Materials Today  Volume 19, Number 3  April 2016

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RESEARCH: Review

Stimuli-deformable graphene materials:

from nanosheet to macroscopic assembly
Fei Zhao, Yang Zhao, Nan Chen and Liangti Qu*
Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Key Laboratory of Cluster Science, Ministry of Education, School of Chemistry,
Beijing Institute of Technology, Beijing 100081, PR China

Stimulus-induced deformation (SID) of graphene-based materials has triggered rapidly increasing

research interest due to the spontaneous response to external stimulations, which enables precise
configurational regulation of single graphene nanosheets (GNSs) through control over the
environmental conditions. While the micro-strain of GNS is barely visible, the deformation of graphenebased macroscopic assemblies (GMAs) is remarkable, thereby presenting significant potential for future
application in smart devices. This review presents the current progress of SID of graphene in the manner
of nanosheets and macroscopic assemblies in both the experimental and theoretical fronts, and
summarizes recent advancements of SID of graphene for applications in smart systems.
Introduction
Considerable interest has been paid to Graphene [1] due to its
potential in a variety of research areas, such as structural materials
[27], electronics [812], and energy storage [1320]. Graphene has a
carrier mobility of up to 200,000 cm2 V 1 s 1, a thermal conductivity of 30005000 W m 1 K 1 at room temperature [1,21], a high
surface area of 2630 m 2 g 1 [22], good optical transparency of
97.3% [23] and excellent mechanical strength with a Youngs
modulus of 1.0 TPa [24] by its two-dimensional (2D) single-atom
layer conjugate structure. However, the chemical activity and dispersibility of single layered graphene nanosheets (GNSs) are limited
by their unreactable and tightly stacked honeycomb conjugate
structure, hindering further applications of graphene. In this context, the functionalization of graphene is a promising strategy for
the large scale preparation of graphene derivatives, which presents
unexpected properties and partially maintains the performance of
pristine graphene at the expense of producing structural defects.
Various functionalization methods, including chemical modification, physical mixture and self-assembly have been developed in the
past few years to promote intensive study of graphene derivatives
[2529]. As a consequence, a series of novel graphene-based smart
materials, which provide advanced functions beyond the intrinsic
properties of graphene, were presented [3040].
*Corresponding author. Qu, L. (lqu@bit.edu.cn)

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Smart materials refer to those lifeless materials that assimilate

animated functions such as sensing, deformation, coloring and
self-healing to adaptively react to changes in the environment in a
constructive and mostly repeatable way. Among them, the stimulus-induced deformation (SID) enabled materials that shrink,
swell, bend or swing in response to external stimuli have attracted
enormous attention owing to their potential for use in intelligent
robots, biomedical devices and electro-mechanical systems
[41,42]. Currently, deformable materials can be constructed from
polymer and/or nano-materials which are able to spontaneously
vary their conformation with environmental changes such as pH,
temperature, electrical, light and other stimuli [4353]. The microcosmic change of morphology induced by conformation variation was amplified in their macroscopic assemblies, hence
causing remarkable deformations. In view of the excellent electrical, thermal and mechanical properties mentioned above, graphene-based environmentally responsive materials have
emerged as promising candidates for next generation smart deformable materials with special functions (e.g. conductivity or
chemical stability) in comparison to other stimuli deformable
materials based on polymers or metals, and have become a fastgrowing research field.
Benefiting from the mass production of the building blocks
based on GNSs, the fabrication of graphene-based macroscopic
assemblies (GMAs) with functional micro- and/or nano-structures

1369-7021/ 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). http://dx.doi.org/10.1016/
j.mattod.2015.10.010

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hydrogen bonding and electrostatic forces, which have been used

for the assembly of GO to generate a microcapsule capable of
releasing the drug molecule [62]. It suggests that the oxygencontaining groups provide an adjustable surface state for the
regulation of inner- and inter-sheet interactions. Moreover, as
molecular-weight dependent weak interactions, Van der Waals
forces become significant in the GNSs, and hence the surface
adhesion effect allows the GNSs to conform to other surfaces, which
is useful for manipulating their deformation [63]. The interplay
mentioned above is affected by the environmental conditions of
GNSs, leading to a variety of deformation behavior. Additionally,
the deformation induced inner-sheet stress could act as a restoring
force, tending to bring the GNSs back to initial planar configuration.
Therefore, GNSs will maintain a folded conformation when the
attractive force is stronger than the restoring force, and return back
to planar configuration once the force balance reversed.
FIGURE 1

Schematic illustration of strategies toward stimuli-deformable graphene

materials from nanosheet to macroscopic assembly.

became possible. Characteristic of the building blocks and assembling method, GMAs exhibit enhanced chemical, electrical and
mechanical properties together with many new functions such as
ionic adsorption, electrochemical catalysis and stimuli response
[5457]. Therefore, the development of functionalized architectures derived from GNS-based building blocks is indeed of considerable interest, and research toward GMA enabled smart
deformable materials has been a central focus for materials scientists in recent years.
To date, a number of synthetic methods have been presented to
prepare GMA with novel functions, which have previously been
summarized by comprehensive reviews [5861]. However, a targeted overview on GMA based smart deformable materials is still
absent. Thereby, in this review, we will summarize recent advancements on the fabrication of graphene-based SID systems contributed by us and other groups, mainly focusing on the
environmentally responsive graphene nano-materials and their
SID enabled assemblies as shown in Fig. 1. Since the GNSs are able
to act as an actuating component and passive platform, the actuation-mode-dependent SID behaviors of GMAs are also discussed.

SID mechanism of GNSs

The SID of GNSs, including planar expansion and spatial warping
through a fold event of graphene, depends on the stretch and
rotation of carboncarbon bonds, which are predominated by the
surface chemical state. For instance, on a defect-free surface of
GNS, the remarkable pp interactions between the polycyclic
aromatic hydrocarbon structures enabled graphite-derived or graphene lattice-derived aggregations. While there are many possible
routes toward the regulation of the surface chemical state of GNSs,
the current widely accepted strategy is the modified Hummers
method [25], which can oxidize graphite to graphite oxide
nanosheet, where the graphene oxide (GO) are obtained by the
subsequent solvent-exfoliation of the graphite oxide. The oxygencontaining groups are bonded on the GNS, introducing structural
defects and surface charging. Meanwhile, the presence of
the oxygen-containing groups will facilitate the interactions of

Deformation by stretching chemical bonds

Chemical bonds stretching in GNSs
Theoretical studies of expansion behavior in GNSs induced by
charge injection and ionic liquid immersion have revealed that the
electrostatic double layer (EDL) could lead to a strain of more than
1% and its contribution to the overall strain is always higher than
that of quantum-mechanical strain (0.2%) from charge injection
of 0.08 e per C atom with electric potentials of 1 V (Fig. 2a) [64].
Meanwhile, these results also show that maximizing the electrolyte-accessible surface areas will enhance the EDL effect, and hence
enlarge the deformation of GNSs.
Despite the lack of direct experimental observation of the
expansion behavior for a single GNS, the stretching effect of
graphene chemical bonds has been determined to be in part
due to the stabilization of thermal fluctuations across the sheet
when freely suspended on a micro-fabricated scaffold in air or
vacuum [65]. The atomic scale observation revealed that the single
layered GNS were not perfectly flat but exhibited microscopic
deformations with a local strain of up to 1% induced by carbon-carbon bond stretching, which was as large as theoretical
predictions and was sustainable without plastic deformation
and the generation of defects. Furthermore, this inner-sheet strain
was also presented in those solution-dispersed GNSs [66]. When
the average sizes of GNSs ranged hundreds of nanometers, the
partial stretch of chemical bonds resulted in small wrinkles on the
surface of planar structure. For the smaller GNSs, a slight bending
behavior has also been demonstrated.

Chemical bond stretching in GO

The simulation study of GO demonstrated that a highly ordered
compound of GO is able to mimic the behavior of mammalian
skeletal muscle to provide large expansive strain of 10% and
contractive strain of 4.8% upon electron injection of 0.15 e per
C-atom within 1 ns (Fig. 2b) [67]. More impressively, beyond a
reversible strain of 6.3%, the huge 28% irreversible strain is shown
to be the result of a change in the atomic structure of GO from a
metastable clamped state to a stable unzipped configuration
(Fig. 2c) [68]. Significantly, this strain generation mechanism
makes it possible to hold a constant strain of 23.8% upon removal
of the input power, enabling this material for long-term, lowpower switching applications.
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FIGURE 2

(a) Schematic illustration of charge injection induced strains of GNSs. Reproduced with permission from Ref. [64] Copyright American Chemical Society
(2012). (b) Unit cell (denoted by dotted lines) of C4-asym-unzip GO. The inset table lists the a and b lattice parameters for C4O-asym-unzip GO and pristine
graphene, as well as the associated ab initio k-point grids. C and O atoms are represented by small-silver and large-purple spheres, respectively. Reproduced
with permission from Ref. [65] Copyright AIP Publishing LLC (2013). (c) Schematic illustration of hole injection induced strains of GNSs. Reproduced with
permission from Ref. [66] Copyright American Chemical Society (2012).

Deformation by carbon skeleton bending

Carbon skeleton bending in GNSs
Recent theoretical investigations have demonstrated a series of
out-of-plane deformation of GNSs dominated by carbon skeleton
bending, which can be controlled by various external stimuli, such
as temperature change [69,70], edge-stress [71,72], and surface
tension [73]. For instance, Iijima and coworkers demonstrated
that the edges of adjacent GNSs can be closed by a thermal
treatment, and hence equivalently achieve the folded GNSs
[69]. Xu et al. [70] further reported that the conformation of GNSs
can be controlled by a cooperation of thermal effect and other
experimental conditions such as surface modifications, substrate
and size of GNS. Shenoy et al. [71] showed that edge stresses
introduced intrinsic ripples in GNSs even in the absence of thermal
effect. Compressive edge stresses of the sheets result in various
warping shapes with a certain amplitude and penetration depth
proportional to the strength. This effect can lead to the twisting,
scrolling and shrinking conformation for rectangular GNSs. Moreover, the results from both finite deformation beam theory and
molecular dynamic simulations indicate that the flattened GNSs
are metastable [72], and hence water nanodroplets can activate
and guide the deformation of planar graphene nanostructures
[73]. Once the nanodroplets initiate conformational changes
and overcome deformation barriers associated with the nanostructures, the rapid bending, folding, sliding, rolling or zipping of
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the planar sheets was achieved. Since GNSs are flexible in 2D plane,
a stretch deformation can be geometrically achieved by curl
(Fig. 3a) and fold process with a self-overlap of GNSs (Fig. 3b). If
the graphene is hydrogenated on one side, it can completely scroll
up and remains stable at room temperature [74] with a certain
radius depending the water content [75].
The experimental results agree very well with those theoretical
investigations. As described by Xie et al. [76], the surface tension
exerted on the GNS during drying can lead to the scrolling of the
planar layer. Therein, the substrate, edge condition and shape
strongly influenced the ability of GNSs to deform. Additionally,
since the initial energy barrier associated with the deformation was
overcome by capillarity of solvent evaporation, the regulation of
the drying process also altered the scrolling behavior of GNSs.
Furthermore, GNSs can be dispersed with the aid of a range of
surfactants at low concentration in solvent systems, where zeta
potential of the GNSs is largely controlled by ionic surfactants,
hence the shape of GNSs can be controlled by the use of surfactants
with a certain concentration. Zhang and coworkers demonstrated
that surfactants can accurately control the deformation of GNSs by
tuning the electrostatic potential barrier and steric potential barrier of graphene [77]. However, depending on the type of surfactant, the residual surfactants are not easily removed from carbon
nanomaterials, and may lead to a decrease in electrical performance [78]. Furthermore, defamation of GNSs can also be

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by electrostatic interaction in acidic environments. In line with

the self-overlap strategy for folding GO, the flat GO layer can be
converted into the crumpled paper-ball-like morphology, presenting a new possibility for scalable control of their deformation [83].

FIGURE 3

(a) Roll and (b) fold of a GNS, which is activated and guided by a
nanodroplet of water. Reproduced with permission from Ref. [73] Copyright
American Chemical Society (2009). Model sheets of (c) GO and (d) SLG with
the geometry calculated with the PM6/MOZYME method: unfolded bands
and maximum folded structures corresponding to local minima on the
potential energy surface. Reproduced with permission from Ref. [81]
Copyright American Chemical Society (2012).

achieved by the exertion of an electrostatic field of appropriate

intensity. Along with the mechanism for edge stress induced
conformational changes of graphene, electric fields introduce
charged edges and lift GNSs from the substrate surface. The
combination of these two factors is sufficient to cause the scrolling
or folding of GNSs [79].

Carbon skeleton bending in GO

On the other hand, different from the pure graphene system, GO
nanosheets have remarkable dispersibility and chemical reactivity,
where the presence of oxygen groups on the graphene surface
introduces a charging effect, making GO more attractive in terms
of processability [80]. Therefore, the deformation of GO can be
realized in efficient ways including salt induced assembly [81], pHdriven conformational change [82] and the surface charge effect
[83]. The conformation of GO is directly inferred from functionalized regions that render inter-sheet interactions. For example,
repulsion between GO caused by surface charges can be overcome
by adjusting the concentration of salt, and thus the GO tends to
aggregate, which is useful for deformation control of GO [81].
Additionally, this surface charge induced interaction can also be
controlled by pH. The high pH value of the chemical environment
results in deprotonation of the hydrophilic oxygen-containing
groups in GO, establishing negative surface charge. It is reported
that the zeta potential of GO is below 30 mV when the pH is less
than 3 and can reach 45 mV at the pH approaching 10 [82]. The
GO sheet has sufficient charge to repulse the other GO sheets and
remains isolated when the zeta potential is more negative than
30 mV. Additionally, at low pH, GO is observed to appear folded
as shown in Fig. 3c, presenting tighter folded configuration than
GNS (Fig. 3d). Thereby, the self-overlap of the GO sheet was guided

GMAs have been attracting significant attention as they not only

possess the intrinsic properties of 2D graphene but also provide
advanced functions with improved performance in various applications. Benefiting from the remarkable interactions mentioned
above, GMAs can be obtained through different procedures, including the direct growth of graphene on metal foams [7], selfassembly of GO during reduction [84], solvent exchange and
evaporation induced self-assembly [85], freeze-drying of GO solution [86], hydrothermal treatment [8789], and so on. Considering
that GMAs are constructed by incomputable GNSs, the tiny deformations of each single sheet as mentioned above will be amplified
in different degrees and hence obvious deformations can be
achieved. Moreover, beyond the intra-sheet interaction, various
inter-sheets bridging effects are presented by those assembled
structures. Therefore, the regulation of the interplay between
architecturally connected sites can be of use to control the deformation of GMAs. In this section, the SID behavior of GMAs are
generally classified as SID achieved by a graphene active component and SID supported by a graphene flexible skeleton.

Graphene as an active component of SID

Graphene-based SID
The excellent electrical, thermal and optical properties of graphene enable a series of graphene-based stimuli-sensitive deformable structures. For instance, utilizing the electrical properties of
graphene, Chen and coworkers demonstrated an electrically actuated deformation of free-standing flexible graphene-based papers
[90]. An elongation strain of 0.064% was observed at an applied
potential of 1 V versus saturated calomel electrode in 1 M NaCl
solution, and the strain could be improved to 0.1% by the addition
of magnetic Fe3O4 nanoparticles to lessen the sheet stacking of
GNSs. In a different way, we have realized an all-graphene based
deformable structure by asymmetrically modifying the opposite
surfaces of a monolithic graphene film using hexane plasma (HexP) and oxygen plasma (O-P), respectively (Fig. 4a). Therein, the O-P
treated graphene strip displayed a reversible length change of up to
0.2% in response to the applied voltages, which was about 2050
times larger than that of its Hex-P treated counterpart (Fig. 4b)
[91]. As a result, the GMA presented a saturated curvature of ca.
0.6 cm 1 despite the rigidity of the graphene strip and its displacement decreased only by ca. 10% over 90 measurement cycles. It
was also found that O-P treatment of a freestanding graphene film
made by direct filtration of aqueous graphene colloidal suspensions could notably improve the deformation of the graphene film
to a strain of ca. 0.85% at 1.2 V [92], which is four times higher
than that for carbon nanotube (CNT) based deformable structures,
hence demonstrating that tiny deformations of each single sheet
was amplified in GMAs to achieve the macroscopical deformations
[93]. The deformation of the O-P treated GMA was adequately
load-tolerant, only suffering a slight reduction at 6.1 MPa
(Fig. 4c,d). In order to further increase the deformation, a polypyrrole (PPy)graphene bilayer GMAs was fabricated (Fig. 4e) [94].
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SID behavior of GMA

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FIGURE 4

(a) Illustration of asymmetric plasma treatments of the GMA with hexane

and oxygen, and the corresponding surface wettability. Water contact
angles for the Hex-P (left inset) and O-P (right inset) treated surfaces are ca.
908 and ca. 158, respectively. (b) The length changes of the GMA treated
with Hex-P and O-P under applied square wave potential of 1.2 V, L and DL
are defined as the length and length change of the GMA. Reproduced with
permission from Ref. [89] Copyright American Chemical Society (2010). (c)
The apparatus used for characterizing the load-tolerant, highly strainresponsive GMA, and (d) the image of a final fabricated device. Reproduced
with permission from Ref. [91] Copyright The Royal Society of Chemistry
(2011). (e) Schematic illustration of the SID mechanism, where the charges
in each electrode are completely balanced by ions from the electrolyte.
Reproduced with permission from Ref. [92] Copyright The Royal Society of
Chemistry (2012).

The combination of graphene and PPy film was devised to harvest

their synergetic function for remarkable deformation, and the
PPygraphene bilayer film demonstrated reversible warping with
a large bending ability of about 1208, superior to that of the pure
graphene films and overcoming the relatively poor mechanical
strength of PPy films. As another improved all-graphene deformable structure, Hu et al. [95] presented a low voltage induced
deformation of foldable corrugated structure of GMA, as shown
in Fig. 5a,b. A macroscopic length contraction with a strain of
2.4% is presented for the GMA under applied voltage of 10 V
within 0.5 s (Fig. 5c,d), which is probably due to the interlayer
gas expansion and the collective effect of the GNSs with intrinsic
negative coefficient of thermal expansion (CTE). The negative
CTE of this GMA along the length direction is estimated to be
150

FIGURE 5

Cross sectional SEM images of (a) a GO paper and (b) spumous GMA paper.
Schematic setup for measuring the thickness displacement of the spumous
GMA paper. (c) Displacement of the spumous GMA paper along the
thickness direction under 0.1 Hz square wave voltage. (d) Schematic
diagram of the corrugated structure-causing deformation process under the
applied voltage. Reproduced with permission from Ref. [93] Copyright The
Royal Society of Chemistry (2014). (e) Schematic diagram of the proposed
polymer-improved spumous GMA paper. Reproduced with permission from
Ref. [94] Copyright The Royal Society of Chemistry (2014).

approximately 10 4/8C while the positive CTE along thickness

direction is about 10 3/8C. Later, they selected polydimethylsiloxane (PDMS) to improve the deformable GMA (Fig. 5e) and realized
an ultra-large bending curvature of about 1.2 cm 1 at 10 V for 3 s
with a high displacement-to-length ratio of ca. 0.79 [96], which is
much larger than that of the other electromechanical deformable
GMA [9799].
On the other hand, beyond the electrothermal effect, direct
heating is also an efficient way to fabricate deformable structures
based on the CTE of graphene. Theoretically, graphene has demonstrated distinctive large negative CTE (contraction upon heating)
values ranging from
7 ppm K 1 for single-layer GNS to
1
81.2 ppm K for graphene nano-crystal [100,101]. Conley et al.
[102] studied the curvature of bimorph grapheneSiNx and grapheneAu cantilevers and compared the strain, CTE, and the adhesion force acting on GNS attached to SiNx and Au substrates (Fig. 6a).
They found that all the cantilevers were made to be considerably
bent toward the graphene side at room temperature, and the degree

FIGURE 6

(a) Schematic illustration of temperature dependence of curvature for

graphene bimetallic-like cantilevers. (b) Temperature dependence of the
cantilever during the initial heating (red)/cooling (blue) cycle immediately
after fabrication. (c) The temperature-dependence of the profile for the
same device in subsequent heating/cooling cycles. Reproduced with
permission from Ref. [100] Copyright American Chemical Society (2011).

of bending became temperature dependent following an initial

annealing step (Fig. 6b,c). Meanwhile, some irreversible deformation during the initial heating/cooling process turned reversible in
successive temperature cycling.

SID in GO-based assemblies

Zhu et al. [103] presented a deformable GO paper that experienced
reversible contraction/expansion upon heating/cooling between
30 and 808C, which is similar to the negative thermal expansion of
graphene. They carefully investigated this large equivalent negative thermal expansion of GO up to 130.14 ppm K 1 and found
that it in fact originated from thermo-hydration effects that were
highly dependent on the relative humidity and the state of water
in GO. Along with this mechanism, Mu et al. [104] prepared GMA
with a gradient reduced graphene oxide/graphene oxide (rGO/
GO) structure, which provided reversible, fast (0.3 s), powerful
(7.5  105 N kg 1 force output) and controllable mechanical deformation and recovery.

Graphene as flexible skeleton of SID

Apart from playing an active role in deformable GMAs, graphene
has been used as a mechanical support in the active component/
graphene composite systems for deformation purposes. Ruoff and
coworkers showed a deformable GMA prepared by sequential
filtration of multi-walled carbon nanotubes (MWCNTs) and then
GO platelets to form a bilayer of MWCNTGO paper [105]. The
water content of 17% in the GO layer was confirmed by thermal
gravimetric analysis, while the MWCNT layer was free of water
content, indicating an asymmetric swell of GO and MWCNT layers
depending on the water. As a result, the bilayer paper initially
rolled up with the MWCNT side facing outward at a low RH of 12%
at room temperature, gradually unrolled to an almost flat state
around a RH of 55% to 60%, started to curl in the opposite

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direction of GO side when the RH exceeded 60%, and eventually

fully curled at a RH of 85%. Lu et al. [106] demonstrated that ionic
liquid could be inserted to separate the layers of paralleled GNSs
(Fig. 7a), producing a GMA with ionic liquid of 66.7 wt%, and
presenting variation in thickness as large as 98% under a 2 V
electrical stimulation. However, the unstable parallel structure
(due to the lack of binder and large volume deformation) led to
the breakdown of the electrode under high voltage, long duration
time or repetitive cycles. To address this issue of instability, an
improvement was carried out by introducing MWCNTs to reduce
the restacking of rGO, and the rGOMWCNT system exhibited an
excellent long-term stability of up to a million cycles [107]. The
GO presented excellent hydrophilia so that water molecules can
act as inserts in a GO-water system (Fig. 7b), while the desiccation
of GO will lead to a shrinking of GO papers (Fig. 7c). Consequently,
the deformation was deemed to originate from the difference
between the amounts of inserted water in both layers under
different RH values.
Recently, the region-asymmetric deformable fibriform GMA
was fabricated by our group in virtue of the laser positioning
reduction of the freshly spun GO fibers [108]. The asymmetric
graphene fiber was conveniently fabricated by scanning a laser
beam along the preformed GO fiber, where the scanned area was
converted to rGO and the unexposed region remained unchanged.
As expected, a rapid bending to the rGO side occurred once the
GMA was exposed to moisture with a RH of 80%, while the fiber
recovered its initial state as the environmental humidity regressed
to the ambient condition of 25%. This process was fully reversible
with an average motion rate of ca. 88 s 1. Moreover, a regionspecific asymmetric GMA was also designed for use as complex
deformation-predefined systems. By rational design and localization of the laser-induced rGO regions along the GO fiber, more
sophisticated shape changes can be achieved. Furthermore, we
also reconstruct the intrinsic configuration of GNSs within the
GMA and achieved a new type of moisture-driven rotational motor
by rationally designing the rotary processing of the freshly spun
GO fiber hydrogel [109]. As schematically illuminated in Fig. 8a,
the deformable GMA can be conveniently fabricated by simply
rotating the freshly spun GO hydrogel fiber along the axis. The
twisting process has largely remolded the intrinsic structure of GF.
As shown in Fig. 8b, the initial axis oriented arrangement of GO
sheets becomes a helical configuration after the twisting process
and the compact GNSs on the surface of the GO fiber conform to
the rotary direction (Fig. 8c). The formed helical geometry of
obtained GMA would enable the reversible torsional rotation
under the alternation of humidity with stable speed of up to
5000 rpm (Fig. 8d,e). Along with this asymmetric moisture inserting strategy, more and more SID systems based on GMA have been
presented recently (Fig. 8f,g) [110113].

State-of-the-art applications
The SID process has enabled lifeless GMAs to work as living
organisms, thereby these GMAs were able to realize some complex
functions of living organisms through specific design. For instance, a voltaic-responsive smart claw was fabricated by GMA/
polymer bilayer [96]. As shown in Fig. 9a,b, a tri-finger mechanical gripper could quickly grab and put down objects with an
applied on and off voltage. Considering that the weight of these
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FIGURE 7

(a) Illustration of ion insertion induced graphite expansion (Reproduced with permission from Ref. [104] Copyright Royal Society of Chemistry 2012.) and (b)
water adsorption/desorption process in GO paper (Reproduced with permission from Ref. [101] Copyright American Chemical Society 2011). (c) Structural
changes in response to water absorption and desorption are shown in the AFM images. The resulting deformation is clearly visible. The blue regions in the
sketches indicate the rGO face of the GMA, while the brown regions indicate the GO face. Reproduced with permission from Ref. [105] Copyright Nature
Publishing Group (2011).

three fingers is about 36 mg and the weight of the grabbed small

objects (plastic foams) was 40 mg, this gripper can grab objects
which are a little heavier than the gripper itself. On the other hand,
the SID effect was applied to transform various chemical, optical
and thermal energies to mechanical energy, which was considered
as an ideal energy source for electrical power. Cheng et al. [109]
developed a new type of humidity triggered electric generator
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(Fig. 9c,d), which will produce power using mechanical work

induced by the variation of ambient moisture. To demonstrate
this idea, a twisted GO fiber was attached with a magnet bar at one
end, which was located in the center of several copper coils. When
the whole device was exposed to the varied humidity, the fast
rotation of twisted GO fiber could drive the magnet, behaving in
the same way, thus inducing the generation of electricity in the

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FIGURE 8

(a) Scheme of the twisted GMA fabrication. (b and c) SEM images of directly as-prepared GMA and twisted GMA, respectively. (d) Schematic rotation of a
twisted GMA with a paddle at the low (left) and high (right) humidity. When the moisture increases (right), the GMA can drive the paddle rotating fast; then
the paddle can reverse to the initial state when the moisture decreases (left). (e) The durability test of GMA undergoing repeated RH changes, showing
forward (the environment humidity changed from RH = 20% to 85%) and backward (RH = 85% to 20%) rotation speed versus cycle numbers. Reproduced
with permission from Ref. [107] Copyright Wiley-VCH (2014). (f ) Dependence of the curvature of the GO/rGO bilayer GMA upon RH. (g) Schematic illustration
of SID properties and mechanism of the GO/rGO bilayer GMA. Reproduced with permission from Ref. [111] Copyright Wiley-VCH (2014).

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FIGURE 9

(a) A photograph of tri-finger mechanical grippe (b) A larger object is grabbed by the tri-finger gripper with applied voltage of 10 V. Reproduced with
permission from Ref. [94] Copyright The Royal Society of Chemistry (2014). (c) The scheme of the designed alternating current generator. (d) The short-circuit
current of the generator tested under humidity changes between 20% and 85%. Reproduced with permission from Ref. [107] Copyright Wiley-VCH (2014).
(e) A crawler paper robot fabricated by using GO/RGO bilayer paper as smart legs. On and off means turning on and turning off the humidity,
respectively. Reproduced with permission from Ref. [111] Copyright Wiley-VCH (2014).

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Summary and outlook

SID enabled GMA can be constructed by mass produced GNSs.
Upon the formation of asymmetric structures, the GMAs exhibit
bend, curl and swing behaviors, while the homogeneous structures
normally correspond to strain changes. The deformation ability of
GMAs is controlled by a configuration change of each GNS,
inducing an enlargement of the interlayer spacing and/or a synergistic effect of them. Since various shapes can be easily obtained by
structural design, these SID enabled GMAs have been used to
fabricate smart devices and their performance is comparable to
those of counterparts based on polymers with high cost. The SID
effect of GMA is also promising for applications in sensing, drug
delivery and energy transformers.
Nevertheless, several challenges still remain in this field. Firstly,
as described above, all the techniques developed for fabricating
GMAs have to face the problem of scaling up, thus a low-cost and
productive method for construct GMAs with critically controllable
micro-/nano-structures is still required. Secondly, the mechanical
strength of GMAs without assistance of polymers is unsatisfactory.
It is of great theoretical and practical interest to develop an allgraphene based SID system with both flexibility and toughness for
important applications (e.g. structural materials and reinforcement). Thirdly, theoretical simulations have predicted the great
potential of the SID effect for practical applications. However,
these applications have rarely been realized experimentally. Undoubtedly, more effort from both academia and industry will
speed up the development of this emerging area, and the wide
applications of graphene-based smart deformable systems will be
realized.

Acknowledgements
We thank the financial support from the 973 Program of China
(2011CB013000) and NSFC (21325415, 21174019, 21301018),
Beijing Natural Science Foundation (2152028) and 111 Project
807012.
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RESEARCH: Review

copper coils. Mu et al. [104] presented an electrostatic spinning

strategy to prepare poly(vinylidene fluoride) (PVDF) attached
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and generates an open circuit voltage of up to 4 V. Furthermore, as
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moisture-responsive crawler robot was fabricated with GMA legs
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gathered up, leading to significant bending performance toward
the right. Once the moisture was replaced by dry air, the GMA legs
became unbent, pushing the whole robot toward the right. These
results indicate that the SID enabled GMAs holds great promise for
the development of smart materials and devices.

RESEARCH

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RESEARCH: Review

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