction between magnetic NPs in
the magneto-rheological fluid (MRF). Self-assembled FePt NPs
have also been encapsulated within poly(e-caprolactone) (PCL)
nanofibres by coaxial electrospinning, assisted by electrostatic
interactions, the encapsulated array of the discrete FePt NPs
can reach as long as 3 mm along the fibre axis (Fig. 8D).99 Other
magnetic composite fibres with core–sheath structure, such
as polyarylene ether nitriles (PEN)–Fe-phthalocyanine–Fe3O4,
Fe3O4–PEO and Fe3O4–PET, have also been fabricated by a
similar method.98,100,101 Thus the coaxial electrospinning tech-
nique is a simple and effective method for separating magnetic
NPs. In these composite nanofibres, Fe3O4 NPs were all in
linear arrangement in the middle of the fibres, and the mag-
netic performance of the mats as a function of the orientation
of the fibres has been investigated.
In addition, electrospinning a copolymer rather than a homo-
polymer, the polymers would self-assemble and form coaxial
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structures within the fibres.102 Surface treatment of NPs could
control the spatial location of NPs in polymer matrices.103 For
example, coaxial nanofibres with poly(styrene-block-isoprene)
(PS-b-PI)/magnetite NPs as core and silica as shell were fabri-
cated using electrospinning technique, in which the magnetite
NPs were surface coated with oleic acid to provide marginal
selectivity towards an isoprene domain, the TEM images of the
composite fibres confirmed that the NPs were uniformly dis-
tributed within the PI domain.103
2.3.1.2 Fluorescing NPs of quantum dots and rare-earth metals.
Many metal and inorganic fluorescing NPs have been electro-
spun and their luminescent properties investigated.104,105
These phosphor NPs include boron carbonitride (BCN) oxide,
sodium yttrium fluoride, quantum dots and rare-earth metals,
etc. It is well known that the rare-earth elements have good
luminescent properties, and various composite electrospun
fibres of rare-earth NPs and polymers or ceramics have been
prepared, such as Sm3+/TiO2, NaYF4:Yb3+, Er3+/SiO2, YVO4:Eu3+/PEO,
X1–Y2SiO5:Ce3+/Tb3+.106–109 Besides good luminescent proper-
ties, the composite fibres also have certain applications in
controlled drug release. Quantum dots, such as CdTe and
CdS, also have been successfully electrospun within polymer
fibres, the fabricated mats/fibres exhibit corresponding lumines-
cent property, and photoluminescence spectra of the electrospun
fibres are blue-shifted compared to the quantum dot solutions,
this is because the NPs have different quantum confinement
effects in different media.110,111
Fluorescent molecules also have been electrospun. For
example, a thermoplastic polyurethane (TPU)–fluorescein com-
posite nanofibrous mat is used to identify latent fingerprints on
various substrates within 30 s and produce inkjet-printed
patterns. In contrast to classical approaches, the method is easy-
to-operate, environmentally friendly, and has implications in
other applied systems including chemical sensors, drug delivery,
biological detection and microreactors (Fig. 9).112
2.3.1.3 Polymer NPs. Recently, considerable research has
been focused on the therapeutic applications of electrospun
fibres for gene, drug or protein delivery in tissue engineering,
due to the similarity between a porous nanoscale electrospun
matrix and the naturally occurring fibrillar extracellular matrix
(ECM). The encapsulation of bioactive compounds, such as
drug or proteins, using NPs is widely investigated as a delivery
method because NPs can pass through cell membranes, allowing
for facilitated delivery of bioactive compounds to cells. There are
several methods for encapsulating bioactive compounds, and
the simplest way is encapsulating the compounds within poly-
mer NPs, followed by hardening of the formed NPs via electro-
spinning. Besides, crosslinking among or within the particles
could further improve the mechanical properties and thermal
stability of the fibres.
Microgels have been widely investigated because of their
conformation state: this can control the release of the materials
confined within the gels by applying an external stimulus.
Poly(NIPAM-co-AA-co-MBAAm) microgel, which is sensitive to
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Fig. 9 (A) Representation of the electrospinning setup using a rotated
drum collector. (B) SEM image of the TPU–fluorescein composite nano-
fibres, inset is the photograph of the composite fibrous mat. (C) Bright field
image of a fingerprint on the hybrid mat touched by a finger and then
developed with hot air for 5 s. Reprinted with permission from ref. 112.
Copyright 2011 Wiley.
temperature and pH, was electrospun in cross-linked PVP
fibres.113 Piperno and co-workers found that the microgel could
be electrospun without polymers as long as the concentration
reached a certain concentration, and this process was not
limited to the electrospinning polymer particles distributed in
the polar medium.114 PMMA–PVA composite fibres also have
been fabricated, and this study results from the fact that
swollen polymeric colloids can be localized in the core region
of electrospun fibres and packed close to each other to form a
continuous core (Fig. 10a).115 Besides, core–sheath fibres con-
sisting of a PCL sheath and PNIPAM microgel particles in the
core have been synthesized (Fig. 10b). PS NP is another kind of
often used polymer spheres in electrospinning for delivery
(Fig. 10c),107 and other polymer NPs, such as polyacrylamide,
PMMA/PAN, poly(lactide-co-glycolide), polyurethane (PU) and
poly(hexamethylene adipate)-PEO block copolymers (PHA-b-PEO),
have also been electrospun.116–121 Most research uses electro-
spinning for delivery focuses on the encapsulation and release
of one component, while for many applications, multiple
compounds are needed. Recently, Wnek et al. developed a
novel method for the fabrication of biocompatible polymeric
fibres with the encapsulation of two distinct biological components,
as shown in Fig. 10d.122 Two-luminophore nanowires with a poly-
phenylenevinylene (PPV) shell and (n-Bu4N)2(Mo6Br8F6)@PMMA
core were synthesized by coaxial electrospinning. The two
luminophores, (n-Bu4N)2[Mo6Br8F6] compound and PPV, were
selected to restrain the absorption and emission spectral
overlapping, while a spatial separation was achieved by the
coaxial geometry.
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Fig. 10 (a) Schematic diagram for producing core–sheath nanofibres that
contain an array of colloids in the core. (b) Combination of optical and
fluorescence mode images of the core–sheath fibres, consisting of a PCL
sheath and PNIPAM microgel particles in the core. Reprinted with permis-
sion from ref. 115. Copyright 2009 Wiley. (c) Two-color stimulated emis-
sion depletion microscopy (STED) image of PVA fibres immobilized with PS
NPs. Two fluorophores, B504-MA and PTCA, were used to label PS NPs
and PVA, respectively. Reprinted with permission from ref. 107. Copyright
2011 American Chemical Society. (d) Fluorescence image of the PU
electrospun fibres containing PVA/EGF-AF488 and PVA/BSA-TR particles
with three times more EGF-AF488 and BSA-TR loaded during particle
synthesis. Reprinted with permission from ref. 122. Copyright 2009 Wiley.
Other NPs, such as molecular imprinted polymers and PVA
NPs loaded with protein, have also been electrospun.122,123
2.3.2 1D NPs–electrospun fibres
2.3.2.1 Organic nanochains. Materials with anisotropic structure,
such as NRs and NWs, have a large surface-to-volume ratio and
two-dimensional confinements. 1D materials have been widely
investigated for their unique optical, electrical and magnetic
properties.12 When these oriented materials are electrospun,
electrospinning shows its potential ability for assembly: the
nanocomposites are usually aligned along the long axial direc-
tion of the electrospun fibres. Ranging from organic molecule
chains to inorganic 1D nanomaterials, even big biological mole-
cules, could be aligned. Especially for those materials whose
properties are determined by their aggregation or orientation
state, such as AuNRs, electrospinning could facilely control the
spaces among particles at the same time, just by varying the
amount of NPs directly added into the electrospun solution.
Rabolt and co-workers reported for the first time that an
electric field can be used to macroscopically align polymer
nanofibres and the polymer chains are parallel to the fibre
axis. This important result indicates that anisotropic structural
properties can be induced in polymer nanofibres during the
electrospinning process.124 In 2008, the Chirachanchai group
induced the electrospinning technique for controlling the
crystal orientations the poly(oxymethylene) (POM) fibres. The
author emphasized that this finding opened a new research
field in polymer science where we can understand the relation-
ship between structure at the molecular level and the properties
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Fig. 11 (a) SEM image of a single polyoxymethylene (POM) nanofibre
collected at 630 m min1. (b) Schematic illustrations of nanofibril within
a single POM fibre. (c–e) Schematic illustration of the crystal orientation at
0 m min1, 630 m min1 and 1890 m min1, respectively. (f) Crystal confirma-
tion of the helical structure of the POM chain. Reprinted with permission from
ref. 125. Copyright 2008 American Chemical Society.
at the macroscopic level (Fig. 11).125 Becker and co-workers
used a primary amine-derivatized 4-dibenzocyclooctynol (DIBO)
to initiate the ring-opening polymerization of poly(g-benzyl-
L-glutamate) (DIBO-PBLG). This initiator yields well-defined
PBLG polymers functionalized with DIBO at the chain termini.
The DIBO end group further survives an electrospinning
process that yields nanofibres that were then available for
post-assembly functionalization with any number of azide-
derivatized molecules.126 Soft self-assembled photonic materials
such as cholesteric liquid crystals are attractive due to their
multiple unique and useful properties, and a short-pitch
cholesteric confined in the core of polymer fibres produced
by coaxial electrospinning, showing that the selective reflection
arising from the helical photonic structure of the liquid crystal
is present even when its confining cavity is well below a
micrometer in thickness, allowing as little as just half a turn
of the helix to develop. At this scale, small height variations
result in a dramatic change in the reflected color, in striking
difference to the bulk behavior. Liquid crystals have also been
electrospun within polymer fibers.127 It is notable that if
monomers are aligned within the fibre, the polymerized chains
can also be arranged. Recently, hybrid mechanoresponsive
polymer wire composed of polydiacetylene (PDA) and PEO
have been fabricated. Because the attractive forces among
diacetylene molecules were much larger than those between
the monomers and the matrix, the monomers self-assembled
within the fibres and oriented along the stretching direction.
Finally, mechanoresponsive fibres were fabricated through
exposure to UV light within which the polymer chains of PDA
were aligned.128
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Fig. 12 (a) Typical SEM image of the Au/PVA nanofibre mat. (b) Photograph
of AuNRs/PVA fibrous mat fabricated by electrospinning for 1 h with AuNRs
particle concentration of 200 nM. (c) High magnification TEM image of the
composite fibre in (a), in which the NRs were all aligned along the axes
direction of the electrospun fibres. (d) The UV-Vis-NIR absorption spectra of
the Au/PVA electrospun mats with different AuNRs concentrations. Reprinted
with permission from ref. 14. Copyright 2011 Wiley.
2.3.2.2 Inorganic 1D NPs. AuNR is one important kind of NP
for its localized surface plasmon resonance (LSPR) performance,
and have been widely investigated in the fields of catalysis,
biomedicine and sensors. Several works have been reported that
AuNRs can be electrospun within the fibres.14,129,130 Our group
applied the electrospinning technique to readily assemble AuNRs
on a large scale, which has the advantage of simple and con-
venient preparation, and the fabricated free-standing film is
flexible and stable (Fig. 12a and b). To investigate the assembly
effect on the properties of the mat, the optical and SERS property
are investigated. By controlling the amount of the NRs added into
the electrospun solution, the side-to-side and tip-to-tip distances
can be adjusted, and therefore the optical properties of the
composite mats could be controlled. Compared with the AuNRs
solution and corresponding casting films, both the transverse
plasmon band (TPB) and the longitudinal plasmon band (LPB) of
the electrospun mat red shifted; when increasing the AuNRs
concentrations, the LPB of the electrospun mats blue shifted and
broadened, while there is no significant change on TPB, which
confirms the effect of assembly on their optical properties.
In addition, the electrospun mat could be used as a surface
enhanced Raman scattering (SERS) substrate. The resulting
electrospun mat makes a significant SERS enhancement to
3,3 0 -diethylthiatricarbocyanine iodide (DTTCI) molecules with
large-area uniformity and good reproducibility.
NWs with high aspect ratio, such as calcium silicate hydrate
(Fig. 13a),131 CNTs (Fig. 13b),132 AgNWs (Fig. 13c and d),133 and
AuNR–AgNW assemblies (Fig. 13e and f),134 have been electro-
spun, which play a critical role in the mechanical and electronic
reinforcement of the polymers. For example, CNTs consist of
rolled graphene sheets as first reported by Oberlin and Endo,135
and have been electrospun within polymer fibres. The purpose of
electrospun CNTs is to functionalize the polymer fibres (in terms
of conductivity, mechanical performance or thermal conductivity)
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Fig. 13 (a) TEM image of a hybrid electrospun fibre with 10 wt% calcium
silicate hydrate (CSH) NWs. Reproduced from ref. 131. (b) The high magni-
fication bright field TEM images of electrospun MWNT–PAN hybrid nano-
fibres containing 10 wt% oxidized MWNTs. Reprinted with permission from
ref. 132. Copyright 2004 American Chemical Society. (c) Photograph of
AgNWs/PVP electrospun mat with a AgNW concentration of 15 mg mL1 and
an electrospinning time of 15 min fabricated by magnetic-assisted electro-
spinning technique, by which the composite nanofibres were all parallel
aligned in the whole mat. (d) High-magnified TEM image of the AgNWs/PVP
electrospun fibres, in which more than ten AgNWs could be assembled
within a single fibre and aligned along electrospun fibres. Reprinted with
permission from ref. 133. Copyright 2012 Wiley. (e) Photograph of AuNR–
AgNW/PVA electrospun mat. The mass concentrations of AgNWs and
particle concentration of AuNRs in the electrospun solution were 4 mg mL1
and 20 nM, respectively. (f) The corresponding TEM image of the fibres
containing AuNR–AgNW nanocomposites. Reproduced from ref. 134.
or make CNTs align within the fibres. At present CNTs have
been electrospun within many different polymers, such as PAN,
PEO, PVA, PLA, PMMA. It has been demonstrated that when
well dispersed in the polymer fibres, CNTs can fully complex
with polymer and be aligned within the axial direction of the
fibres. Unexpectedly, when calcining the CNTs/PAN fibres to
make polymer transferred into carbon, CNTs aligned on the
surface of the carbon fibres with nanobrush-structure.136 Recently,
both TiO2 NRs and CNTs were electrospun within fibres. After
calcining, the composite showed high electronic collection capa-
city when used as an electrode of a dye fuel cell.137
Our group has confirmed that AgNWs could be aligned on
the macroscopic scale by using the magnetic-field-assisted
electrospinning technique (Fig. 13c and d).133 With this
method, ultralong AgNWs can be assembled within the PVP
electrospun fibres and arranged in parallel. The number of
AgNWs confined within the PVP fibres can be controlled by
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changing the concentration of NWs in the electrospun solution
while the polymer nanofibres can also be arranged by the
magnetic-assisted-field electrospinning technique and the
AgNWs manipulated to align parallel to each other throughout
the entire film. AgNWs can be further aligned as a result of the
flexibility of the polymer fibres, and mats with variable cross
angle and the fibre assemblies with hierarchical structures can
be prepared. Other complex 1D nanostructures, such as AuNR–
AgNW assemblies that were prepared by electrostatic adsorption,
also have been assembled by electrospinning.134 Compared with
the normal casting films composed of randomly dispersed
AuNRs and AgNWs, or electrospun mats with monometallic
components, the resulting AuNR–AgNW/PVA electrospun mats
show red-shifted and broader absorption bands, also higher
SERS performances, due to the ordered alignment of AuNR–
AgNW nanocomposites on a large scale.
Other NWs, such as cellulose nanowhiskers,138 and halloysite
nanotubes,139 also have been electrospun and greatly improved
the mechanical performance of the composite fibres.
2.3.3 2D NPs–electrospun fibres
2.3.3.1 Clay nanosheets. Clay has a sheet structure, and itself
has good mechanical properties and thermal stability. The
addition of layered nanostructures enhances the mechanical
properties, thermal stability and barrier properties of polymers.
This is attributed to the high aspect ratio and available surface
area of the nanosheets. Theoretical analysis has shown that
addition of materials with high aspect ratio could highly
enhance the mechanical properties of the composites. Three
methods have been investigated for preparing traditional
sheets/polymer nanocomposite materials: melt mixing, liquid
phase polymerization and liquid-phase-coordination. Much
work have been done to investigate whether the electrospinning
technique could be used to prepare fibres containing plates
rather than 0D or 1D NPs.
The main problem for electrospinning 2D NPs is how to
make the clay sheets disperse in the electrospun solution
uniformly. Without sufficient stripping, clay sheets will deposit
in the bottom of the electrospinning solution or form irregular
electrospun fibres with ridge or bead structure, and thus
affecting its performance. To solve this problem, there are two
main methods: one is by using one of the three methods above-
mentioned for preparing sheet/polymer composite material,
and then electrospinning; the other is to dissolve clay tablets
and polymer in a particular solvent, or mix two different
solutions together that dissolve the polymer and clay tablets
separately. In the former case, the dispersion of the clay tablets
mainly depends on the preparation process, while the second
method mainly depends on the dispersion state of NPs in the
solvent. Many related research works have been published, and
clay tablets are coated in a variety of electrospun fibres. For
example, after modification with a quaternary ammonium salt,
organiclay/polyamide-66 (PA66) electrospun fibres with organo-
clay content as high as 7.5 wt% could be obtained (Fig. 14a).140
In the choice of polymer, in addition to considering the compati-
bility with clay tablets, polymers with good mechanical proper-
ties are considered, such as PMMA, PS, PU, PAA, polyamide-6
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Fig. 14 (a) TEM image of organoclay–PA66 composite nanofibres with
organoclay content of 7.5 wt%. Reprinted with permission from ref. 140.
Copyright 2012 Springer. (b) TEM image of montmorillonite (MMT)/Ag/PVA
nanofibres with MMT and Ag contents of 5 wt% and 1 wt%. Reprinted with
permission from ref. 145. Copyright 2010 Springer. (c) HRTEM image of
GO/PNA nanofibre, in which GO nanosheets were modified by 1-pyrene-
butanoic acid, succinimidyl ester. The arrows indicate the flakes inside the
fibres. Inset is an enlarged image of GO embedded within the sidewall of a
fibre. Reprinted with permission from ref. 151. Copyright 2010 Wiley.
(d) SEM image of graphene oxide-templated PAN nanofibres, inset is an
SEM image of a thicker area showing wrinkled structure. Reprinted with
permission from ref. 155. Copyright 2013 Wiley.
(PA6) and PA66.140–144 By electrospinning AgNPs and mont-
morillonite clay tablets together (MMT), the Ag–MMT–PVA
composite nanofibres show good mechanical performance
and bactericidal effect (Fig. 14b).145
2.3.3.2 Graphene and graphene oxide. Due to its special
structure (consisting of a single layer of carbon atoms in a sheet),
graphene nanosheets (GNS) which has the strongest interlayer
force among all the materials, also has excellent thermal and
electrical conductivity, making it among the best candidates for
nanofillers.146 It has been demonstrated that, with the same
loading, the graphene-reinforced composites significantly
mechanically out-perform their counterparts with single-
walled/multi-walled carbon nanotubes as nanofillers. Thermal
stability can also be greatly improved as evidenced by the 30 1C
increase in glass transition temperature with only 0.05 wt% of
graphene in PMMA.147
Conjugated graphene or graphene oxide sheets can be readily
prepared by non-covalent p–p stacking or covalent coupling
reaction between C–C bonds. Different functionalizing organic
groups can be dissolved in different solvents and can complex
with graphene and form donor–acceptor composites, which can
adjust the conductivity, optical and optoelectronic properties.
It can be expected that based on the various excellent perfor-
mance of graphene and its derivatives, significant improvement
of the viscosity, electrical, mechanical and thermal properties
of graphene–polymer composites can be achieved. The feature of
graphene sheets provides maximum surface area of p–p
stacking with the polymer, thus it can be well dispersed in
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the polymer matrix. Carboxylic acid and hydroxyl functional
groups on the edge of graphene can also be used as cross-
linking agents and connect with the organic portion of the
polymer, thereby enhancing the mechanical properties.147,148
In addition to the traditional methods for preparing graphene–
polymer composites, graphene can be fixed to the polymer fibres
by the electrospinning technique, and various functional compo-
site fibres could be fabricated. The main polymers that have been
used are PVA, PAN, and PMMA. By changing the added amount of
graphene, the mechanical and electrical properties of the compo-
site fibre can be well adjusted.146,148,149 For example, when adding
4 wt% of graphene, the Young’s modulus of the PAN electrospun
fibres can be doubled. Similarly, the distribution state of graphene
in the fibres will have a significant impact on the mechanical
properties: when uniformly dispersed, the modulus of PVA
electrospun fibre can be increased 205%.150 It has been shown
that graphene can accelerate the photon movement within PVA
fibres, and thus increase their conductivity. A small loading
(0.07 wt%) of functionalized graphene enhanced the total
optical absorption of PVA by 10 times (Fig. 14c).151 In addition
to the mechanical and electrical aspects of applications, graphene–
PVA electrospun fibres can also be used as scaffolds in tissue
engineering aspects.152 Furthermore, when graphene was electro-
spun with another substance at the same time, such as chitosan,
besides improving the mechanical strength, the composite fibres
can also be used in biosensor applications.153
Graphite layers could be separated through intercalation and
exfoliation, and thin nanoplates can be formed. It has been
reported that by electrospinning graphite nanoplates with poly-
acrylonitrile, fibres with an average diameter of about 300 nm
could be fabricated. The composite nanofibres demonstrate a
modest increase in thermal stability with increasing wt% graphite
nanoplatelets, and the Young’s modulus doubled with only 4 wt%
incorporation of graphite nanoplates.146 Besides, by a combination
of electrospinning and thermal treatment, free standing CNF–GNS
composite paper is prepared and the paper exhibits a large specific
capacitance, about 24% higher than that of pure CNF paper.154
Continuous carbon fibres present an attractive building
block for a variety of multifunctional materials and devices.
However, the carbonization of PAN precursors usually results in
CNFs with weak graphic structures and thus modest properties.
The Dzenis group found that the graphitic structure of carbon
nanofibres can be improved with an addition of a small amount
of graphene oxide into PAN prior to processing, and continuous
CNFs with 1.4 wt% of graphene oxide NPs were prepared from
PAN solutions (Fig. 14d).155 After calcining the graphene–polymer
electrospun fibres, graphene–metal oxide composite fibres could
also be obtained. For example, Ramakrishna and co-workers
electrospun graphene and tetra-n-butyl in the polymer fibres,
and then prepared graphene–TiO2 composite fibres by calcina-
tion. Experiments confirmed that, compared to TiO2 fibres,
graphene–TiO2 composite fibres showed a better performance
of superior photovoltaic parameters in the dye cell, and can
photocatalyze methyl orange more rapidly.156 Furthermore, such
material can also be used as the anode electrode in lithium ion
batteries and dye-sensitized solar cells.157,158 If the polymer is not
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removed during the calcination process and is converted to
carbon, then graphene–C composites can be easily fabricated.
Other composite fibre materials, such as graphene–SiC,
graphene–Li4Ti5O12, graphene–C–TiO2, and graphene–MnO2
have been successfully prepared, and show excellent energy
conversion and storage performance in catalysis, batteries and
supercapacitors, etc.149,159–163
2.3.4 Other organic or biological NPs–electrospun fibres.
Controlled release of therapeutically active agent through
polymers is an established technique, and has been in clinical
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use. Electrospun fibres have important applications in drug release
and tissue engineering for their structural and morphological
similarly to the native ECM. Therefore, in this section, we will
focus on the electrospinning of organic molecules and biological
NPs to prepare functional composite fibres.
Packaging can accordingly improve the efficacy of drugs,
specificity, tolerability and therapeutic index. Understanding
the mechanism of controlled release is an important factor to
design effective release systems. Drugs can be uniformly dis-
persed in the polymer fibres, and also can be encapsulated in
the core. Much work has been done for controlled release of
drugs through electrospun fibres, and several relevant reviews
have also been published.164–168 In addition to controlling
drug release, various active cells have also been successfully
electrospun.169–175 When active bacteria are electrospun, a
requirement of the polymer is that it is water-soluble and with
good oxygen barrier properties after drying, such as PVP, PEO
and PVA. In 2004, Belcher and co-workers electrospun M13
virus within PVP fibres for the first time, and established virus
infection of bacterial hosts coming from the virus within the
electrospun membrane.176 Then in 2006, Zussman and co-workers
successfully prepared E. coli and Staphylococcus aureus-containing
PVA electrospun fibres, and experiments showed that the bacteria
in the fibres showed no loss of biological function.177 Because of
the formation process of electrospun fibres, the solvent (water)
evaporates quickly, and this will change the osmotic pressure of
bacteria and affect its activity. Therefore, Greiner and co-workers
dissolved water-soluble polymer in an aqueous solution containing
active bacteria (Micrococcus luteus that can still survive when
moisture content is very low, as well as relatively weak Gram-
negative E. coli) and subjected to electrospinning; composite
fibres were prepared and the survival of different bacteria
within the polymer were investigated.173 It was found that these
bio-composite materials could be used as ‘‘active membranes’’
in separation, catalysis and tissue engineering (Fig. 15a). In
addition, various proteins also could be electrospun within
polymer fibres and have important applications in biological
tissue engineering.172,175 The researchers found that it is con-
ducive to neuronal cells adsorbed on the fibres when the
protein-containing polymeric nanofibres were aligned.171
Biological enzymes are another kind of active substances, and
their immobilization has attractive sustained attention in fine
chemicals, bio-medicine and bio-sensing areas. The performance
of immobilized enzymes largely depends on the support struc-
ture, and nanocarriers are considered to be able to retain catalytic
activity and to ensure high efficiency of enzyme immobilization.
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Fig. 15 (a) SEM image of M. luteus–PEO composite fibres. Inset is the optical
fluorescence of the composite fibres under UV illumination. Reprinted with
permission from ref. 173. Copyright 2007 Wiley. (b) SEM image of the chitosan/
siRNA-Cy5NP-encapsulated PLGA fibres and inset is the fluorescence
microscopy image. Reprinted with permission from ref. 170. Copyright
2012 American Chemical Society. (c) Fluorescence microscopy image of
stretched DNA molecules embedded in PEO fibres that of two overlapping
‘‘ribbons’’ formed from 100 mg DABCO solution when the electrospinning
jet became unstable and spurted. Reprinted with permission from ref. 169.
Copyright 2006 American Chemical Society. (d) Living scaffold encapsulating
GFP expressing N2A cells generated by cell electrospinning. Reprinted with
permission from ref. 181. Copyright 2013 Wiley.
Electrospinning provides a simple and flexible way to produce
nanofibrous scaffolds. Compared with other nanostructure
supports (such as a porous silica, NPs), nanofibre scaffolds
show a number of advantages in terms of their high porosity
and interconnectivity. Based on this, numerous articles have
been published on the use of electrospinning to immobilize
enzymes, along with relevant reviews. Currently, the main
research focus in this area is the use of biological enzymes
for catalysis and sensing research.42,153
RNA interference (RNAi) is a promising method for inter-
rupting gene expression, and siRNA release through electro-
spun nanofibres has been demonstrated successfully using PCL
and PEG. Until 2012, the mechanism of release was fully inves-
tigated by Besenbacher and co-workers (Fig. 15b).170 Chitosan/
siRNA NPs were encapsulated in PLGA by electrospinning, and
the composite nanofibres were successfully prepared. Through
the study of acidic/alkaline hydrolysis and bulk/surface degrada-
tion mechanism the optimal release process can be ascertained
in order to achieve long-term and effective gene control.
Previous studies have proven electrospinning technology can
fix the DNA as well as part stretched large DNA (200–900 KBP)
within the interior of polymer fibres.178,179 In the first study,
DNA molecules that were much larger than single molecules
were directly fixed within the polymer fibres, while in the second
study, large single DNA molecules were deposited on the surface
of mica and then electrospun. Another study confirmed that
DNA molecules released from the electrospun film also
maintained structural integrity and biological activity.180
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Craighead and co-workers prepared polymer fibres containing
stretched isolated DNA molecules in 2006, and discovered for
the first time that the DNA molecule within a single electrospun
fibre was stretched and arranged along the fibre orientation
(Fig. 15c).169 Recently, Robertson et al. has demonstrated that
neither cell electrospinning (CE) nor aerodynamically assisted
biothreading (AABT) have any detectable effect on the in vitro or
in vivo growth of the cells (Fig. 15d).181
Conjugated polydiacetylene (PDA)-embedded electrospun mats
can be used to detect adulterated gasoline.182 Cyclodextrins are
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electrospun within the polymer fibres to filter the molecules.183
Another report found that spiropyran–cyclodextrin functionalized
fibres show photoresponsive behaviour.184 Effects of nanoclay on
the thermal, mechanical and crystallization behaviour of nanofibre
webs of Nylon-6 has also been investigated.185
3. Applications of NPs–electrospun
fibres
3.1 NPs–electrospun fibres for energy
With the development of industry, new energy sources is one of
the most important issues that need to be solved, and many
scientists are seeking for appropriate strategies or materials to
solve this problem. Nowadays, miniaturization, multifunction-
ally, flexibility and low energy consumption have become the
development trend of electronic devices. In earlier reports,
electrospun nanofibres have been used to prepare electrodes
either by milling the nanofibre meshes and mixing them sub-
sequently with carbon black and binder to form the electrode,
or they were directly used as self-supporting electrodes without
any additives.
3.1.1 Supercapacitors. Supercapacitors have been intensively
investigated as one of the main energy storage systems because
they can carry high power density and have long life-cycles, rapid
charging–discharging capacity and potential applications in many
fields, such as mobile devices and electric vehicles. Many carbon
nanostructures have been proven to be supercapacitor electrode
materials. Among them, 1D carbon nanotubes have attracted
substantial attention, because they have large accessible surface
area and relatively high electrical conductivity, which make them
likely to become the dominant electrode material of high-power
supercapacitors.186 Currently, the problems for using carbon
nanotubes as the electrode material are their low effective surface
area, the limited charge capacity and higher costs compared with
other materials. These all limit CNTs being used as an electrode
material of supercapacitors.186,187 Alternatively, carbon fibres can
be prepared by the combination of electrospinning and calcina-
tion, which are mainly used as a capacitor electrode material, by
controlling the pore size of the fibre and loading metal NPs
on/within the fibres in order to increase the standard capacitance.
Carbon nanofibres prepared by electrospinning have been widely
studied, because of their free-standing nature, high mat porosity
and low fibre diameter. Carbonized electrospun fibres are
expected to be an excellent alternative material for making
electrodes.188 A further report found similar results.189
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The electrospun fibres based on polymer (such as PAN, PI,
etc.) substrate can be used as electrodes of electric double layer
capacitors prepared after stabilization, carbonization and activa-
tion at high temperature. With the development of capacitors,
it has been found that the specific surface area and pore-size
distribution of the carbon fibres are the major factors which
influence the electric performance. For example, after activation
under different temperatures (70% N2/30% water steam), the
PAN-based electrospun fibres transform into carbon fibres, and
the capacitance of fibres activated under 700 1C is 173 F g1
under low current density (10 mA g1), while the capacitance of
fibres activated under 800 1C is 120 F g1 under high current
density (1000 mA g1): the specific surface area of the former is
1230 m2 g1 and of the latter is 850 m2 g1.187
The importance of pores presented within the carbon fibres
on their electronic properties also has been investigated.
Various additives, such as cellulose acetate and polymers that
can be removed, have been electrospun within the fibres. After
the activation process, pores would form within the carbon
fibres and thus the specific surface area increased. Moreover,
inorganic metal salts could influence the pore structure within
the formed carbon fibres. For example, Yang and co-workers
prepared self-sustained thin webs consisting of porous carbon
fibres via electrospinning of PAN solutions containing ZnCl2,
that can be removed by HCl and a porous structure can be
formed without any activation process. Carbon nanofibres with
5 wt% ZnCl2 exhibited the highest surface area, the highest
capacitance, and good rate capability because of their high
surface area and smaller fibre diameters.189 Liu and co-workers
used KOH to tune the fibre diameter and to improve porous
texture. By adjusting KOH content in the spinning solution, the
fibre diameter, the microporous volume and specific surface
areas could be greatly improved.190
In order to increase the pseudo-capacitance in the double-
layer capacitor, many kinds of NPs, such as CNTs and metal
oxides, have been electrospun within carbon fibres. For example,
hybrid carbon nanofibres containing multiwalled carbon
nanotubes (MWCNTs) were produced by electrospinning CNTs
suspended in a PAN–DMF solution, followed by carbonization
and activation using a H2O2–water steam mixture at 650 1C. The
specific capacitance of electric double-layer capacitors reached
310 F g1, which was almost double that obtained for capacitors
containing pristine carbon fibres as electrodes (170 F g1).191
Moreover, flexible films derived from electrospun carbon nano-
fibres incorporated with Co3O4 hollow NPs as self-supported
electrodes for electrochemical capacitors were prepared. Benefiting
from intriguing structural features, the unique binder-free hybrid
film electrodes exhibited high specific capacitance of 556 F g1
with loading of 35.9 wt% Co3O4 at a current density of 1 A g1.
Remarkably, almost no decay in specific capacitance was found
after continuous charge–discharge cycling for 2000 cycles at
4 A g1. Co3O4 hollow NPs/CNF shows excellent rate capability
and cycling stability (Fig. 16).192
3.1.2 Lithium-ion batteries. For the past few decades lithium-
ion batteries have been regarded as one of the most useful energy
sources for mobile electric devices and hybrid vesicles because of
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Fig. 16 (a–c) CV curves of Co3O4/CNFs film electrodes with different
amounts of Co3O4 in 6 M KOH aqueous solution. (d) Specific capacitance
of Co3O4–CNFs film electrodes in (a) as a function of current density.
(e) Cycling performance and coulombic efficiency of the Co3O4–CNFs3
film electrode at a current density of 4 A g1. Reprinted with permission
from ref. 192. Copyright 2013 Wiley.
their high energy density and long cycle lifetime. To serve as
cathodes or anodes for lithium ion batteries, nanostructured
active materials should have a short Li-ion insertion/extraction
distance, facile strain relaxation upon electrochemical cycling,
and very large surface-to-volume area to contact with the
electrolyte, which can improve the capacity and cycle life of
lithium ion batteries. However, nanomaterials tend to aggregate,
owing to their high surface energy and reduce the effective contact
areas of active materials, electrolyte and conductive additives. The
hierarchical structures of materials, such as hollow, porous,
and nanowire-on-nanowire can ensure that the surface remains
uncovered to keep the effective contact areas large even if a
small amount of self-aggregation occurs. Moreover, when ID
nanomaterial are up to several hundred micrometers or even
several millimeter scale, such as for ultralong NWs or nano-
belts, self-aggregation of the nanomaterials could be effectively
prevented. Therefore, ultralong hierarchical nanowires are one
of the most favourable structures as cathode/anode materials
for high performance.
Among the variously of nanomaterials used for battery
electrodes, the phosphoolivines with the chemical formula
LiMPO4 (M = Fe, Co, Ni, Mn) have attracted great interest due
to their high cell voltage, cycling stability and capacity. In the
case of Mn and Fe, the materials are non-toxic and can be
produced in large volumes at low cost, which make them highly
attractive for industrial applications. However, their intrinsic
electrical conductivity is poor, which makes a coating with
conductive matrices (e.g., carbon) necessary. The olivine-structured
LiFePO4 has high theoretical capacity (170 mA h g1) and acceptable
operating voltage (3.4 V vs. Li+/Li). LiFePO4 NWs offer a better
percolation behavior than NPs, but to date there are only a few
reports on the synthesis of LiFePO4 NWs, and electrospinning
has been confirmed as one powerful method to synthesize
the NWs. Hosono and co-workers synthesized carbon-coated
LiFePO4 NWs as well as triaxial NWs with a carbon nanotube
and a carbon shell. However, the large diameter of LiFePO4
NWs (4500 nm) constrains their performance.193 Thinner NWs
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Fig. 17 (a) Schematic diagram for the preparation of single-crystalline
LiFePO4 NWs by electrospinning. (b) SEM image of as-prepared LiFePO4
NWs. (c) Cyclic voltammetry of LiFePO4 NWs with a scan rate of 0.1 mV s1.
(d) Cycling stability of LiFePO4 NWs at 1 C rate at 25 1C and 60 1C,
respectively. Reprinted with permission from ref. 76. Copyright 2011 Wiley.
are needed for the applications in lithium batteries. Maier and
co-workers using LiH2PO4, Fe(NO3)3 and PEO in the electro-
spinning process, fabricated single-crystalline carbon-coated
LiFePO4 NWs with diameter of 100 nm, which showed very
good rate performance and cycling capability (Fig. 17).76 The
addition of Mn to form LiFe1yMnyPO4 solid-solutions increases
the cell voltage and thereby the energy density of the cell. There
have been many efforts to improve the more ionic members
of this family, and electrospinning represents a promising
approach to prepare LiFe1yMnyPO4 nanofibres with control
over their nanostructure and allowing in situ incorporation of
carbon into the structure. For example, Mathur and co-workers
fabricated LiFe1yMnyPO4–C nanofibre composites by electro-
spinning of commercially available precursors, and the nano-
fibres were then calcined at 850 1C under Ar/H2 atmosphere.194
The fibres are directly used as self-supporting electrodes with-
out any conductive additive or polymer binder.
3.1.3 Dye-sensitized solar cells. Dye-sensitized solar cells
(DSSCs) are promising low-cost, high-efficiency photovoltaic
devices for solar energy conversion. However, nanoparticle-based
devices result in a lower efficiency because electron transport is
limited by a trap-limited diffusion process, and the slow charge
diffusion increases the probability of recombination. Moreover,
the grain boundaries encountered during electron transport
lead to fast recombination prior to their collection at the
electrode. To solve the above problem, one strategy is by using
1D nanostructures to replace the NPs, which provides direct
pathways for collection of charges generated throughout the
device. It has been confirmed that electron transport in 1D
nanostructures is several orders of magnitude faster than that
of NPs. Another approach is to incorporate highly electrically
conductive materials in photoanodes, such as carbon tubes and
graphene. The presence of conductive materials in a photo-
anode is expected to improve the charge transport properties
and extend the electron lifetime, thereby improving the per-
formance of the device. For example, Leung and co-workers
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Fig. 18 Electron transport across a photoanode of CNTs totally surrounded/
embraced by (a) TiO2 NPs, (b) NRs and (c) CNTs inside TiO2 NRs. The
thickness of the arrow represents the electron transport speed, the thicker
arrow representing faster electron transport. (d) J–V characteristics of
different photoanodes, (e) the effect of MWCNT concentration in the
precursor solution on Jsc and fill factor (FF). Both in (d) and (e): hollow
and solid symbol curves represent thinner (6.6  0.7 mm) and thicker
(14.3  0.3 mm) photoanodes, respectively. Reprinted with permission from
ref. 137. Copyright 2013 Wiley.
introduced MWCNTs within TiO2 NRs via electrospinning.137
This configuration was successfully applied in a photoanode to
improve the performance of a DSSC device. When 0.1%
MWCNTs was incorporated, the DSSC device exhibited the
highest efficiency of 10.24%, with a high Jsc of 18.53 mA cm2
and a fill factor (FF) of 74% (Fig. 18). These positive results
confirm that incorporate CNTs in the electrospun NTs provides
an effective strategy to improve the charge transport perfor-
mance for realizing solar energy conversion in the future.
3.1.4 Catalysis. The use of electrospun fibres/mats for
catalysts is also an upcoming field of interest. The surface area
is the dominant factor that decides the extent of catalysis and
its efficiency, and catalyst material having fibrous morphology
is superior to particles as far as the recycling and aggregation
are concerned. Fibres with hollow, porous or multichannel
structures have been readily fabricated by electrospinning as
previously discussed (Fig. 3), which further improve the specific
area of the fibres, and thus their catalytic performance.
Ceramic nanofibres have been widely used in photocatalysis
for the degradation of organic pollutants with high activities,
durability and low cost.195,196 Among various oxide and non-
oxide photocatalysts, titania has proven to be the most versatile
material because of its high catalytic activity and long-term
stability.197 The electrospinning of concentrated TiO2 nano-
particle dispersions in PVA matrices followed by calcination
allowed the fabrication of nanofibres with narrow poly-
dispersity, displaying tunable mesopores volumes and diameters.
This approach is more flexible than the electrospinning of sol–gel
precursors and therefore it is relevant for the production of
easy-to-handle and versatile catalytic substrates.198 Besides,
TiO2 hollow fibres with mesoporous walls or rice grain-shaped
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mesostructures were fabricated using electrospinning combined
sol–gel method, and exhibited enhanced photocatalytic activities
compared to commercial TiO2 NPs (P25) and mesoporous TiO2
powers.199–201 Furthermore, the photocatalytic activity of multi-
channel TiO2 hollow fibres achieved by multifluidic electro-
spinning method have also been investigated. A quite interesting
phenomenon is that the percentage increase for photocatalytic
activity is higher than that for surface area. The authors proposed
that multichannel hollow structures offered a cooperative effect of
trapping more gaseous molecules inside the channels and multi-
ple reflection of incident light, which further improved the photo-
catalytic activity of TiO2 hollow fibres.202
Because of the fast recombination rate of photogenerated
electron–hole pairs in the bulk ceramic materials lowers their
photocatalytic efficiency, composite materials are being fabri-
cated in order to extend the light absorption spectrum as well
as suppressing the recombination of photogenerated electrons.
The metal–metal oxide composite materials will serve as a
better catalyst, with the ceramic as the substrate material and
the metal acting as the reactive sites. For example, Xia’s group
coated the surfaces of TiO2 fibres with Pt NPs 2–5 nm in size
using a simple chemical reduction process. The Pt NPs could
also serve as seeds for growing Pt NWs. The composite fibre
membranes exhibited excellent catalytic activity for the hydro-
genation of azo bonds in methyl red, which could be prepared
in a continuous mode by passing the solution through the
membrane at a flow rate of 0.5 mL s1.203 Similarly, the
surfaces of TiO2 and ZrO2 nanofibres could also be function-
alized with Pt, Pd, and Rh NPs via the similar method, and the
composites could be used to catalyse the Suzuki coupling
reactions and be operated in a continuous flow fashion.204
Other fibre heterostructures achieved by electrospinning
technique with high photocatalytic activity, such as SrTiO3/
TiO2,205 Ag/TiO2,206 Ag/SiO2,207 ZnO/BaTiO3,208 and rare-earth
doped TiO2,209 have also been reported.
Besides using for the degradation of organic pollutants, the
composite fibres also exhibit high catalytic performance for the
reduction of 4-nitrophenol (4-NP) with NaBH4,210 preferential
CO oxidation (CO-PROX),211 and oxygen reduction reaction
(ORR).212 The Shao group fabricated several nanocomposite
catalysts for 4-NP by combining electrospinning and an in situ
reduction approach.213–216 For example, tubular nanocompo-
site catalysts with size-controlled and highly dispersed AgNPs
assembled on the inner and outer surfaces of SiO2 NTs were
successfully fabricated and the composites exhibited excellent
catalytic performance for the reduction of 4-NP. Besides their
high specific surface area, the authors believed that the size
effect of AgNPs played a leading role in enhancing the catalytic
activity. Furthermore, the nanocomposite catalysts could be
easily recycled without a decrease of the catalytic activity
because of their 1D nanostructure property.217 Pt–CeO2 com-
posite oxide catalysts are promising candidates for the CO-
PROX owing to the strong metal–support interaction effects
with potential to enhance the catalytic activities. However, they
show low thermal stability and loss of catalytic activity owing to
sintering. Recently, CeO2 hollow fibres with PtNPs embedded
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in the inner surfaces were fabricated by the Xia group via using
PS electrospun fibres as the template. This catalytic system
could resist thermal sintering up to 700 1C and the turnover
frequency (TOF) for CO oxidation was 2–3 orders of magnitude
higher than those based on the conventional Pt–SiO2 system,
which was the result of a unique structure and composition for
maximizing the Pt/CeO2 interface.218 For proton exchange
membrane fuel cells, the short life and high cost are two main
problems of carbon-supported Pt nanoparticle catalysts (Pt/C).
Porous Pt alloy NWs fabricated by dealloying have more dur-
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ability and catalytic activity than Pt/C, but the process of
porosity formation is difficult to control. Shui and co-workers
fabricated long, thin and yet nano-porous Pt–Fe alloy NWs via
electrospinning and chemical dealloying techniques.219 It was
found that non-uniform composition in the precursor PtFe5
alloy NWs benefited the formation of a nanoporous structure.
The overall wire diameter is about 10–20 nm and the ligament
diameter only 2–3 nm. These porous long nanowires interweave
to form a self-supporting network with a high specific activity,
2.3 times that of conventional Pt/C catalysts, and also have
better durability.
3.2 NPs–electrospun fibres for mechanical enhancement
The research on mechanical enhancement of composite nano-
fibre/membrane prepared by electrospinning can be divided
into two types: one is to reinforce the composite nanofibre itself,
and the other is to reinforce the other substrate material, i.e.,
fibre reinforced composite material. The mechanical properties
of composites mainly depend on the nanofibres’ composition,
size, fibre orientation, molecular structure, the arrangement of
fibres and some post-processing conditions, such as calcination
temperature and time.
Engineering plastic itself can lead to good mechanical
properties; the electrospun nanofibres tend to have better
mechanical properties, because the fibres are formed through
the formation of self-organized control in the electrospinning
process. It is well known that decreasing the diameter of fibres
can increase their strength though often at expense of their
toughness. Recently, it has been reported that both the strength
and toughness of PAN electrospun fibres were increased.220 When
the diameter of the fibres was less than 250 nm, the fibres became
tougher, but did not lose their strength. The fabricated fibres were
up to 10-times tougher and stronger than the best commercial
fibres. The authors suggested that the toughness was possible as
the less crystalline of the nanofibres than the coarse ones.
Moreover, adding nano-additives into the fibres could further
improve their mechanical properties. For example, by electrospin-
ning the solution of CNTs and polymers, such as PAN, PU, PS, PLA,
poly(m-phenylene isophthalamide) (PMIA), etc., the mechanical
property of composite fibres could be greatly enhanced.13,221–223
Highly aligned MWCNT–PMIA composite fibres were prepared
with robust mechanical strength, and the mats with a MWCNT
content of 1.5 wt% exhibited the highest tensile strength of
316.7 MPa (Fig. 19a and b).221 In addition, the polymer could
be transferred into carbon after calcination, which could
further enhance the mechanical performance of the fibres.
Chem. Soc. Rev.
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Chem Soc Rev
Fig. 19 (a) Stress–strain curves of MWCNT/PMIA nanofibres with CNT
contents of 0, 0.5, 1 and 1.5 wt%. (b) Photographs showing the as-prepared
nanofibrous membrane (MWCNT content was 1.5 wt%) supporting a
weight of 5 kg, the membrane has 20 mm width and 1.8 mm thickness.
Reproduced from ref. 221. (c) Schematic illustration of the fabrication
process. (d) Digital image of the as-obtained composite bulks with differ-
ent NW contents. (e, f) TEM images of ultrathin sections of the planes as
indicated in (d). (g) Three-point bending strength and corresponding
modulus of the composite bulks. The error bars represent the standard
deviation of the mean. (h) Typical stress–strain curves of composite bulks
with different nanowire contents in three-point bending tests. Reproduced
from ref. 131.
Carbon materials with 2D structure, such as graphene, also could
enhance the mechanical properties.146,148,224 Besides carbon
materials, different drugs could be incorporated within the fibres
by emulsion electrospinning, and the mechanical properties of
the single electrospun fibre could be affected. When 10–20 wt%
retinoic acid was encapsulated, the fibre’s mechanical strength
was enhanced, while the fibre’s strength decreased if 10–20 wt%
bovine serum albumins was encapsulated. Alignment of nano-
fibres will greatly increase their hardness to the orientation
direction and improve the anisotropy of the stent. This is an
important analog function similar to anisotropic materials, such
as tendons, fibrous rings and myocardial tissue. Various silicates,
such as hydroxyapatite, tubular clay, montmorillonite, etc., can
improve the mechanical properties of fibres.138,142,143,225
Combining nanofillers and polymers leads to substantial
improvements in the mechanical, thermal, antifouling and electric
properties of polymer nanocomposites. Many researches in industry
and academia use microfibres as filler material, thereby creating
a microcomposite. Comparing with a microfibre, nanofibres are
several orders of magnitude lower in size, thus making them
ideal as nanofillers because of their availability of very high
surface area for interfacial interaction. The mechanical properties
of fibre-reinforced composite materials are mainly controlled by
the mechanical properties and the aspect ratio of the fibre itself,
and the mechanical coupling between the fibre and matrix. In
composite applications, if there is a refractive index difference
between matrix and fibre, the resulting composite becomes
opaque or non-transparent due to light scattering. One possible
way of circumventing this limitation would be to use fibres with a
diameter significantly smaller than the wavelength of visible
light. Owing to their small diameter, nanofibres cause only
negligible refraction of light so that a nanofibre-reinforced
transparent matrix can maintain the transparency even when
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Chem Soc Rev Review Article

the refractive index of the fibre and matrix do not match.
Finally, a large surface area between the nanofibres and matrix
increases the relaxation process, thereby improving the impact
strength of the reinforcing matrix. Chang and co-workers first
electrospun calcium silicate hydrate within the polymer, and
aligned the composite fibres to a certain orientation through
the collection device, finally obtaining bulk composites after
hot-pressing,131 as shown in Fig. 19c–h. It was found that with
calcium silicate hydrate at 20 wt%, the bending strength of the
composite material reached up to 188 MPa, which was much
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concentration in important biological processes. Using electro-
spun nanofibrous membranes as highly responsive fluores-
cence quenching-based optical sensors for metal ions (Fe3+
and Hg2+) and 2,4-dinitrotoluene (DNT) for the first time is
reported by Sarnuelson and co-workers.233 Poly(acrylic acid)-
poly(pyrene methanol) (PAA-PM), a fluorescent polymer, was
used as a sensing material.
Another type of chemical sensors, optical sensors, were
fabricated by electrospinning PAA-PM and thermally cross-
linkable polyurethane latex mixture solutions, which showed

higher than the pure polymer (86 MPa).131 Li and co-workers
prepared a PDMS hybrid silica aerogel (xerogel) thin film
reinforced by continuous electrospun nanofibres for the first
time.226 The nanofibre reinforcement was accomplished through
the electrospinning of nanofibres into the sol whose gelation
kinetics were delayed so that the nanofibres could easily pene-
trate the cast wet sol film while it still exhibited low viscosity. The
controlled gelation kinetics of the sol ensured that nanofibres
are embedded in the gel film or at least anchored to it, creating
continuous nanofibre reinforcement to improve the mecha-
nical performance. Other electrospun fibres composed of poly-
mer or inorganic/polymer, such as PVA, Nylon-4,6, PDMS/PEO,
PMMA/PDMS, CNTs/PU and MWCNTs/poly(styrene-co-glycidyl-
methacrylate) (P(St-co-GMA)), also have been used to reinforce
the epoxy or silicon matrix.226–231
high sensitivities compared to traditional sensors due to the high
surface area-to-volume ratio of the nanofibrous membrane, which
is in favor of the target molecules transferring to the active point of
the fibres. Tian et al. fabricated low-cost fully transparent ultra-
violet photodetectors based on electrospun ZnO–SnO2 hetero-
junction nanofibres (Fig. 20).71 The photodetector showed excellent
operating characteristics: high UV-sensitivity and photo-dark current
ratio, and fast response speed when used as a visible-blind UV-light
sensor within an optoelectronic circuit.
Among the chemical sensors, humidity nanosensors are very
important for their practical applications in environment moni-
toring, our daily life and industrial process. Many humidity nano-
sensors have been successfully fabricated. However, the sensing

3.3 NPs–electrospun fibres for sensors

Design and fabrication of chemical sensors has become one of
the most active research fields due to their diverse practical and
potential applications. To improve the sensing characteristics,
nanoscale sensors have been widely investigated for their large
surface areas. In particular, nanosensors based on 1D materials
are of great interest because of their high surface to volume
ratio and special physical and chemical properties. Here,
several kinds of sensors are briefly introduced.
Solid-state real-time chemical sensors are important for
biomedical research and medicine. Traditionally, the target
molecules are dissolved in a liquid for detection, and then
react with the target or the cell that release the chemicals, then
the colour or fluorescence changes. On the other hand a solid-
state sensor is non-invasive and it transforms the real-time
chemical concentration into electronic signals without inter-
ference with the biological processes under study. Zinc ion play
key roles in normal physiology and is the second most abun-
dant transition metal ion in the human body after iron.
In order to study the dynamics of biological processes such
as a stroke, it is important to detect the zinc ion concentration
Fig. 20 (a) Spectroscopic photoresponse of the ZnO–SnO2 heterojunction
every few minutes, while the real-time detection is impossible
nanofibres measured at a bias of 5.0 V at different wavelengths ranging from
for traditional molecular probes dissolved in solution. Recently, 250 to 630 nm. The inset is the optical absorption spectrum. (b) I–V spectra
Wang and co-workers dispersed a probe molecule for Zn2+ in of the device illuminated with a light of different wavelengths, and under dark
polymer host by electrospinning, with the fibrous film detect- conditions. (c) Logarithmic plot of (b). (d) Photocurrent as a function of light
ing zinc ions with a concentration as low as 106 M with time- intensity and corresponding fitting curve using the power rule under 300 nm
light illumination. (e) I–V curves of the device under 300 nm wavelength light
resolution of 5 min and showing high stability as well as
illumination measured under air and vacuum conditions. Inset is I–V curves
unchanged sensing function in highly acidic conditions.232 under dark. (f) Time-dependent response of the device measured under air
The sensitivity and response speed make it possible for a conditions at a bias of 9.0 V under 300 nm light illumination. Reprinted with
non-invasive and real-time study for the variation of zinc ion permission from ref. 71. Copyright 2013 Wiley.

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Review Article
characteristics, such as their responsiveness, reproducibility
and stability, still need to be improved. A highly sensitive and
stable humidity nanosensor based on LiCl-doped TiO2 nano-
fibres through electrospinning and calcination has been
reported.234 The sensor exhibited ultrafast responsive and
recovery behavior, which are important in humidity detection
and control. It also provides a useful platform to design and
construct effective humidity nanodetectors. Additionally, KCl-
doped TiO2 nanofibres also show similar results.235 Further,
Lei’s group reported the fabrication of a novel fluorescent
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nanofibrous membrane via electrospinning for the direct
naked eye vapor detection of ultra-trace nitro explosive and
buried explosives under UV excitation, and this is a new report
about the detection of buried explosives without the use of any
advanced analytical instrumentation.236
Strain sensors with ultrahigh flexibility and stretchability
have great potential applications in personal health monitoring,
human-benign devices, and highly sensitive robot sensors, etc. A
novel strain sensor prototype based on ZnO NW–PS NF hybrid
structure coated on a poly(dimethylsiloxane) (PDMS) film has
been demonstrated.56 The device can withstand strain up to 50%,
with high durability and high gauge factors. The device also
demonstrated a good performance on small and rapid human
Fig. 21 Electromechanical behaviors of the strain sensor. (a) The I–V
curves of the device under different strain. (b) The relative change in
resistance of the device in (a). The inset of (a) is the schematic illustration of
the strain sensor. (c, d) Current response of the strain sensor device at
different static strain state under a fixed bias of 10 V. (e) The current–time
response curve of the strain sensor device that was fixed on a finger at four
different bending and release motions under a fixed bias of 10 V. The upper
insets I, II, III and IV display the four different finger motion states.
Reprinted with permission from ref. 56. Copyright 2011 Wiley.
Chem. Soc. Rev.
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Chem Soc Rev
motion measurements (Fig. 21). With flexibility and stretchability,
the device will have potential applications in nanosensor systems
for precision measurements, human skin, and personal health
monitoring. Moreover, the device can be driven by solar cells and
has potential applications as an outdoor sensor system.
The composite nanofibres also could be used as biosensors,
which are defined as devices that can transform biological signals
into electric output signals and have a biological recognition
mechanism. A variety of enzymes can be encapsulated within
fibres via electrospinning, and the high surface-to-volume area
favors the enhancement of adsorption rate and reduction of the
response time. The Wei group electrospun horseradish peroxide
enzymes within porous silicon nanofibres. The high surface area
and freedom of encapsulating various enzymes make porous
silica nanofibres excellent biosensors.237 Zhao and co-workers
demonstrated a new CTC-capture platform that combined a high-
affinity cell enrichment assay based on electrospun nanofibres-
deposited substrate coated with cell-capture agent. This substrate
may have potential applications in isolating rare populations of
cells that can not be easily realized using current technologies.238
Other NPs, such as Au and graphene, also could be used for
biosensors.42,239
4. Concluding remarks
In summary, recent advances have clearly demonstrated that
the electrospinning technique affords us a remarkably simple
and versatile method for the preparation of NPs–electrospun
fibres with different functionalities. The composite fibres fab-
ricated by a post-treatment of the as-prepared electrospun
fibres or directly adding NPs into electrospun solution exhibit
many superior properties. In particular, the applications in
energy, sensor and mechanical enhancement have been high-
lighted in this review.
The direct fabrication of composite fibres by electrospinning
is facile and versatile, however, there are still several challenges
in this field. For example, a large amount of NPs is needed to
make them encapsulated within each fibre, while only some
NPs can be synthesized on a large scale so far. Besides, as the
NPs are encapsulated within polymer fibres, the NPs can be
more stable, however, this also limits their applications, for
example, for catalysis or sensing. Some rational methods are
still needed to remove the outer shell and yet not disturb the
assembled state at the same time.
Besides, recently emerging primary research works on the
self-assembling effect of electrospinning on the ordering of NPs
has appeared, which is of high value. So far, although the
nanomaterials have superior properties to those of their bulk
counterparts, it still remains a challenge in assembling these
individual nanocomponents into macroscopic materials on a large
scale and retain the stability of the assemblies. Electrospinning fits
well with the above conditions and has several advantages, i.e., the
NPs can be readily assembled on a large scale and a free-standing
film with high stability could be obtained. Until now, in nearly all
reports, only one kind of 1D nanomaterial has been electrospun
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Chem Soc Rev
within the same fibre to investigate the assembly effect of
electrospinning. Further work is needed to study the affect on
the performance of the composite fibres when more than one
kind of NPs are assembled via electrospinning, because a
synergistic effect may occur among the NPs and also the matrix,
and new or enhanced performance could be realized. Moreover,
only some 1D NPs have been electrospun so far, and the scope
needs to be extended further, and thus more functional or
multifunctional nanocomposite materials are expected to be
produced.
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In addition to enhancing and improving the device perfor-
mance by controlling their morphology and composition, the
state of the NPs (randomly or aligned) in the device should also
be considered. Especially for energy and sensor applications,
assembling of NPs may be conductive to the electron transport.
For mechanical enhancement, further work needs to be done to
create the interactions between NPs and matrix (as ‘‘binder’’).
For example, organic molecules could be used to functionalize
the NPs and act as a ‘‘bridge’’ to enhance the force between NPs
and the matrix. Moreover, further textiling the fibres into
bundles may increase the mechanical strength of composites.
Although many technical issues still need to be resolved or
improved upon, there is no doubt that electrospinning utilizing
NPs can become one of the most powerful tools for fabricating
functional 1D nanomaterials and composite materials with
ideal compositions and structures. Combining and assembling
NPs with fibres via the electrospinning technique will introduce
a new field on fabrication of diverse multifunctional materials
in the future.
Acknowledgements
This work is supported by the National Basic Research Program
of China (Grants 2010CB934700, 2013CB933900, 2014CB931800,
2012BAD32B05-4), the National Natural Science Foundation of
China (Grants 91022032, 91227103, 21061160492, J1030412), the
Chinese Academy of Sciences (Grant KJZD-EW-M01-1), the Funda-
mental Research Funds for the Central Universities, and the
China Postdoctoral Science Foundation.
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