Materials Today Nano 5 (2019) 100027

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Materials Today Nano

j o u r n a l h o m e p a g e : h t t p s : / / w w w . e v i s e . c o m / p r o fi l e / # / M T N A N O / l o g i n

Synthesis and applications of three-dimensional graphene network

structures
Z. Chen a, *, L. Jin a, W. Hao a, W. Ren b, **, H.-M. Cheng b, c, ***
a
State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China
b
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
c
Shenzhen Geim Graphene Center, Tsinghua-Berkeley Shenzhen Institute (TBSI), Tsinghua University, 1001 Xueyuan Road, Shenzhen 518055, China

a r t i c l e i n f o a b s t r a c t

Article history: Integration and assembly of atomically thin two-dimensional graphene sheets into three-dimensional
Received 10 December 2018 (3D) macroscopic structures is essential for practical applications of graphene in the fields of compos-
Received in revised form ites, energy, environment, and biomedicine. Based on the chemical exfoliation and chemical vapor
8 January 2019
deposition, several approaches have been developed for the synthesis of 3D graphene structures with a
Accepted 17 January 2019
Available online 28 January 2019
unique network structure, ultrahigh porosity, large specific surface area, excellent electrical/thermal
conductivities, and outstanding mechanical flexibility. These significant advantages of the 3D graphene
network structures suggest great extended functionalities and potential applications of graphene. This
Keywords:
Macroscopic-porous structures
review article summarizes the recent progresses in the synthesis of 3D graphene network structures,
CVD their property characterizations, and promising macroscopic applications.
Composites © 2019 Published by Elsevier Ltd.
Energy
Environment
Biomedicine

1. Introduction high mobility of 200000 cm2/V s can be achieved by minimizing the

Graphene is a fascinating two-dimensional (2D) crystal with a
single layer of carbon atoms packed into a honeycomb lattice. Over
the past few years, graphene has become a rapidly rising star on the
horizon of physics, chemistry, materials science, and engineering
and demonstrates great promise for applications in nano-
electronics, composite materials, energy storage and conversion,
sensors, environment management, thermal management, and
biomedical materials because of its various exceptional properties
[1e3]. The instinct graphene is a zero band gap semiconductor,
which displays an ambipolar electric field effect, and charge car-
riers can be tuned continuously between electrons and holes, with
room temperature mobilities of up to 15000 cm2/V s [3]. Moreover,
the observed mobilities in graphene depend weakly on tempera-
ture, which could be realized at room temperature rather than at
very low temperature. In suspended graphene, an exceptionally
* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: chenzp@zju.edu.cn (Z. Chen), wcren@imr.ac.cn (W. Ren),
cheng@imr.ac.cn (H.-M. Cheng).
impurity scattering from substrates [4]. The strong CeC bond of
graphene in sp2 hybridization endows it with extraordinary elas-
ticity and stiffness. It can be elastically stretched by as much as 20%,
more than any other crystal. Moreover, graphene is the strongest
material ever measured with record Young's modulus (~1 TPa) and
intrinsic strength (~130 GPa) [5]. A record value for room temper-
ature thermal conductivity of graphene (~5000 W/m K) was also
reported [6].
To take full advantage of these fascinating properties of gra-
phene for macroscopic applications in the fields of composites,
energy, environment, and biomedicine, both large-scale synthesis
and integration of individual graphene sheets into three-
dimensional (3D) multifunctional structures are required. With a
relatively short history from 2009 since the first report of 3D gra-
phene macroporous structures synthesized by ice
segregationeinduced and template-direct self-assembly method,
many approaches, such as self-assembly of chemically derived
graphene and template-direct chemical vapor deposition (CVD),
have been developed for the production of 3D graphene network
structures. In these 3D graphene network structures, the 2D gra-
phene sheets interconnected with each other to form a high-
conductive network, which endows the graphene structures with

https://doi.org/10.1016/j.mtnano.2019.01.002
2588-8420/© 2019 Published by Elsevier Ltd.
2 Z. Chen et al. / Materials Today Nano 5 (2019) 100027
ultrahigh porosity, extremely low density, high surface area, and
outstanding electrical and mechanical properties. By assembly and
integration of the 2D graphene sheets into 3D form, the functions
and potential applications of graphene are greatly extended. In this
article, we will summarize the methods for synthesis of 3D gra-
phene network structures, their property characterizations, and
promising macroscopic applications.
2. Synthesis of graphene
Since the report of the first isolated graphene prepared by
simple mechanical cleavage of graphite crystals [1], many ap-
proaches, including epitaxial growth on SiC [7] or metals [8],
chemical exfoliation of graphite oxide [9e11], liquid-phase ultra-
sonic exfoliation of graphite [12], electrochemical exfoliation of
graphite [13], CVD growth on metal substrates [14e18], and so on,
have been developed for the synthesis of graphene. Among all the
approaches for synthesis of graphene, the mechanical cleavage
method can produce the highest quality graphene, although it has a
low productivity and controllability. The epitaxial growth method
can produce large-area graphene films, but the cost of the sub-
strates is very high and the graphene is difficult to transfer. The
chemical exfoliation method can realize mass production of gra-
phene with a low cost, and the rich functional groups of chemically
derived graphene make it easy for assembly and integration into
complicated structures, but the obtained graphene has a large
amount of defects and low quality. The liquid-phase exfoliation
method can also synthesize graphene in large scale, but the gra-
phene sheets are in small size. The CVD growth method can pro-
duce large-area and high-quality graphene with a reasonable
productivity, and it is easy to transfer. In this section, we will give a
brief introduction on the chemical exfoliation and CVD growth
methods, which are the two most important methods used for
synthesis of 3D graphene network structures.
2.1. Chemically derived graphene
Graphite oxide consists of a layered structure with oxygen
function groups and water molecules intercalated between the
graphene basal planes. Graphite oxide was first prepared in 19th
century mainly by the Brodie [19], Staudenmaier [20], and Hum-
mers [21] methods, which involved the oxidation of graphite in the
presence of strong acids and oxidants. For example, in the typical
Hummers method, the graphite powder was heavily oxidized by
KMnO4/NaNO3 in concentrated H2SO4 to form graphite oxide [21].
The level of oxidation can be varied on the basis of the method, the
reaction conditions, and the graphite precursor, which results in
the interlayer distance of graphite oxide varying from 6 to 12 Å [22].
Owing to the large interlayer distance and week interaction of
graphite oxide, it can be completely exfoliated into graphene oxide
(GO) sheets in water by mild sonication to form a stable aqueous
colloidal suspensions [9]. To avoid the explosion risk and serious
environmental pollution in aforementioned method, Ren et al. [23]
have recently developed a scalable, safe, and green method to
synthesize GO with a high yield based on water electrolytic
oxidation of graphite. The graphite lattice can be fully oxidized
within a few seconds in the electrochemical oxidation reaction,
which was more than 100 times faster than traditional Hummers
methods. Moreover, this method enabled continuous production
and easy control on the oxidation degree, number of layers, and
lateral size of the GO sheets.
GO itself is non-conducting owing to the heavy oxidation. How-
ever, it can be reduced to conductive graphene (reduced graphene
oxide, rGO) sheets by various reduction agents in aqueous solution.
Ruoff et al. first demonstrated the use of hydrazine hydrate to
eliminate the oxygen function groups and restore the sp2 graphitic
structures [9]. Unfortunately, the removal of oxygen groups caused
the rGO sheets to become less hydrophilic and quickly aggregate in
solution. Li et al. later reduced the GO by hydrazine in an aqueous
ammonia solution and showed that raising the pH value during
reduction could lead to charge-stabilized colloidal dispersions of
rGO [24]. Owing to the high toxicity and potential explosivity of
hydrazine, other mild reduction agents such as hydrohalic acids
[25,26] and ascorbic acid have been developed. For example, GO
films can be effectively reduced by 55% hydroiodic acid into integrate
and flexible graphene paper with an electrical conductivity as high
as 298 S/cm and a C/O ratio above 12 [25], both of which are much
higher than the GO films reduced by hydrazine [9,24]. The possible
reaction mechanism in the reduction process may be as followed:
the ring-opening reaction of an epoxy group and the substitution
reaction of a hydroxyl group by a halogen atom, which is expected to
be easily eliminated from the carbon lattice to produce reduced
graphene. The chemical exfoliation and reduction method have been
demonstrated as a promising method for large-scale production of
graphene for commercial applications. However, the quality and
electrical conductivity of these graphene sheets are much poor than
the pristine graphene, owing to the severe structural defects and
significant amount of oxygen residues introduced during oxidation,
exfoliation, and reduction processes [11].
2.2. CVD growth of graphene
Large-area high-quality graphene films have been grown by
CVD and transferred for use as transparent conductive films, whose
conductivity were much superior to those films fabricated using
chemically derived graphene sheets [16,27]. CVD appears to be the
most promising technique for large-scale production of high-
quality graphene films. Monolayer to few-layer graphene with a
large area was first prepared by ambient pressure CVD on the
surface of polycrystalline nickel (Ni) [14e17]. The films contained
domains of one to two layers in thickness and 1e20 mm in lateral
size. The quality of the films was supposed to be comparable with
that of mechanically exfoliated graphene because of the low D/G
ratio in the Raman spectrum [15]. After etching of the metal sub-
strate, the graphene films can be transferred to an arbitrary sub-
strate. The transferred graphene films show very low sheet
resistance of 280 U/sq with 80% optical transparency [16]. The
monolayer graphene sample shows electron mobility higher than
3700 cm2/V s and exhibits the half-integer quantum Hall effect,
suggesting again the high quality of the CVD-grown graphene [16].
These studies opened up a new graphene synthesis route; however,
several issues such as controlling the number of layers and mini-
mizing the folding of graphene are still unsolved. In 2009, Ruoff
et al. have found that large-area monolayer graphene can be grown
on Cu foil by CVD [18]. The graphene film predominantly consists of
a monolayer, and the few-layer region is less than 5%. This success
in getting monolayer graphene is due to the low solubility of carbon
in Cu, in contrast to the large solubility in Ni. The obtained gra-
phene film also shows high quality with extracted carrier mobility
typically in the range of 2000e4000 cm2/V s. However, these gra-
phene films were still polycrystalline with small crystal sizes.
Recently, lots of efforts have been focused on the synthesis of large-
sized single-crystal graphene, in which the absence of grain
boundaries guarantees its excellent intrinsic properties. Many
creative methods have succeeded in the synthesis of large-area
single-crystal graphene with ultrafast growth speed [28,29].
These new methods include the growth on noble metal substrates
such as Pt [30,31] or single-crystal substrates such as Ge(100) [32]
and Cu(111) [33,34];local carbon feeding growth [35,36]; oxygen-
assisted growth [37,38]; and so on. Besides the improvement in
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027
CVD growth, new methods for transferring graphene to arbitrary
substrates are also desirable. Hong et al. developed an efficient roll-
to-roll transfer process of graphene grown on a flexible Cu foil [27].
This process has been applied to transfer a large-size graphene film
with size as large as 30 inches in the diagonal direction, and
multilayered graphene films can be prepared by repeating this
process on the same substrate. The graphene film had a sheet
resistance of about 125 U/sq and an optical transmittance of 97.4%.
By repeating the roll-to-roll process four times on the same sub-
strate, a four-layered graphene film can be prepared with a low
sheet resistance down to ~30 U/sq and a transmittance of only
~90%. A bubbling transfer method has been also developed, which
makes the repeated use of noble metal or single-crystal substrates
available and greatly reduces the cost [30].
3. Synthesis of 3D graphene network structures
Based on the chemical exfoliated graphene and direct CVD
method, several approaches have been developed for the synthesis
of 3D graphene network structures. In this section, the main stra-
tegies for integration and assembly of 3D graphene network
structures are briefly summarized, including self-assembly of
chemically derived graphene sheets during reduction or with the
assist of cross-linking agents, template-directed assembly of gra-
phene sheets, gas expansion of graphene films, 3D printing,
template-directed CVD growth on various 3D porous substrates,
and so on.
3.1. GO-derived 3D graphene network structures
Owing to the ease of preparation and processing, chemical
exfoliated GO sheets have been extensively used for assembly into
various 3D graphene macroscopic structures by means of self-
assembly or template-directed assembly of GO sheets. Gas expan-
sion inside GO papers has also been demonstrated as an efficient
way to form 3D graphene porous structures.
3.1.1. Self-assembly of GO sheets in solution
Owing to the abundance of hydrophilic oxygen function groups,
GO sheets can be dispersed in water and form a high concentrated
and stable aqueous solution with the aid of electrostatic repulsion
force between the oxygen function groups. At the same time, the
GO basal plane is highly hydrophobic because of the 2D arrange-
ments of sp2 carbon structures. The balance between Van der Waals
force and electrostatic repulsion of GO and rGO platelets regulates
their solution properties and accounts for their self-assembly
behavior in aqueous media. Self-assembly of the GO and rGO
colloidal can then be controlled for synthesis of 3D graphene
hydrogel and porous macrostructures.
3.1.1.1. Cross-linking gelation of GO. Self-assembly of 3D graphene
hydrogel was achieved by gelation of GO sheets with the aid of
cross-linking agents, such as polymers [39,40], DNA [41], protein
[42], noble metal nanocrystal [43], small quaternary ammonium
salts, and metal ions (Fig. 1) [44e46]. For example, Shi et al. re-
ported a graphene-based hydrogel using poly(vinyl alcohol) (PVA)
as a physical cross-linking agent [39]. GO aqueous solutions were
mixed with PVA aqueous solutions followed by violently shaking
the mixture for 10 s and sequent sonication for 20 min resulted in
the formation of a GO/PVA hybrid hydrogel. In this hydrogel, oxy-
gen function groups on the surface of GO sheets can form strong
hydrogen bonds with hydroxyl-rich PVA chains as the cross-linking
sites. When the number of cross-linking sites was sufficiently high,
a GO composite hydrogel was generated due to the formation of a
continuous GO network. They further systematically studied the 3D
3
self-assembly of GO sheets in aqueous media to form hydrogels,
which were promoted by different supramolecular interactions,
including hydrogen bonding, p-stacking, electrostatic interaction,
and coordination by using various cross-linkers such as small
organic molecules, polymers, ions, and so on (Fig. 1bef) [44].
Worsley et al. also synthesized a graphene hydrogel by cross-
linking GO sheets with organic solegel polymerized phenolic
resin (Fig. 1h) [40]. Subsequently, supercritical dry and pyrolysis of
the hydrogel resulted in an ultraelow-density graphene aerogel
with high conductivity (1 S/cm) and large surface areas (584 m2/g).
3.1.1.2. Self-assembly by GO reduction. Although cross-linking
agenteassisted self-assembly method has been shown great suc-
cess in synthesis of 3D graphene hydrogel and porous macro-
structures, the obtained structures are always hybrid and
composites. Additive-free 3D graphene pristine hydrogel and
porous macrostructures can be synthesized by cross-link between
graphene sheets at the reduction process. Before reduction, GO
sheets were randomly dispersed in water because of the presence
of abundance of hydrophilic oxygen function groups and the strong
electrostatic repulsion effect. When the reduction of GO sheets
began, the hydrophobicity and the p-conjugated structures of the
GO basal plane increased owing to the removal of epoxy and hy-
droxyl groups. The increased Van der Waals forces and p-p stacking
between graphene increased the amount of cross-links between
GO sheets, which led to 3D cross-linked graphene networks. The
reduction-induced gelation of GO was first reported by Xu et al. [47]
using a hydrothermal reduction process (Fig. 2aec). A facile one-
step hydrothermal treatment of GO aqueous dispersion sealed in
a Teflon-lined autoclave at 180
C for 12 h resulted in an rGO
hydrogel with well-defined and interconnected 3D porous struc-
tures. The rGO hydrogel shows an electrical conductivity of
5  103 S/cm and a high storage modulus of 450e490 kPa. After
the seminal work by Shi et al., hydrothermal reduction method has
been adopted for synthesis of various 3D graphene macroporous
hybrid and doping structures [48e50]. For example, Qu et al.
demonstrated an ultralight nitrogen (N)-doped graphene frame-
work by hydrothermal treatment of GO and pyrrole mixed sus-
pension in a Teflon-lined autoclave at 180
C for 12 h (Fig. 2d). The
obtained N-doped 3D graphene framework has an ultralow density
of 2.1 mg/cm3, a high electrical conductivity of 12 S/cm, and a large
surface area of 280 m2/g [48]. On the contrary, Ruoff et al. reported
a controllable fabrication of compact high-density graphene mac-
rostructures with various shapes by pH-mediated hydrothermal
reduction of GO dispersion [51]. The compact graphene possessed a
solid microstructure with a high density (~1.6 g/cm3), which was
comparable to conventional graphite products and an ultrahigh
compressive strength. By further high-temperature annealing at
900
C, the compressive strength and electrical conductivity of the
compact graphene macrostructures can reach up to 361 MPa and
7.6 S/cm, respectively.
Inspired by the hydrothermal reduction approach, chemical
reduction has also been developed for self-assembly of GO into 3D
porous structures [52,53]. Sheng et al. [52] first reported the self-
assembly of graphene hydrogels by chemical reduction of GO
with sodium ascorbate. The graphene hydrogels were simply pro-
duced by resolving sodium ascorbate in the GO solution and
heating the mixture at 90
C for 1.5 h. At the same time, Liu et al.
reported graphene hydrogel synthesized by reduction of GO with L-
ascorbic acid (Fig. 2e) [53]. Supercritical drying or freeze-drying of
the obtained hydrogel resulted in mechanically strong graphene
aerogels with a high surface area of 512 m2/g and high electrical
conductivity of ~1 S/cm. Based on these pioneer works, other types
of reducing agents, such as hypophosphorous acideiodine [54],
ethylenediamine [55,56], KMnO4 [57], NaHSO3, Na2S, HI,
4 Z. Chen et al. / Materials Today Nano 5 (2019) 100027

Fig. 1. Cross-linking gelation of GO in solution. (a) The procedure of preparing GO/DNA hydrogel and the proposed gelation mechanism. (b) Photographs of 5 mg/mL GO solutions
mixed with different cross-linkers: (1) 0.5 mg/mL poly(vinylpyrrolidone) (PVP); (2) 1 mg/mL hydroxypropyl cellulose (HPC); (3) 1 mg/mL poly(ethylene oxide) (PEO); (4) 0.1 mg/mL
polydimethyldiallylammonium chloride (PDDA); (5) 0.2 mg/mL polyethylenimine (PEI); (6) 0.3 mg/mL cetyltrimethyl ammonium bromide (CTAB); (7) 1.9 mg/mL tetramethy-
lammonium chloride (TMAC); (8) 0.3 mg/mL melamine; (9) 20 mM Liþ; (10) 20 mM Kþ; (11) 20 mM Agþ; (12) 15 mM Mg2þ; (13) 9 mM Ca2þ; (14) 3 mM Cu2þ; (15) 3 mM Pb2þ; (16)
3 mM Cr3þ; and (17) 3 mM Fe3þ. SEM images of lyophilized GO solution and three typical GO hydrogels: (c) GO solution, (d) GO/PDDA hydrogel with 0.1 mg/mL PDDA, (e) GO/PVP
hydrogel with 1 mg/mL PVP, and (f) GO/Ca2þ hydrogel with 9 mM Ca2þ. CGO ¼ 5 mg/mL, and scale bar ¼ 10 mm g. (g) A photo showing an iron plate weighing 167 g placed on a 3D
GO macrostructures promoted by noble-metal nanocrystal; the inset showed that the sample can endure two iron plates. (h) SEM image of a graphene aerogel cross-linked by
solegel polymerized phenolic resin. GO, graphene oxide; SEM, scanning electron microscope. Reproduced with permission from Ref. [41] (a) [44], (bef) [43], (g), and [40] (h).
Copyright: 2010 American Chemical Society (a), 2011 American Chemical Society (bef), 2010 Wiley (g), and 2010 American Chemical Society (h).

hydroquinone [58,59], and Cu nanoparticles [60], have been used as
well for the preparation of 3D graphene porous structures.
3.1.2. Template-directed assembly of GO sheets
Different from the self-assembly methods, 3D porous graphene
networks with well-defined and order structures can be produced
by template-directed assembly methods. Various templates, such
as sphere colloidal particles [61e65], ice crystals [66,67], aqueous
droplets [68], bubbles [69], and so on, have been used for the as-
sistant assembly of the graphene sheets.
Polystyrene (PS) colloidal particles were used to guide the as-
sembly of graphene sheets into micrometer-sized hollow spheres
[61]. In this process, the PS sulfonateestabilized graphene (PSS-G)
sheet dispersions were mixed with poly(allylamine hydro-
chloride)ecoated PS colloidal solution. Electrostatically induced
templating of negatively charged PSS-G sheets on the positively
charged PS particle surface was then taken place under high-speed
vortexing. Subsequently, treatment with toluene removed the
entire core template and leaved the freestanding hollow PSS-G
microspheres. But the resulting hollow graphene shells were
extremely fragile and often considerably deformed into deflated
and fractured structures. Choi et al. [62] also fabricated a well-
ordered macroporous graphene film using PS colloidal particles
as a sacrificial template. The macroporous graphene films were
prepared in two steps: fabrication of freestanding PS/chemically
modified graphene (CMG) films by vacuum filtration of a mixed
aqueous colloidal suspension of CMG and PS, followed by removal
of PS to generate freestanding porous films. The porous structure
did not collapse after the removal of the PS template because of the
interconnected nature of the multilayered CMG walls with high
mechanical flexibility. The macroporous graphene films also
showed a high electrical conductivity of 12 S/cm. Using the similar
vacuum filtration strategy and poly(methyl methacrylate) (PMMA)
latex spheres as the hard templates, Su et al. fabricated a 3D bubble
graphene film with controllable and uniform macropores and
tailorable microstructure [63]. Vacuum filtration of GO hydrosol
and PMMA spheres suspension mixture was first conducted to
realize the sandwich assembly film of PMMA spheres and GO
sheets. The composite film was subsequently calcinated at 800
C to
remove the PMMA template and thermally reduce GO into hollow
graphene shells simultaneously, resulting in a 3D macroporous
graphene film.
Template-directed assembly of graphene on the surface of
polymer colloid has been proved to be an effective strategy to
control the pore structures of the 3D graphene networks. However,
the pore size of the obtained graphene networks is generally
limited in the micrometer range. Zhao et al. designed a hydrophobic
interactionedriven hard templating approach to synthesize nano-
porous graphene foams (GFs) with a controllable pore size
(30e120 nm) [64]. In this process, methyl groupegrafted silica
spheres with hydrophobic surface and uniform size were chosen as
the hard template to fabricate porous GFs. When the silica spheres
and GO were mixed in a neutral aqueous solution, hydrophobic
interaction between the silica templates and GO planes induced a
self-assembled lamellar-like structure. The as-made composites
were then calcined under inert atmosphere to reduce GO sheets
into graphene. Subsequent HF etching removed the silica templates
and resulted in the nanoporous GFs. Using silica spheres with a
uniform particle size of 27.7 nm as the hard templates, the obtained
nanoporous GFs had a high surface area of 851 m2/g and total pore
volume value of 4.3 cm3/g. The majority pore size of the foam was
narrowly distributed at 32.5 nm, which was close to the size of the
silica templates. Using alumina-coated silica sphere as template, Liu
et al. prepared a 3D hollow carbon sphere/rGO composite structure
by an in situ synthetic assembling strategy [65]. In this strategy, the
alumina-coated silica sphere (~100 nm) acted as both templates for
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027 5

Fig. 2. Self-assembly of GO by reduction. (a) Photographs of a 2 mg/mL homogeneous GO aqueous dispersion before and after hydrothermal reduction at 180
C for 12 h. (b)
Photographs of a strong graphene hydrogel allowing easy handling and supporting weight. (c) SEM image of the graphene hydrogel interior microstructures. (d) Photographs of an
as-prepared superlight graphene framework standing on a dandelion. (e) Digital photos of the graphene hydrogel in a vial prepared by heating the mixture of GO and L-ascorbic acid
without stirring. GO, graphene oxide; SEM, scanning electron microscope. Reproduced with permission from Ref. [47] (aec) [48],(d), and [53] (e). Copyright: 2010 American
Chemical Society (aec), 2012 Wiley (d), and 2011. The Royal Society of Chemistry (e).

carbon shells and graphene sheets to form a 3D hollow structure.
The carbon precursors were polymerized on the alumina catalytic
sites of the templates, followed by carbonization at 900
C in Ar. The
GO sheets were folded around the spherical templates during the
catalytic reaction, and the spherical particles can be removed to
leave a 3D hollow composite structure. By changing the GO content,
the composite can be systematically tuned from layered composites
to 3D hollow structures to microporous materials. A very small
amount of rGO (4 wt%) was capable of creating and maintaining the
desired hollow pore structure in the carbon matrix, and the surface
area was as high as 1175 m2/g, which was much higher than that of
either pure rGO or carbon sphere. Yang et al. have also developed a
3D graphene macroassembly with a coreeshell structure by a one-
pot self-assembly of rGO under very mild conditions in the pres-
ence of KMnO4 [57]. It has been revealed that KMnO4 transformed
to MnO2 nanoparticles, which played a role to some extent in the
formation of the coreeshell macroassembly.
Ice crystals formed by unidirectional freezing are also an effec-
tive template for assembly of graphene into 3D macroporous
structures. Vickery et al. [61] demonstrated the production of
grapheneepolymer nanocomposites with higher order 3D macro-
scopic structures by ice segregationeinduced self-assembly of
frozen aqueous dispersions containing homogeneous mixtures of
PSS-G and PVA (Fig. 3aed). For this technique, a syringe containing
homogenized mixtures of PSS-G and PVA at weight ratios of 1:10
was subjected to unidirectional freezing in liquid nitrogen, followed
by freeze-drying of the frozen samples to produce intact porous
monolith scaffold as long as 5 cm. Close-packed ice crystals were
grown on unidirectional freezing and compacted the PSS-G and PVA
components between the boundaries of adjacent crystals.
Subsequent high-vacuum sublimation of the ice produced well-
ordered microchannel structures oriented along the freezing di-
rection. After the seminal work by Mann et al., Estevez et al. [66]
synthesized a multifunctional graphene/platinum/Nafion macro-
porous hybrid via a similar ice templating method. The hybrids were
synthesized by a two-step process: (a) an aqueous suspension
comprising Nafion, GO, and chloroplatinic acid was plunged into the
nitrogen slurry to form a microcellular porous network and (b) mild
reduction in hydrazine or monosodium citrate resulted in graphene-
supported Pt nanoparticles on a Nafion scaffold. The morphologies
obtained were highly anisotropic due to the intrinsic temperature
gradient. The microcellular scaffolds combined high levels of ionic
(Nafion) and electronic (graphene) conductivity along with catalytic
activity (Pt). Qiu et al. [67] reported an ultralight and superelastic
graphene-based cellular monolith by freeze casting of partially
reduced GO with no requirement for any additional polymer binders
(Fig. 3g). The GO solution was first mixed with ascorbic acid and
heated in boiling water bath for 30 min to obtain a partially reduced
GO dispersion. Then, this dispersion was freezing in a dry ice bath,
and the partially reduced GO sheets were rejected from the forming
ice and entrapped between neighboring ice crystals to form a
continuous network. The obtained graphene network copied the ice
crystal template, which was grown in a highly anisotropic way with
a highly ordered layer structure, resulting in a cellular monolith
hierarchical structure. The graphene monolith was ultralight and
superelastic, which can support more than 50000 times of its own
weight under 80% strain without collapsing and was able to almost
completely recover to its original shape rapidly when the loading
was removed. And the graphene monolith also showed a good
electrical conductivity as high as 0.12 S/cm.
6 Z. Chen et al. / Materials Today Nano 5 (2019) 100027

Fig. 3. Template-directed assembly of GO sheets. SEM images of (a, b) longitudinal sections and (c, d) cross-sections of a PSS-G/PVA freeze-dried monolith (1:10 wt ratio). Scale
bars: a, c, d ¼ 10 mm, b ¼ 5 mm. Arrows in a, b indicate direction of freezing. (e) Self-assembly of rGO into macroporous carbon films by a ‘Breath-figure’ procedure. (f) Plane-view
SEM images of an rGO film. (g) Typical top-view SEM image of a graphene monolith fabricated by a freezing method. (h) Foam-like graphene formation from the seed and bubbles.
GO, graphene oxide; SEM, scanning electron microscope; PSS-G, polystyrene sulfonateestabilized graphene; PVA, poly(vinyl alcohol). Reproduced with permission from Ref. [61]
(aed) [68], (eef) [67], (g), and [69] (h). Copyright: 2009 Wiley (aed), 2010 Wiley (eef), 2012 Macmillan Publishers limited (g), and 2013 Nature Publishing Group (h).

Besides the solid templates mentioned previously, the soft
aqueous droplets and even bubbles can be used for assembly of
graphene into 3D macroporous structures. For example, the
‘Breath-figure’ procedure has been used for self-assembly of PS-
grafted GO (PS-GO) platelets into a mechanically flexible macro-
porous structure (Fig. 3eef) [68]. In this procedure, drop casting a
dispersion of PS-GO/benzene onto a SiO2 substrate and exposing to
a stream of humid air resulted in endothermic evaporation of the
volatile benzene. The spontaneous condensed and close-packed
aqueous droplets at the PS-GO/benzene solution surface were
served as a template, which rejected and entrapped the PS-GO
platelets between neighboring aqueous droplets to form a
continue macroporous network after solvent evaporation. Subse-
quently, pyrolysis of the PS-GO networks facilitated the thermal
reduction of the GO platelets into mechanically flexible and
superhydrophobic graphene macroporous films. Scanning electron
microscope (SEM) images of the graphene films show the closely
packed macropores with an open porous morphology. Further N-
doping of the macroporous film increased the electrical conduc-
tivity up to 649 S/cm. Self-assembled foam-like graphene (SFG)
structures have also been self-assembled on various target sub-
strates with the aid of bubbles generated by the nucleate boiling
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027 7

method (Fig. 3h) [69]. In the nucleate boiling method, a thin sub-
strate can be placed on a heater in the rGO colloid solution. First,
50- to 100-nm base graphene layers were stacked on the substrate
surface in the boiling rGO solutions. When the heat flux of nucleate
boiling was higher than 300 kW/m2, the SFG began to form on the
base graphene layers through the self-assembly of rGO platelets
with the aid of bubbles as template. The process was governed by
the dynamics of bubble generation and departure in the graphene
colloid solution, and the pore size and film thickness were tunable
by adjusting heat flux and boiling time. The SFG film obtained was
highly porous and retained both hydrophobic and hydrophilic
properties due to hydrophobic rGO planes exposed to the surface
and carboxylic groups buried in the structures by self-assembly.
The SFG film also showed high conductivity, which can reach
11.8 S/cm after annealing at 400
C.
3.1.3. Gas expansion
Gas expansion inside a graphene film will create some pores and
space between the graphene sheets, resulting in 3D porous gra-
phene structures. For instance, El-Kady et al. [70] developed a laser
scribing method for the direct reduction of GO films to 3D porous
graphene films (Fig. 4a). Initially, a GO thin film was made onto a
flexible substrate by either drop-casting or vacuum filtering of GO
dispersions. Then, the GO film was affixed on top of a LightScribe
enabled DVD media disc and moved into the DVD optical drive for
laser treatment. The laser irradiation process resulted in the
removal of oxygen functional groups to form gaseous species and
re-establishment of the sp2 carbons, which caused a change in the
conductivity of the film from the insulating GO to highly con-
ducting laser-scribed graphene (conductivity up to 17.38 S/cm). The
SEM images showed that the initially stacked GO films were
converted into well-exfoliated porous graphene films with a high
specific surface area of 1520 m2/g through the rapid release of the
gaseous species by laser irradiation.
Leavening is usually a process used for creating gas before or
during baking or steaming to produce porous bread from the more
compact dough. Inspired by this technique, Niu et al. [71] devel-
oped a leavening strategy to transform the compact graphene films
to porous GF structures (Fig. 4b). In the first step, aqueous GO
dispersions were filtered through a porous anodized aluminum
oxide membrane to form freestanding GO films with compact
layered structures and an interlayer distance of 0.83 nm. Then, the
freestanding GO films were put into a Teflon vessel prefilled with
hydrazine monohydrate. The vessel was sealed in a stainless steel
autoclave and heated to 90
C for 10 h. The role of the hydrazine
vapor was to initiate the chemical reduction of GO with the rapid
evolution of gaseous species such as H2O and CO2. The gas released
during chemical reduction of GO could be incorporated into the
compact GO layered film, and then, a porous GF with 50-fold vol-
ume expansion could be formed. The GF showed an open porous
network with a pore size in the range of submicrometer to several
micrometers.
Korkut et al. [72] reported a scalable tape casting method for
producing continuous graphene networks (Fig. 4ced). In this
method, surfactant-stabilized graphene suspension was controlled,
casting through a slit by the motion of a substrate relative to a
doctor blade. The graphene sheets used for casting were produced
by the simultaneous thermal exfoliation and reduction of GO and
then dispersed in water to form a highly dispersed graphene sus-
pension using a triblock copolymer as surfactant and poly(ethylene
oxide) as binder. The suspension was cast on the silane-coated glass
plate using a doctor blade and dried at ambient temperature for

Fig. 4. Three-dimensional porous graphene structures by gas expansion. (a) Schematic illustration of the fabrication of laser-scribed graphene (LSG) films. A GO film supported on a
flexible substrate was placed on top of a LightScribe-enabled DVD media disc, and a computer image was then laser-irradiated on the GO film in a computerized LightScribe DVD
drive. As shown in the photograph, the GO film changed from golden brown color to black as it reduced to laser-scribed graphene. The low-power infrared laser changed the stacked
GO sheets immediately into a well-exfoliated few-layered porous graphene film, as shown in the cross-sectional SEM images. (b) Cross-sectional SEM image of rGO foams formed
after 10 h in an autoclave at 90
C with 80-mL hydrazine monohydrate. (c) Schematic describing the production of porous graphene tapes. (d) Graphene tapes after thermolysis of
polymer and surfactant. GO, graphene oxide; SEM, scanning electron microscope. Reproduced with permission from Ref. [70] (a) [71], (b), and [72] (ced). Copyright: 2012, American
Chemical Society (a), 2012 Wiley (b), and 2011 American Chemical Society (ced).
8 Z. Chen et al. / Materials Today Nano 5 (2019) 100027
several days to form large-area freestanding tapes. Subsequent
thermolysis of the composite tapes at 315
C removed most of the
polymer and surfactant, resulting in flexible and porous graphene
tapes with a large specific surface area of 400 m2/g, lower apparent
densities of 0.15e0.51 g/cm3, high conductivities up to 240 S/cm,
and strong tensile strengths more than 10 MPa. Sun et al. have also
developed a heating-assisted spray method for fabrication of the
porous graphene film [73]. The porous structures may be ascribed
to the rapid evaporation rates of ethanol solvent at high heating
temperature of 70
C. Moreover, the rapid preparation of the film
with area as large as ~216 cm2 in only 6 h has been successfully
achieved.
Inspired by an ancient food art of ‘blown sugar’, Bando et al. have
developed a sugar-blowing technique for template-free growth of
3D self-supported strutted graphene macroporous structures
[74,75]. Graphene relative materials were not used in this blowing
process, but glucose was chosen as the precursor, which was mixed
with ammonium salts (NH4Cl), and then heated under a desired
heating rate (4
C min1 was recommended) and finally treated at
1350
C. The obtained strutted graphene structures revealed a
foam-like architecture packed by large polyhedral bubbles with an
average diameter of 186 mm, resulted in an ultralow density of
3.0 mg/cm3, comparable to a carbon aerogel. The strutted graphene
structures consisted of continuous graphitic membranes, which
were homogenously connected and spatially supported by the
networks of micrometer-width graphitic struts. Because no catalyst
was used in this process, the obtained graphitic membranes can be
only crystallized by annealing at a very high temperature. The ob-
tained strutted graphene structure, thus, possessed an overall low
conductivity of 1 S/m1, since its low graphitic crystallinity and high
content of defects compared with those graphene films grown by
metal-assisted CVD (see section 3.2).
3.1.4. Three-dimensional printing
Three-dimensional printing is widely considered as a revolu-
tionary manufacturing technology, which enables the direct pro-
duction of 3D bulk objects with arbitrarily designed structures,
demonstrating significant promise in a broad range of fields. Direct
ink writing is an extrusion-based 3D printing technique by depo-
sition of a liquid ink that rapidly solidifies on extrusion. Direct ink
writing allows the fabrication of 3D objects layer by layer and is also
compatible with multimaterial printing, allowing the integration of
multiple functionalities in one 3D printing format. Shah et al.
developed a 3D printable graphene ink which can be used under
ambient conditions via 3D printing to create electrically conduc-
tive, mechanically resilient, and biocompatible graphene scaffolds
with a high graphene content (60 vol% of solid) (Fig. 5a) [76]. This
solvent-based graphene ink comprised graphene flakes and
biocompatible, biodegradable, and hyperelastic polyester
polylactide-co-glycolide. The 3D printed graphene structures
possessed features as small as 100 mm and composed of as few as
two layers (<300-mm thick object) or many hundreds of layers
(>10-cm thick object). The graphene structures were also me-
chanically robust and plastic in nature, with thin constructs dis-
playing a high degree of flexibility. Overall, this 3D graphene ink
enabled rapid fabrication of 3D graphene objects with novel and
desirable mechanical, electrical, biological, and handling
properties.
Tun~ on et al. reported a water-based graphene ink with visco-
elastic property optimized to print self-supporting 3D structures
(Fig. 5b, c) [77]. They functionalized the GO with a responsive
copolymer surfactant to create ‘responsive’ graphene sheets whose
interactions in water can be regulated using an external stimulus
such as pH value. Using this approach, it was possible to formulate
water-based inks with viscoelastic properties suitable for printing
self-supporting 3D structures through nozzles with diameters
ranging from 100 to 500 mm.
The added polymer was still essential to achieve a printable
grapheneepolymer composite ink with highly viscous and non-
Newtonian fluid properties. To create a 3D periodic pure gra-
phene aerogel macroarchitecture without polymer, Worsley et al.
fabricated a high-viscosity printable GO suspension with concen-
tration as high as 40 mg/mL, which was gelation under (NH4)2CO3
basic conditions to directly cross-link graphene sheets via the
functional groups (for example, epoxide and hydroxide) (Fig. 5d, e)
[78]. Addition of hydrophilic fumed silica powders to the GO sus-
pensions imparted additional increases in viscosity. Silica filler
served as a removable viscosifier by imparting both shear thinning
behavior and a shear yield stress to the GO suspension to further
enhance the printability of the GO inks. Using this high-viscosity
GO ink, they printed woodpile, ‘simple cubic’elike lattices con-
sisting of multiple orthogonal layers of parallel cylindrical filaments
successively in a layer-by-layer fashion. A series of graphene aer-
ogel microlattices with varying thicknesses and a large-area gra-
phene aerogel honeycomb have also been fabricated, further
demonstrating the flexibility of this 3D printing technique. After
printing, the GO aerogel microlattices were thermally reduced at
1050
C and finally etched in hydrofluoric acid solution to remove
the silica nanoparticle filler. The obtained 3D graphene aerogel
microlattices were lightweight, highly conductive, and exhibited
super compressibility (up to 90% compressive strain). Fan et al. have
also reported the 3D printing of graphene aerogels and graphene-
based mixed-dimensional hybrid aerogels with complex architec-
tures (Fig. 5f) [79]. They used urea as a key precursor to trigger the
mild cross-linking of GO sheets by progressively releasing ammo-
nium ions during urea hydrolysis. Negatively charged 0D (Ag
nanoparticles), 1D (multiwall carbon nanotubes [MWCNTs]), and
2D (MoS2 nanosheets) materials were mixed with GO ink for
further extension to the fabrication of various mixed-dimensional
hybrid aerogels. Guo et al. [80] reported a highly stretchable neat
graphene/CNT binary carbon aerogel by 3D printing method
(Fig. 5gel). The aerogel was fabricated by ink-printing homoge-
neous aqueous mixtures of GO and purified CNT, followed by
freeze-drying and reduction under a confined state. Trace calcium
ions (15 mM) were added as gelator to enable readily direct writing
monolithic lattices under ambient surroundings. The programmed
direct writing allowed the design of bending-dominated macro-
lattices to control their tensile behaviors and Poisson ratios, e.g. the
re-entrant auxetic honeycomb with a negative, positive, and almost
zero Poisson ratio. Through such hierarchical synergistic assembly,
the binary aerogel showed preponderant elongation of ~200%. The
hierarchical buckled structures and synergistic reinforcement be-
tween graphene and CNTs enable a temperature-invariable,
recoverable stretching elasticity with small energy dissipation
(~0.1, 100% strain) and high fatigue resistance more than 106 cycles.
3.2. Template-directed CVD growth of 3D graphene network
structures
As mentioned previously, chemically derived graphene sheets
have shown great success in self-assembly and/or integration with
other materials such as polymers into various 3D macroscopic
network structures. However, these 3D integrated graphene
structures show poor electrical conductivity, owing to severe
structural defects in the chemically derived graphene sheets and
their high intersheet junction contact resistance. Alternatively, CVD
can synthesize graphene with high quality, although the yield is
low because of the limited growth area of flat metal substrates.
Dato et al. [81] developed a substrate-free gas-phase CVD method
to produce graphene sheets with a promising large scale, but the
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027 9

Fig. 5. Three-dimensionally printed graphene porous structures. (a) 3D printable graphene composite consisting of majority graphene and minority polylactide-co-glycolide for
variety of potential applications, including those relating to energy storage and bioelectronics, as well as tissue and organ engineering. (b) Building a filament pile through a 100-mm
nozzle with a low concentrated GO/BCS (branched copolymer surfactant) ink. (c) 3D printed graphene structures using robotic assisted deposition. (d) Optical image of a 3D printed
graphene aerogel microlattice. (e) SEM image of a 3D printed graphene aerogel microlattice. (f) 3D printing of graphene-based mixed-dimensional hybrid aerogels. (g) Schematic
illustration of the hierarchical synergistic assembly for fabrication of stretchable binary carbon aerogels (bCAs) through 3D printing (I) followed by freeze-drying (II) and prebuckled
reduction (III). (h) A digital photograph of ultralight bCAs with density of 5.7 mg/cm3 floating on a flower. (j-i) SEM images of a quaternary structure of bCAs across multisize scales.
Scale bars, 5 mm (d), 200 mm (e), 5 mm (h), 500 mm (i), 100 mm (j), and 5 mm (k). GO, graphene oxide; SEM, scanning electron microscope; MWNT, multiwall nanotube. Reproduced
with permission from Ref. [76](a) [77], (bec) [78], (dee) [79],(f) [80], (gel). Copyright: 2015 American Chemical Society (a), 2015 WILEY (bec), 2015 Macmillan Publishers Limited
(dee), 2018 American Chemical Society (f), 2018 Macmillan Publishers Limited (gel).
10 Z. Chen et al. / Materials Today Nano 5 (2019) 100027

produced graphene sheets were usually small. Cheng et al. pro-
posed a CVD method for bulk growth of monolayer to few-layer
graphene on Ni particles, instead of flat Ni substrate, to realize
the large-scale synthesis of high-quality graphene. A graphene
yield of about 2.5% of the weight of Ni particles was achieved within
a growth time of 5 min [82]. Considering the fact that graphene is
grown on the metal surface, it is reasonable to expect that various
3D graphene macrostructures can be obtained by choosing 3D
porous metal rather than flat metal as templates and growth sub-
strates. The CVD-grown 3D macrostructures enable the production
of graphene monoliths with seamlessly interconnected networks in
a large quantity. The morphology and composition of the templates
play key roles in modulating the geometric microstructures and
physical properties of the resultant 3D graphene structures. In this
section, we classify the CVD templates into metal and insulator,
both of which possess various morphology and pore structures.
3.2.1. Three-dimensional metallic templates
3.2.1.1. Metal foam. Cheng et al. [83] have developed a general
template-directed CVD strategy for synthesis of 3D graphene
macroscopic structures with a foam-like network, i.e. GFs (Fig. 6a).
Ni foam, a porous structure with an interconnected 3D scaffold of
Ni was chosen as a template for the CVD growth of GF. A thin layer
of graphene was first grown on the surface of Ni foam by decom-
posing methane at 1000
C under ambient pressure (Fig. 6aec).
After the CVD growth, a thin layer of PMMA was first coated on the
surface of the graphene as a mechanical support. Then, Ni substrate
was etched away by hot HCl/FeCl3 solution. Finally, the PMMA layer
was carefully dissolved by hot acetone, resulting in a monolith of
3D interconnected graphene network (Fig. 6def). Different from
the 3D graphene macroscopic structures constructed by small
pieces of chemically derived graphene sheets, the CVD-grown GF
was a monolith of graphene 3D network, in which charge carriers
can move rapidly with a small resistance through the high-
conductive and seamless graphene. The free-standing GF was
extremely light with an ultralow density of ~5 mg/cm3, close to that
of the lightest aerogel (2e3 mg/cm3), and corresponding to a high
porosity of ~99.7%. The GF also had a very high specific surface area
of ~850 m2/g. This template-directed CVD technique is versatile in
controlling both the macrostructure and the microstructure of GF
and can be a general strategy for fabricating a broad class of 3D
macroscopic structures of graphene and even other 2D materials.
Similar high-quality GFs have been achieved by other groups
using ethanol as the carbon source or with minor variations in flow
and temperature [84,85].
Using Cu foams as template, Cheng et al. [83] have also prepared
GFs with monolayer graphene sheets due to the surface-catalyzed
growth mechanism of graphene on Cu. However, such a GF ten-
ded to collapse and break because its building blocks, monolayer
graphene, were not able to bear the liquid capillary force caused by
acetone evaporation. Based the similar procedure, Kim et al. [86]
reported an intact and continue 3D GF using Cu foams as CVD
template, which was used as transparent conductive electrodes for
GaN-based blue lighteemitting diodes. By using a woven copper
mesh as the template, Zhu et al. reported a graphene-based woven
fabric (GWF) grown by CVD (Fig. 7b) [87]. The GWF retained the
network configuration of the copper mesh and was constructed by
interlacing two sets of graphene micron-ribbons where the ribbons
passed each other essentially at right angles. In this approach,
graphene was first grown on the surface of the copper mesh by
atmospheric CVD. After the copper wires were etched away by
FeCl3/HCl aqueous solution, the graphene was collapsed to form
double-layered graphene micron-ribbons. By controlling ratios and
spacing of these graphene micron-ribbons, GWF with different
conductivity and transparency can be obtained. The film trans-
parency was varied from 50 to 90% owing to the cavity of the GWF,
with resistance of 500e2500 U/sq and 200e1200 U/sq after HNO3
treatment.

Fig. 6. CVD growth of 3D interconnected GFs using Ni foam template. (a) Synthesis scheme of a GF. (bec) SEM images of the as-grown graphene films adhering to the surface of a Ni
foam. Ripples and wrinkles of the graphene films were observed. (d) Photograph of a 170  220 mm2 freestanding GF. (e) SEM image of a GF. (f) Typical Raman spectra of a GF. CVD,
chemical vapor deposition; GFs, graphene foams; SEM, scanning electron microscope. Reproduced with permission from Ref. [83]. Copyright: 2011 Macmillan Publishers Limited.
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027 11

Fig. 7. CVD growth of 3D graphene structures using metal templates. (a) Synthesis scheme of nanoporous graphene by CVD growth on nanoporous Ni template. (b) Optical images
of GWF films floating on water. Scale bars, 5 mm. (c) Schematics of powder metallurgy for preparation of 3D graphene foam. (d-e) SEM images of the predefined 3D pyrolyzed
photoresist films and the resulting well-defined 3D graphene structures, respectively. CVD, chemical vapor deposition; GWF, graphene-based woven fabric; SEM, scanning electron
microscope. Reproduced with permission from Ref. [90] (a) [87], (b) [95], (c), and [92] (dee). Copyright: 2014 Wiley (a), 2012 Nature Publishing Group (b), 2015 American Chemical
Society (c), and 2012 American Chemical Society (dee).
12 Z. Chen et al. / Materials Today Nano 5 (2019) 100027
Using the same Ni foam template-directed CVD method, Ruoff
et al. reported ultrathin graphite foam by precipitation of a very
thin layer of graphite on Ni foam and subsequent removal of the Ni
[88]. To obtain robust graphite foam, they exposed the Ni foam in
CH4 at 1050
C for 1 h and subsequently cooled slowly. In this
procedure, carbon can saturate the Ni foam at high temperature
and most of the Carbon precipitated at the surface of the Ni foam
struts during the slow cooling, forming a continuous graphite
coating with a wall thickness of tens of nanometers. The PMMA-
supporting layer was unnecessary when etching the Ni due to the
thick and rigid graphitic wall. The ultrathin graphite foam had a
density of ~9.5 mg/cm3 and a volume fraction of ~0.42 vol %, and the
solid electrical conductivity of the ultrathin graphitic wall within
the graphite foam was ~1.3  105 S m1 at 300 K.
The feature size of the as-obtained GF at a scale of 100 mm re-
mains extremely difficult to achieve 3D nanostructures with
multilevel porosity, which promises high surface areas and
enhanced ionic transport. By using porous Ni-Cu alloy engineered
from Ni foams via an electrodeposition/etching process, a 3D thin
graphite microstructure with tunable porosity was synthesized
[89]. Cu was first conformably coated on the entire surface of Ni
foam by electrodeposition followed by alloying at high temperature
of 1100
C. The obtained Cu-Ni alloy foam was etched electro-
chemically to form arrays of micropores with a controllable size
and morphology. By using such a 3D porous Cu-Ni template, thin
graphite layer can be readily grown via a low-temperature CVD. The
final resulted freestanding thin graphite microstructures possessed
two levels of porosity of 100 and 5 mm copied from the alloy
template.
3.2.1.2. Nanoporous Ni structures. To further decrease the pore size
of the graphene structures, Mingwei Chen et al. developed a
nanoporous Ni structure for template-directed CVD synthesis of 3D
nanoporous graphene structure with tunable pore sizes from
100 nm to 2 mm (Fig. 7a) [90]. The nanoporous Ni structure was
prepared as template by electrochemically leaching Mn from a
Ni30Mn70 alloy in a weak acid solution. The as-prepared Ni nano-
porous structure had an average nanopore/ligament size of ~10 nm.
Graphene was then grown on the surface of the nanoporous Ni
ligament structure by CVD at 900
C for 5e30 min under a mixed
atmosphere of H2, Ar, and benzene. The pore size of the graphene
can be tailored from 100 nm to 2 mm by controlling the CVD growth
time and temperatures. The nanoporous graphene was achieved by
dissolving the Ni substrate in a hydrogen chloride solution. The as-
prepared nanoporous graphene retained a 2D coherent electron
system of massless Dirac fermions and high electron mobility,
paving a new way for the practical application of graphene in 3D
devices in future. Moreover, nitrogen and sulfur codoped nano-
porous graphene can be also synthesized by using pyridine and
thiophene as carbon, nitrogen, and sulfur sources in the CVD
growth [91].
Xiao et al. [92] demonstrated a well-defined 3D graphene
nanoporous structures using predefined 3D pyrolyzed photoresist
films as template (Fig. 7dee). This 3D porous carbon had an
approximately face-centered cubic structure by interference
lithography method. The porous carbon structures were converted
into graphitic structures by sputtered with Ni film and annealed at
750
C in H2/N2 atmosphere for 50 min, resulting in a 3D inter-
connected multilayered graphene monolith structure with pore
sizes around 500 nm, which was two orders of magnitude smaller
than GF synthesis from Ni foam.
3.2.1.3. 3D-assembled Ni particles. After the report on the use of Ni
particles instead of flat Ni substrate for the bulk growth of graphene
sheets by CVD from CH4 [82], Shan et al. [93] also reported the CVD
growth of 3D graphene networks by using Ni powder as a sacrificial
template and PMMA as a solid carbon source. A mixture of Ni
powder and PMMA was introduced into a quartz tube at 1000
C
under low pressure, and then, graphene was precipitated on the
surface of Ni by fast cooling. The Ni was removed by dissolving in
HCl solution. The Ni powder agglomerated at high temperature and
generated 3D networks with many tiny holes for growth of gra-
phene. So, the graphene was interconnected into a 3D network and
did not aggregate after removal of Ni particles. Liu et al. developed a
rapid CVD growth of high-density 3D graphene macroscopic
structures on 3D porous cross-linked Ni skeleton obtained by
reduction of nickel chloride hexahydrate [94]. At the first step, the
nickel chloride hexahydrate precursors were reduced to form 3D
porous cross-linked Ni skeletons in Ar/H2 atmosphere at 600
C.
The highly efficient growth was then performed using methane as
carbon source for only several seconds to minutes. After removing
Ni skeletons by FeCl3/HCl solution, the 3D graphene macroscopic
structures with high conductivity (12 S/cm) and large specific
surface area (560 m2/g) were obtained.
Tour et al. reported a mesoporous freestanding 3D GF by powder
metallurgy and CVD approach [95]. Ni powders and sucrose were
mixed and cold-pressed into pellets, which acted as the CVD tem-
plate and solid carbon source, respectively (Fig. 7c). Graphene was
then grown by annealing the pellets in CVD furnace with an at-
mosphere of H2/Ar at a chamber pressure of ~9 Torr. Removal of the
Ni in FeCl3 aqueous solution resulted in the mesoporous 3D gra-
phene networks connected by particle-like carbon shells with size
of ~1 mm. The BET (Brunauer-Emmett-Teller method) specific sur-
face area of the 3D graphene network was up to ~1080 m2/g.
Moreover, it also showed an electrical conductivity of 13.84 S/cm
and a good resilience under loading of more than 150 times of its
weight. Using Ni powders and sucrose as the precursors, they have
further developed a laser-assisted 3D printing method for in situ
synthesis of freestanding 3D GFs [96]. The sucrose acted as the solid
carbon source, while the sintered Ni metal acted as the catalyst and
template for graphene growth. After removal of the Ni, a free-
standing 3D printed GF with the designed shape was obtained. The
method was simple and efficient, with no high-temperature CVD
furnace used and no extended growth process applied. The 3D
printed graphene showed high porosity (~99.3%), low density
(~15 mg/cm3), and high electrical conductivity (~8.7 S/cm). It also
had a remarkable storage modulus of ~11 kPa, as well as a high
damping capacity of ~0.06, comparable to the reported graphene
porous structures made by other processes. Zhu et al. have also
used a 3D printed Ni template for the fabrication of 3D graphene
structures [97]. In this process, they first 3D printed a framework
with pure Ni, which was then used as template for CVD growth of
graphene. However, the printed Ni framework with agglomerated
Ni particles had rough surface even after annealing at high tem-
perature. Besides Ni particles, Ni nanowires have also been used as
template for CVD growth of 3D porous graphene networks [98]. The
Ni nanowires were assembled into 3D foam-like structures by
either a simple filtration or pressing process. Graphene was then
grown on the surface of the Ni template at 670
C, resulting in an
interconnected porous graphene structure after the removal of Ni.
The obtained graphene porous structure displayed high electrical
conductivity (17.5 S/cm) and high mechanical stability under
deformation.
3.2.2. Three-dimensional insulator templates
Owing to the limited choice of metal templates, porous metal
oxides have become a new candidate for CVD growth of 3D porous
graphene structures because the metal oxides can actively
decompose the carbon source and deposit graphitic carbon on their
surface. For example, Mg(OH)2 sheets and MgAl double hydroxide
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027 13

plates were adopted as templates for CVD growth of mesoporous
graphene structures [99,100]. Especially, the graphene porous
structure derived by MgAl double hydroxide was composed of two
unstacked graphene layers separated by a large amount of meso-
sized protuberances (Fig. 8a, b). Before the CVD process, hexagonal
MgAl-layered double hydroxide plates (approximately 10 nm in
thickness) were calcined into mesoporous MgAl-layered double
oxide nanosheets, which maintained the initial plate-like
morphology and layered structure. Graphene was then grown on
both sides of the double oxide nanosheets and casted onto all the
mesoporous frameworks by CVD using CH4 as carbon source.
Removal of the nanosheet template resulted in mesoporous gra-
phene structures in hexagonal morphology with two unstacked
graphene layers separated by a large amount of mesosized pro-
tuberances. The graphene mesoporous structures showed a high
specific surface area of 1628 m2/g with large quantity of mesopores
with sizes of 2e7 nm. Silica aerogels have been also used as tem-
plates for direct CVD growth of monolith porous graphene struc-
tures [101]. The monolith silica template had a hierarchical macro/
mesoporous structure, and the graphene was grown on the tem-
plate by CVD at 1100
C. After the etching of the silica skeleton in
HF, the 3D graphene monolith can be obtained which inherited the

Fig. 8. CVD growth of 3D graphene structures using insulator templates. (a) Scheme for the synthesis of unstacked double-layer template graphene. (b) TEM images of the calcined
MgAl-layered double hydroxide with a well-preserved flake morphology after being treated at a high temperature of 950
C. (c) SEM image of 3D graphene nanonetworks created
from CVD growth of graphene followed by removal of iron. (d) Fabrication of scallop-derived 3D graphene foams. (e) Schematic diagram showing graphene growth on a diatom
frustule and its hierarchical biomorphic structures.(f) False color SEM image of a diatom frustule. (g) Morphology of a hierarchical biomorphic graphene flake, cross-section of its
central pores, and details of its marginal pores. (h) Fabrication schematic of ordered mesoporous few-layer carbon. (i) Possible locations for N incorporation into a few-layer carbon
network. CVD, chemical vapor deposition; TEM, transmission electron microscope; SEM, scanning electron microscope. Reproduced with permission from Ref. [100] (a, b) [105], (c)
[103], (d) [104], (eeg) [106], (h, i). Copyright: 2014 Nature Publishing Group (aeb), 2013 Nature Publishing Group (c), 2016 American Chemical Society (d), 2016 Nature Publishing
Group (eeg), 2015 Science Publishing Group (h, i).
14 Z. Chen et al. / Materials Today Nano 5 (2019) 100027
hierarchical micro/nanoscale structures. The graphene monolith
possessed a high specific surface area of 1590 m2/g and exhibited
an electrical conductivity of 25.2 S/cm, which can be further
enhanced up to 32.5 S/cm after annealing at 2200
C. Wang et al.
[102] synthesized a new type of graphene sheet with a 3D
honeycomb-like structure by a simple reaction between Li2O and
CO at a low temperature of 550
C, where the Li2O powder and the
by-produced Li2CO3 were used as the template for graphene as-
sembly. The graphene pore sizes were mostly in the range from 115
to 170 nm, and surface area was up to 153 m2/g.
To further decrease the cost of the 3D graphene structures, the
highly abundant natural seashells have been used as template for
CVD preparation of 3D GF structures [103]. The seashells composed
of biological calcium that can be calcined at 1050
C into calcium
oxide with highly porous framework (Fig. 8d). CaO framework was
then heated to 1020
C for graphene growth under a mixed-gas
atmosphere (CH4/H2/Ar). The layer numbers of the grown gra-
phene sheet were ranging from one to three layers and composed
of crystalline domain sizes of 2e10 nm. These polycrystalline gra-
phene films with nanometer grain size may suggest their relative
low quality and conductivity compared with those of graphene
grown on metal such as Ni. After washing the CaO framework away
using dilute acids, self-supporting 3D GFs with low density of
~3 mg/cm3 can be fabricated. Other naturally existing materials
such as diatomite have also been used for CVD growth of graphene
porous microstructures (Fig. 8eeg) [104]. Diatomite has versatile
microstructures comprising a porous layer of silica which was used
as the CVD growth templates. The individual graphene micro-
architectures preserved the 3D fine hierarchical structures of the
original diatom frustules after removal of the biosilica template.
Because of the hierarchical porous structures, the obtained gra-
phene powder exhibited high mesoporosity with a specific surface
area of 1137 m2/g. The curved nature of the graphene sheets
overcame the interlayer stacking and hence gave an excellent
dispersion performance in various solvents for fabricating solution-
processible electrodes. The graphene films derived from the as-
made graphene powders, compatible with either rod-coating or
inkjet and roll-to-roll printing techniques, exhibited a high elec-
trical conductivity up to 0.36 kU/sq or 1107 S/cm at 80%
transmittance.
Because of the low catalysis activity of the aforementioned
insulator templates, the obtained graphene possessed small grain
size and low quality. Therefore, metal sources have been used to
assist the CVD growth of higher quality graphene on insulator
templates. Yoon et al. [105] reported a 3D graphene nanonetwork
by precursor-assisted CVD on 3D-assembled colloidal silica tem-
plate (Fig. 8c). Graphene was grown on the colloidal silica infil-
trated with a PVA/iron precursor solution. Annealing the precursor
in a hydrogen environment reduced the iron, which can serve as a
catalyst for the dissolution of carbon during the subsequent gra-
phene growth process. The 3D graphene nanonetworks exhibited a
substantially improved geometrical surface area of 1025 m2/g and a
conductivity of 52 S/cm. Huang et al. reported a Ni-assisted CVD
method for synthesis of nitrogen-doped ordered mesoporous gra-
phene (Fig. 8h, i) [106]. The graphene was synthesized at 1000
C
using ordered mesoscopic silica impregnated with nickel (SBA-15/
Ni) as the template, polyfurfuryl alcohol and dicyandiamide as the
carbon and nitrogen source, respectively. Nickel-impregnated
templates (SBA-15/Ni) were prepared from SBA-15 by adding
Ni(NO3)2,6H2O solution, followed by drying and calcination under
H2/Ar (10%) flow at 450
C. After CVD growth, the template was
removed by HF etching, a self-supported ordered mesoporous few-
layer graphene superstructure remained. The nitrogen content in
the obtained graphene samples varied from 8.2 to 11.9 at% by
changing the amount of nitrogen source. Further modification of
the graphene sample by a HNO3 oxidation treatment partially
converted the N dopant into N-O. The ordered mesoporous nature
of the graphene superstructure was confirmed by electron micro-
scopy. The few-layer graphene tubes in the superstructure were
porous, containing pores 1e2 nm in diameter and separated by
aligned pore channels of about the same size of diameter. These
relatively homogeneous and uniform mesoporous textures were
largely casted from the SBA-15 template. Similarly, Ryoo et al. have
also reported a lanthanum-catalyzed CVD method for synthesis of
3D periodic nanoporous graphene-like carbons in a zeolite tem-
plate [107]. In this process, lanthanum-containing zeolite was used
as the CVD template, and they found that lanthanum ions
embedded in zeolite pores can serve as catalyst and lowered the
temperature down to 340e600
C for the carbonization of ethylene
or acetylene. The graphene-like carbon can then be selectively
formed inside the zeolite template rather than at the external
surfaces. Nanoporous graphene structures can be exactly repro-
duced with various topologies corresponding to different zeolite
pore sizes and shapes. For example, narrow channels (<0.56 nm in
diameter) in the MFI zeolite can still be used as a template for
graphene nanostructure synthesis, and the morphology of the
resulting graphene closely resembled that of the template with a
sharp peak centered at 0.49 nm in the pore size distribution. After
the zeolite template was removed, the graphene framework
exhibited an electrical conductivity that was two orders of
magnitude higher than that of amorphous mesoporous carbon. This
3D periodic nanoporous graphene architecture should promise a
wide range of applications in batteries, supercapacitors, catalysts,
and so on.
4. Applications of 3D graphene network structures
Compared with the aggregated graphene powders and gra-
phene thin films on substrates, the aforementioned 3D free-
standing graphene macroscopic structures show more unique
properties, such as interconnected network structure, high specific
surface area, and outstanding electrical and mechanical properties,
and should enable many applications, including high-performance
electrically conductive polymer composites, elastic and flexible
conductors, electrode materials for energy storage/conversion,
environment management, thermal management, sensors,
biomedical materials, and so on.
4.1. Polymer composite materials
Many carbon-based nanomaterials, including CNTs [108,109]
and graphene [10], have been used as conductive fillers for com-
posite materials because of their high electrical conductivity,
excellent mechanical properties, lightweight, and large aspect ratio.
For example, Ruoff et al. synthesized an electrically conductive
grapheneepolymer nanocomposite by solution-phase mixing of
the phenyl isocyanateetreated GO sheets with PS, followed by the
chemical reduction of GO sheets [10]. However, in these polymer
composites, individual conductive carbon-based fillers were
randomly distributed inside the polymer matrix and were sur-
rounded by the polymer chains, and therefore, the electrical con-
ductivity of these composites strongly relied on the electron
percolation between the separated filler particles. The relative low
quality of the chemically derived graphene sheets also compro-
mises the electrical conductivity of these composite materials. A
high content and good dispersion of graphene sheets are usually
required to form a conductive network in the insulating polymer
matrix to increase the electrical conductivity. However, if using the
3D graphene networks as the conductive additives for the com-
posites, a conductive interconnected network would have been
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027 15

ready-made for high-conductive composites with a low content of strain up to 20% and 5000 times bending (Fig. 9f). Ye et al. [112]
conductive additives (Fig. 9). fabricated an elastic GO/epoxy composite aerogel by freeze-
drying of mixed suspension of epoxy precursors and GO sheets,
followed by low-temperature curing. The resulting composite
4.1.1. Elastic conductors
showed a 3D porous network structure and exhibited extremely
The bulk synthesis of 3D graphene networks based on chemi-
low density (0.09 g/cm3) and excellent compressive strength
cally derived graphene sheets facilitates the fabrication and appli-
(0.231 MPa). Moreover, the composite was able to withstand repeat
cation of graphene-based composites. Huang et al. [110]
compression and recover with little permanent deformation.
synthesized an inorganiceorganic double network hydrogel of
The unique interconnected network of CVD-grown GFs exhibi-
graphene and poly(acrylic acid) (PAA) by a two-step process. A 3D
ted higher quality and conductivity than the chemically derived
graphene hydrogel was first prepared by a reduction-induced self-
graphene networks, therefore provided a greater potential for use
assembly process. After that, acrylic acid monomer was adsorbed
in high-conductive composite materials for electrical applications
into the graphene network and polymerized to the second PAA
[83]. As an example, Cheng et al. have fabricated a GF/PDMS com-
network. The obtained hydrogel composites were highly elastic,
posite by infiltrating GFs with PDMS matrix. The composite showed
which can be stretched to a high stain of 600%, with high Young
good flexibility, which can be bent, stretched, and twisted without
modulus and tensile strength of 0.27 GPa and 1.61 MPa, respec-
breaking. Infiltration of PDMS matrix did not damage the inter-
tively. Chen et al. [111] fabricated a highly conductive and
connected GF networks, and the electrons can move very quickly
stretchable composite by backfilling a preformed graphene/
through the seamlessly interconnected network. Therefore, the GF/
MWCNT aerogel with poly(dimethyl siloxane) (PDMS). The con-
PDMS composites showed an electrical conductivity as high as
ductivity of the composite was 2.8 S/cm with 1.3 wt% of graphene/
~10 S/cm at an ultralow graphene loading of ~0.5 wt% (~0.22 vol%).
MWCNT loading, which was more than 4 orders of magnitude
This conductivity value was ~6 orders of magnitude higher than
higher than that of the composite prepared by solution blending
that of polymer composites comprising chemically derived gra-
method. The synergistic effect of graphene and MWCNT signifi-
phene [10] and CNT [108,109] at the same loading fraction, sug-
cantly improved the electromechanical property of the composite
gesting the great advantages of using GFs in high-conductive
during stretching, resulting in only 30% decrease in conductivity at
composites. Moreover, the GF also improved the mechanical
30% of tensile strain. And the conductivity of the composite
properties of the PDMS matrix. The excellent electrical and
remained constant during 100 cycles of stretcherelease for tensile

Fig. 9. Polymer composites based on 3D graphene network. (a) Electrical resistance change of a GF/PDMS composite when bending to a radius of 0.8 mm and then straightening for
each cycle. The resistance change became stable after the third cycle. The left inset showed the resistance variation of the composite in a typical bend cycle after becoming stable.
The right inset showed the bending process. (b) Photograph of a GF/PDMS composite under stretching. (c) Photograph of a graphene/PDMS foam composite, showing its high
flexibility. (d) EMI shielding effectiveness of a graphene/PDMS foam composite before and after repeatedly bending to a radius of 2.5 mm for 10000 times. The left inset showed the
resistance change of the composite under repeated bending. The right inset showed a photograph of the bent composite. (e) Snapshots of a water droplet impacting the surface of
the Teflon-coated graphene foam. The impact velocity just before the droplet striking the surface was ~76 cm/s. The sequence of snapshots showed the deformation time history of
the droplet on impact. The droplet spreaded then retracted and successfully rebounded off the surface. The coefficient of restitution (i.e. ratio of droplet impacting velocity to
ejecting velocity) was ~0.37 for the Teflon-coated foam. (f) graphene/MWCNT aerogel/PDMS film as a function of stretchingereleasing cycles with 20% strain, the inset photo showed
the repeated stretching process. GF, graphene foam; PDMS, poly(dimethyl siloxane); EMI, electromagnetic interference; MWCNT, multiwall carbon nanotube. Reproduced with
permission from Ref. [83] (aeb), [117] (ced), [116] (e), and [111] (f). Copyright: 2011 Macmillan Publishers Limited (aeb), 2013 Wiley (ced), 2013 Wiley (e), and 2013 The Royal
Society of Chemistry (f).
16 Z. Chen et al. / Materials Today Nano 5 (2019) 100027
mechanical properties of the GF/PDMS composites together with
the unique network structure of GFs combined the advantages of
both material and structural layout for flexible and stretchable
conductor [83], which is a key component for stretchable and
curvilinear electronics such as sensory skins for robotics, structural
health monitors, and wearable communication devices [113]. The
resistance of the GF/PDMS composites increased ~2.7% only after
bending to a radius of 2.5 mm for 10000 cycles. Even bending to a
very small bend radius of ~0.8 mm, the increase of electrical
resistance remained constant after the fourth cycle, and the elec-
trical resistance under bending was only ~7% higher than that when
straightening (Fig. 9aeb). Moreover, the composites can sustain
large uniaxial tensile strain, and the resistance change of the
composites became stable after the fifth cycles of stretcherelease.
When the strain was released after the sixth cycle, the electrical
resistance was restored to a constant value. These results suggested
that the electromechanical properties of the GF/PDMS composites
under stretching were far superior to those of CVD-grown gra-
phene films [16] and comparable to those of both elastic conductors
fabricated using aligned CNT arrays [114] and CNT-based compos-
ites with a high loading (~20 wt%) of CNTs [115], opening great
potential of GF/PDMS composites for use as high-performance
elastic conductors. Jung et al. have also reported a highly dense
3D GF network by CVD growth on Ni nanowire for use as an elastic
conducting electrode [98]. The resulting 3D graphene exhibited
higher electrical conductivity of 17.5 S/cm. The GF network was
sandwiched between the PDMS matrix to form a hybrid composite
which exhibited excellent electrical and mechanical properties
under repeated mechanical deformations. The resistance of the 3D
GF network gradually increased up to 28% at a bending radius of
1.5 mm, and the resistance was fully recovered when the degree of
bending was relaxed during the 10 cycles. The measured electrical
resistance change tended to increase gradually from 13% to 138% as
the extent of stretching increased up to a maximum of 30%. But as
soon as the stretched substrate was released, the initial resistance
was almost recovered due to the high density of its interconnected
graphene networks.
4.1.2. Superhydrophobic foam materials
Different from the GF/PDMS composites fabricated by fully
infiltrating with PDMS, whose inner pores were sacrificed, Koratkar
and Cheng et al. have also fabricated a highly porous graphene/
polymer foam composite by coating only a thin layer of polymer,
such as Teflon on the GF surface [116]. The Teflon-coated foam
exhibited superhydrophobic behavior with a water contact angle of
~163.01
and ~143.78
, respectively, for advancing and receding
fronts. The microscale porosity (average pore size of ~200 mm) and
low surface energy offered the Teflon-coated foam outstanding
water repellency effect. Besides, the Teflon-coated foam can store
elastic strain energy from the impacting water drop, which was
then delivered back to the drop, making it finally rebounding off the
foam surface (Fig. 9e). Such flexible, superhydrophobic, and me-
chanically robust GF composites could be used in wide range of
applications, including self-cleaning, antifouling technologies, and
as low-friction coatings for micro-fluidics and lab-on-chip
applications.
4.1.3. Electromagnetic interference shielding materials
Chen et al. [117] also developed a one-step process for facile
fabrication of highly porous graphene/polymer composites. In this
process, graphene was first grown on Ni foam by CVD and formed a
3D network. Then, a thin layer of PDMS was coated on the surface of
graphene. After the Ni foam substrate was etched away by HCl, the
graphene/PDMS foam composite was obtained. The graphene/
PDMS foam composite obtained was lightweight, flexible, and soft,
with porosity up to ~95% and ultralow density of <0.06 g/cm3
(Fig. 9c). The electrical conductivity of the foam was as high as 2 S/
cm with a very low graphene loading of <0.8 wt% and demon-
strated high electromagnetic interference (EMI) shielding perfor-
mances. The EMI shielding effectiveness of the foam composite was
as high as 30 dB, with the specific EMI shielding effectiveness up to
500 dB cm3/g, which was about one order of magnitude higher than
those of typical metals and carbon/polymer composites [118e120].
Moreover, this foam composite showed excellent flexibility, and the
shielding effectiveness was almost unchanged after repeatedly
bending to a radius of ~2.5 mm for 10000 times (Fig. 9d). Zhang
et al. [119] have also reported grapheneepolymer nanocomposite
microcellular foam for EMI shielding. The microcellular foam was
fabricated by blending of PMMA with graphene sheets followed by
foaming with subcritical CO2 as an environmentally benign foam-
ing agent. The foam composite with graphene loading of 1.8 vol%
exhibited a high conductivity of 3.11 S/m1 and a good EMI shielding
efficiency of 13e19 dB at the frequencies of 8e12 GHz. Moreover,
the presence of microcellular cells greatly improved the ductility
and tensile toughness of the brittle grapheneePMMA
nanocomposites.
4.2. Energy storage
Owing to their high-conductive networks and large surface area,
3D graphene network structures have been intensely studied for
use as electrode materials in energy storage devices such as
supercapacitors and lithium-ion batteries (LIBs). The 3D porous
graphene electrodes with a high-conductive electron pathway and
a fast ion transport channel facilitate the energy storage devices
with both high energy density and power density.
4.2.1. Supercapacitors
4.2.1.1. Electrochemical double-layer capacitance.
Supercapacitors are attractive as alternative energy storage devices
to rechargeable batteries owing to their fast charging and dis-
charging rates with high power, long life cycle, a wide thermal
operating range, low weight, and easy maintenance [121,122]. The
commercial available supercapacitors are normally based on elec-
trochemical double-layer capacitance (EDLC) using activated car-
bon materials as electrodes. However, owing to the relatively high
electrical resistance of activated carbon, these supercapacitors are
limited in thickness and usually contain large amount of conductive
additives to enable rapid electrical charge transfer from the cell
[123]. The high conductivity, large surface area, and chemical sta-
bility of graphene make it a good candidate for use in EDLC. Stoller
et al. [123] pioneered the application exploration of CMG in
supercapacitors and achieved specific capacitances of 135 and 99 F/
g in aqueous and organic electrolytes, respectively, illustrating the
exciting potential for high-performance electrical energy storage
devices based on graphene. Although the graphene powder used in
this study consisted of agglomerated and restacked graphene
sheets, the specific capacitance was far below the theoretical value
of 550 F/g calculated for single-layer graphene (~21 mF/cm2) [124].
Integration of individual graphene sheet into 3D porous structures
can provide large accessible active surface areas for forming electric
double layers and a fast transport channel for electron and elec-
trolyte transportations in interconnected conductive networks. Xu
et al. [47] prepared a 3D porous graphene hydrogel by a one-step
hydrothermal method without other cross-linking agents. The
graphene hydrogel was cut into slices and used as the electrodes of
supercapacitors without using a binding agent and conducting
additive. The specific capacitance of the graphene hydrogel elec-
trode was evaluated to be about 160 F/g, which was much higher
than that of graphene powder electrodes [123]. However, its
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027
capacitance decreased greatly at a high discharge rate because of
the relatively low conductivity (5  103 S/cm) and large amount of
residual oxygenated groups of the hydrogel [125]. To improve the
conductivity and further remove the residual oxygenated groups,
they further reduced the graphene hydrogel with hydrazine or HI.
The chemically reduced graphene hydrogel showed a much higher
conductivity (1.3e3.2  102 S/cm), resulting in a higher specific
capacitance of 220 F/g at current density of 1 A/g. When the dis-
charging current density was increased up to 100 A/g, 74% of the
capacitance can still be maintained, and the power density was as
high as 30 kW/kg [125].
It is known that the performance of carbon-based super-
capacitors is highly dependent on both the accessible specific sur-
face area and pore structure. So, preventing the restacking of
graphene sheets and increasing the accessible specific surface area
of 3D graphene structures can further improve the performance of
graphene-based supercapacitors. For example, Yang et al. [126]
demonstrated a graphene hydrogel film using water as an effec-
tive ‘spacer’ to prevent the restacking of chemically converted
graphene sheets, and a specific capacitance of up to 215 F/g in an
aqueous electrolyte was achieved. A capacitance of 156.5 F/g can be
obtained even when the supercapacitor was operated at an ultra-
fast charge/discharge rate of 1080 A/g. When the water was
exchanged with ionic liquid and using ionic liquid as electrolyte,
the electrodes offered a specific capacitance of up to 273.1 F/g and
an energy density and maximum power density up to 150.9 Wh/kg
and 776.8 kW/kg, respectively. El-Kady et al. [70] developed a laser
scribing method for synthesis of 3D porous graphene films with a
higher surface area up to 1520 m2/g. The specific capacitance and
areal capacitance of the laser-scribed graphene-based super-
capacitors in ionic liquid electrolyte were as high as 276 F/g and
5.02 mF/cm2, respectively. Moreover, the laser-scribed graphene
can be built into flexible and all-solid-state supercapacitors for
next-generation flexible, portable electronics (Fig. 10 aec). The
bending had almost no effect on the capacitive behavior of the
flexible supercapacitors, and it can be bent arbitrarily without
degrading performance. This performance stability and durability
can be attributed to the high mechanical flexibility of the electrodes
along with the interpenetrating network structure between the
laser-scribed graphene electrodes and the gelled electrolyte. To
further increase the areal capacitance of the supercapacitors, Chen
et al. [127] deposited rGO hydrogel in the micropores of Ni foam to
form a graphene hydrogel/Ni foam composite electrode with a
much larger thickness (1 mm) compared with the reported high-
rate supercapacitors (ultrathin layers of electrode materials on a
nanometer or micrometer scale) [70,128,129]. The distances of ion/
electron transportation in the electrodes were shortened by the 3D
interconnected Ni networks. Owing to the large thickness of the
composite electrode, its areal capacitance was as high as 45.6 mF/
cm2, one order of magnitude higher than those of high-rate
supercapacitors based on other carbon materials such as onion-
like carbon [129] and laser-scribed graphene [70]. The aforemen-
tioned graphene porous structures used for supercapacitors usually
have micrometer or submicrometer pore size, but lack of well-
defined mesopores, which substantially limits the efficiency of
mass transport and charge storage. Müllen et al. reported a hier-
archical porous graphene structure by integrating small meso-
porous channels within interconnected macroporous graphene
aerogel frameworks [130]. This hierarchical porous graphene
structure showed an outstanding specific capacitance (226 F/g)
when used as electrodes of supercapacitor, which was much higher
than that of macroporous graphene aerogel, demonstrating a syn-
ergistic effect of macropores and mesopores.
Besides the aforementioned graphene porous structures syn-
thesized from GO by solution method, CVD-derived 3D graphene
17
nanoporous structures have also demonstrated high capacity and
rate performance for applications in supercapacitor. Yoon et al.
[105] fabricated a 3D graphene nanonetwork structure with a high
surface area of 1025 m2/g and conductivity of 52 S/cm by precursor-
assisted CVD method. The graphene structures showed superior
supercapacitor performance with a specific capacitance of 245 F/g,
and the capacitance loss was less than 13% when the current
density was changed from 5 A/g to 100 A/g. Wei et al. synthesized
gram-scale graphene nanomesh by template growth on porous
MgO layers [99]. The porous structure with large corrugations
helped preventing agglomeration of the nanomesh graphene
sheets, which preserved their large surface area of up to 1654 m2/g
and total pore volumes to 2.35 cm3/g. For the specific capacitance of
255 F/g obtained at 10 mV/s in 6 M KOH aqueous solution for
nanomesh graphene, the capacitance loss was only 21% with a scan
rate variation from 10 to 500 mV/s. Huang et al. reported the
coating of ordered mesoporous carbon on the surface of CVD-
grown highly conductive 3D GF, serving as both a charge collector
and flexible substrate [131]. On further decoration with silver
nanowires, the novel hybrid architecture exhibited exceptional
electrical conductivity (up to 762 S/cm) and mechanical robustness.
The hybrid structure was used as electrodes in flexible super-
capacitors reaching a specific capacitance as high as 213 F/g and
exhibited excellent long-term stability even under a bending angle
of 90
, as well as high energy and power density (4.5 Wh/kg and
5040 W/kg, respectively).
4.2.1.2. Pseudocapacitance. Although the EDLC-based super-
capacitors has some big advantages, especially on their long life
cycle and ultrafast charge and discharge rate, their specific capac-
itance and energy density need to be further increased. Besides the
EDLCs mentioned previously, another class of supercapacitors
based on pseudocapacitance can achieve much higher energy
densities, which is based on faradic, redox reactions using electrode
materials such as heteroatom-doped carbon materials, electrically
conducting polymers, and metal oxides [123]. Huang et al. have
fabricated a nitrogen-doped ordered mesoporous graphene struc-
tures by Ni-assisted CVD using ordered mesoscopic silica as tem-
plate [106]. The material obtained was made of highly conductive
(360 S/cm) mesoscopically ordered few-layer graphitic carbon with
a large surface area (1900 m2/g), which had demonstrated an un-
precedented high capacitance of 855 F/g in aqueous electrolytes
and can be bipolarly charged or discharged at a fast, carbon-like
speed (Fig. 10 def). The great improvement of capacitance mostly
relied on the robust redox reactions at nitrogen-doped defects,
which transformed the inert graphitic carbon into an electro-
chemically active material without affecting its electric conduc-
tivity. These bipolar aqueous electrolyte supercapacitors offered
power densities and lifetimes similar to those of carbon-based
supercapacitors and can store a high specific energy of 41 Wh/kg
(19.5 Wh/L), and the specific power was still as high as 26.0 kW/kg
(12.5 kW/L). These properties were notable for supercapacitor ap-
plications in that high specific power can be simultaneously ach-
ieved along with high specific energy, thus making carbon-based
supercapacitors potentially competitive against batteries. Ren et al.
reported an N-superdoped 3D graphene network structure with an
N-doping level up to 15.8 at% for high-performance supercapacitor,
in which CVD-grown GF with high conductivity acted as skeleton
and nested with N-superdoped rGO aerogels [132]. The hybrid
electrodes can achieve remarkably high capacitance of 380 F/g (in
alkaline electrolyte measured in three-electrode configuration) or
297 F/g (in alkaline electrolyte measured in two-electrode config-
uration), good cycling stability with 93.5% of the capacitance
retention after 4600 cycles, and low internal resistance of 0.4 U,
resulting in high power density with proper high energy density.
18 Z. Chen et al. / Materials Today Nano 5 (2019) 100027

Fig. 10. High-performance supercapacitors based on 3D porous graphene. (a) A schematic diagram of the all-solid-state electrochemical capacitor based on the laser-scribed
graphene. Inset: A digital photograph showing the flexibility of the device. (b) A comparison between performances of the electrochemical capacitor using gelled versus
aqueous electrolytes. Both devices showed similar capacitance values at all the tested charge/discharge current densities. (c) A shelf-life test showed excellent stability for more than
4 months without any obvious degradation. (d) Cyclic voltammetry (at 2 mV/s) from the first cycle for various ordered mesoporous few-layer carbon structures. (e) Capacity versus
square root of half-cycle time. Solid symbols, CV tested from 2 to 500 mV/s; open symbols, CC test data from 1 to 40 A/g. (f) Ragone plot of specific energy versus specific power for
ordered mesoporous few-layer carbon symmetric devices and several standard devices. Reproduced with permission from Ref. [70](aec) [106], (def). Copyright: 2012 Science
Publishing Group (aec), 2015 Science Publishing Group (def).

Müllen et al. synthesized a nitrogen and boron codoped monolithic
graphene aerogel by hydrothermal reaction of GO with ammonia
boron trifluoride [49]. The electrochemical behavior of the gra-
phene electrodes showed that the heteroatom doping can increase
the electrochemical activity and pseudocapacitance contribution,
resulting in an improved specific capacitance (239 F/g) compared
with the non-doping graphene aerogel (181 F/g). Qu et al. prepared
a nitrogen-doped 3D graphene framework by hydrothermal reac-
tion of GO and pyrrole solution, followed by freeze-dry and high-
temperature treatment [48]. The nitrogen-doped graphene elec-
trodes exhibited a specific capacitance of 484 F/g, which was
approaching to the theoretical EDLC capacitance of pure graphene,
and this is one of the highest capacitances that have been achieved
for graphene electrodes. In addition to the ultrahigh capacitance,
this graphene electrode also showed very high charge and
discharge rate. The capacitance can still reach 415 F/g even at a high
current density of 100 A/g. The outstanding performance of this 3D
porous graphene electrode may attribute to the highly exposed
graphene sheets with minimum stack and the possible pseudoca-
pacitance contribution of heteroatom doping. At the same time,
they also prepared a polypyrrole-mediated GF by hydrothermal
reaction of GO and pyrrole solution, followed by electrochemical
polymerization of the pyrrole monomer [133]. The hybrid elec-
trodes showed a specific capacitance of 350 F/g, which was much
higher than that of both compact polypyrrole film and pure 3D GF.
Moreover, the hybrid electrodes showed a highly compression-
tolerant behavior, and no significant change was observed in the
cyclic voltammetry curves when the electrodes were compressed
to 50% strain, demonstrating their excellent mechanical stability
and structural flexibility.
In addition to the heteroatom doping and electrically con-
ducting polymers, various metal oxides, another class of
pseudocapacitance-based electrode materials, can be used to
further improve the energy density of supercapacitors. However,
the phase changes within the electrode due to the faradic reaction
and the low conductivity limit their lifetime and power density. To
resolve this problem, metal oxides have been deposited on the
surface of CVD-grown GF to form a hybrid electrode, which
exhibited a combination of both high energy density and high
powder density (Fig. 11) [85,134e139]. The high surface area and
the porous network structures of GF provided ample area for
deposition and anchor of thin layer nanostructured metal oxides,
resulting in a short solid-state diffusion length and large interfacial
area for fast faradic reaction. Besides, the high-conductive inter-
connected graphene networks provided a highly conductive
pathway for electron and a fast transport channel for electrolytes,
which ensured the hybrid electrodes with fast charge and discharge
rate. For example, Chen et al. synthesized Co3O4 nanowires on a GF
network by hydrothermal reaction to form a hybrid electrode,
which exhibited high specific capacitance of 768, 618, 552, and
456 F/g at the current densities of 10, 15, 20, and 30 A/g, respec-
tively. And the specific capacitance of the hybrid electrode can be
further increased to ~1100 F/g after 500 cycle charge and discharge
at the current density of 10 A/g [138]. Using the similar procedure,
Huang et al. synthesized a hybrid Ni(OH)2 nanosheets/GF electrode
and achieved an ultrahigh capacitance of 1440 F/g at a charge and
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027 19

Fig. 11. Hybrid electrodes based on various metal oxide nanostructures grown on GF networks for supercapacitors. (a) Schematic of the structure of flexible supercapacitors
consisting of two symmetrical graphene/MnO2 composite electrodes, a polymer separator, and two polyethylene terephthalate (PET) membranes. The two optical photographs
showed the flexible supercapacitors when bended. (b) SEM image of typical graphene/MnO2 composite with mass loadings of 0.85 mg/cm2. (c) SEM image of 3D graphene/Co3O4
nanowire composite. (d) SEM image of the Ni3S2@Ni(OH)2/3D graphene network structure obtained at hydrothermal reaction time of 12 h. (e) SEM image of graphene/ZnO hybrids.
The inset showed the morphology of a single ZnO nanorod at a high magnification. (f) SEM image of Ni(OH)2 nanosheets/3D graphene network hybrid after the hydrothermal
process. (g) SEM image of MnO2 deposited on the surface of 3D graphene foams. (h) SEM image of NiO/graphene composites. GF, graphene foam; SEM, scanning electron mi-
croscope. Reproduced with permission from Ref. [136](aeb), [138] (c), [137] (d), [139] (e), [135] (f), [134] (g), and [85] (h). Copyright: 2013 American Chemical Society (aeb), 2012
American Chemical Society (c), 2013 The Royal Society of Chemistry (d), 2012 The Royal Society of Chemistry (e), 2012 Elsevier (f), 2012 Elsevier (g), and 2011 Wiley (h).

discharge current density of 10 A/g [135]. Even at a high current
density of 80 A/g, the capacitance was still as high as 890 F/g. The
performance comparison of the hybrid electrodes based on various
metal oxide nanostructures grown on CVD-grown GF networks is
shown in Table 1.
4.2.2. Batteries
4.2.2.1. Lithium-ion batteries. The LIB has a much higher capacity
than supercapacitors but usually suffers from a low charge/
discharge rate. Therefore, the fabrication of an electrochemical
energy storage system with supercapacitor-like fast charge/
discharge rate and battery-like high capacity is highly desired.
Three-dimensional porous hybrid electrodes with a highly
conductive pathway for electrons, a short ion diffusion length, and
a fast transport channel for the ion flux have been recently fabri-
cated to enable high-rate performance in LIBs [140e142]. For
example, Zhang et al. [142] fabricated a macroporous Ni network
for use as current collector in LIB electrodes with ultrafast charge
and discharge rates, in which 76% of the specific capacity was
retained when discharged at a high rate of 185C (where a 1C rate
represents a 1-h complete charge or discharge). However, these 3D
metal porous structures were heavy and had poor corrosion resis-
tance in electrochemical environments. Similar to these 3D metal
porous structures, 3D porous graphene structures also have high-
conductive interconnected network and high porosity. But the
graphene structures are lighter and have better mechanical flexi-
bility and corrosion resistance compared with metal-based struc-
tures. So, the 3D porous graphene structures show great promise
for use as high-performance LIB electrodes. Zhou and Liu [143] first
tried to directly use a rGO sponge prepared by thermal annealing of
freeze-dried GO sponge as the LIB electrodes. A highest reversible
capacity of 800 mAh/g at 50 mA/g can be achieved, which was
much higher than conventional graphite anodes. However, irre-
versible capacity of the graphene sponge electrodes was very large
due to the large surface area and plenty of active oxygen functional
groups. To overcome this problem and further improve the LIB

Table 1
Performance comparison of the hybrid electrodes based on various metal oxide nanostructures grown on GF networks.

Metal oxide nanostructures Discharge rate Capacitance (F/g) Stability References

Porous NiO 5e40 mV/s 573e816 80 mV/s, 15% increases, 2000 cycles [85]
1.4e20 A/g
ZnO nanorods 5e50 mV/s, 6.7e33.3 A/g 210e316 6.7 A/g, 20% increases, 1000 cycles [139]
Co3O4 nanowires 10e100 mV/s 456e768 10 A/g, 43% increases, 1000 cycles [138]
10e30 A/g
Ni(OH)2 nanosheets 5e50 mV/s 890e1440 20 A/g, negligible losses, 2000 cycles [135]
10e80 A/g
MnO2 nanoflower 0.2e1.2 A/g 250e560 0.2 A/g, 21% decrease, 1000 cycles [134]
Nanoporous MnO2 2e200 mV/s 175e465 3.75 A/g, 23% decrease, 5000 cycles [136]
Ni3S2 nanorod@Ni(OH)2 nanosheet 2e20 mV/s 716e1277 5.1 A/g, 1% decrease, 2000 cycles [137]
5.1e19.8 A/g

GF, graphene foam.

20 Z. Chen et al. / Materials Today Nano 5 (2019) 100027
performance, 3D hybrid structures were formed by deposition of
active nanostructured materials on 3D graphene networks, which
served as both highly conductive pathway for electrons/lithium
ions and light current collector. Chen et al. [58] prepared a 3D
graphene/Fe3O4 structure via an in situ self-assembly of graphene
by a mild chemical reduction of GO with NaHSO3 in the presence of
Fe3O4 nanoparticles. The hybrid structures were used as anode
materials for LIB, and the capacity was as high as 990 mAh/g when
the current density was below 800 mA/g, and it still remained at
730 mAh/g even at a high current density of 1600 mA/g. Feng et al.
synthesized a 3D graphene/Fe2O3 aerogel by hydrothermal treat-
ment of GO and FeCl3 solution [144]. The hybrid structures also
demonstrated improved durability and rate performance when
used as an LIB anode. After 50 cycles of charge/discharge at a cur-
rent density of 100 mA/g, the electrodes still showed a very high
reversible capacity of 995 mAh/g and delivered reversible capacity
as high as 372 mAh/g at a high rate of 5000 mA/g. To suppress the
aggregation of metal oxide nanoparticles and buffer the volume
expansion, Müllen et al. demonstrated an encapsulated structure
by electrostatic assembly of positively charged Fe3O4 nanoparticles
and negatively charged GO [145,146]. They further fabricated an
interconnected 3D graphene network by hydrothermal self-
assembly of the encapsulated structures with GO solution [146].
Such hierarchical graphene/Fe3O4 hybrids provided a high elec-
trical conductivity and double protection against the volume
changes of Fe3O4 nanoparticles during the electrochemical pro-
cesses. As a consequence, superior cycling performance (1059 mAh/
g over 150 cycles) and excellent rate capability (363 mAh/g at
4800 mA/g) were achieved when this hybrid structure was used as
anode materials for LIBs. Yang et al. have developed a strategy
leveraging sulfur as a sacrificial template to precisely control the
void space around SnO2 nanoparticles, including both its size and
location in a shrinking 3D graphene cage for superior volumetric
lithium storage [147]. This design fulfilled the most stringent re-
quirements for balancing the complete expansion of SnO2 and the
high density of the SnO2egraphene hybrids. The resultant
graphene-caged SnO2 delivered ultrahigh volumetric capacities of
2123 mAh/cm3 based only on the active materials and 1075 mAh/
cm3 based on the whole electrode, respectively, and also main-
tained a good cyclic stability.
To further improve the rate performance of LIBs, a better con-
ductivity of the 3D graphene networks and new design of the
hybrid structures are needed. Different from the 3D graphene
structures formed with small pieces of chemically derived GO
sheets, the CVD-grown GF was a monolith of 3D graphene network,
in which the electron can move rapidly with a small resistance
through the high-quality and continuous graphene networks.
Therefore, the CVD-grown GF showed much better electrical
properties compared with the GO-derived structures, therefore
may result in a better rate performance of LIB. For example, Tang
et al. [148] used the CVD-grown graphene networks as conductive
additives to improve the rate performance of a LiFePO4 (LFP)
cathode. The LFP/graphene electrode was prepared by simply stir
mixing the graphene networks with LFP powder suspension. Then,
a poly(vinyl difluoride) (PVDF) binder and acetylene black were
used in the fabrication of the LFP/graphene network electrode. This
LFP/graphene hybrid electrode showed a high-rate performance,
and even at the rate of 10C, the specific discharge capacity still
remained 109 mAh/g, which was 69% of its initial capacity, whereas
the capacity of the LFP electrode without graphene retained only
26% at the same discharge rate. However, the graphene conductive
network was broken during the stirring process, resulting in
damage to the unique structure and degradation in the charge/
discharge capability. Ruoff et al. impregnated a graphite network
with a slurry containing LFP, carbon black, and PVDF to form a
hybrid electrode for LIB [88]. Owing to the high-conductive
graphite networks, this 3D electrodes presented excellent electro-
chemical stability in electrolytes and enhanced both the rate per-
formance and specific capacity of the battery compared with
regular electrodes. However, the graphite networks used were
heavy and brittle than the thinner graphene networks. Besides, the
pores inside the graphite networks were blocked by the LFP slurry,
resulting in a slow transport channel for the lithium ion flux. Using
the 3D interconnected GF network as a high-conductive current
collector for electrons and ions, Li et al. [149] have developed thin,
lightweight, and flexible LFP/GF and Li4Ti5O12 (LTO)/GF electrodes
for LIBs by in situ hydrothermal deposition of active materials on
the surface of GF networks followed by high-temperature anneal-
ing (Fig. 12). No metal current collectors, conducting additives, and
binders were used. These 3D porous hybrid electrodes produced a
highly conductive pathway for electrons, a short ion diffusion
length, and a fast transport channel for a high Liþ flux, which
ensured the electrodes a great capability for fast charge and
discharge. The LTO/GF electrode showed a high charge/discharge
rate up to 200C (equivalent to a full discharge in 18 s), and the
specific capacity still retained 135 mAh/g (corresponding to ~80% of
the specific capacity at 1C rate). This high-rate performance was
much superior to the reference LTO electrode without GF, which
showed a capacity of almost zero at such a high rate. Similarly, the
LFP/GF electrode also showed an excellent high-rate performance,
and the specific capacity still retained 98 mAh/g even at a 50C
discharge rate. Using these flexible bulk electrodes, a thin, light-
weight, and flexible full LIB was assembled, which was capable of
repeated bending to a radius of <5 mm without structural failure
and performance loss. This flexible full battery can be operated at
10C rate with a capacity of 117 mAh/g, 88% of the capacity at 1C rate,
which surpassed most of the reported full batteries.
Mo et al. [150] have also synthesized a Ge quantum dot/
nitrogen-doped graphene yolkeshell nanoarchitecture on the sur-
face of nitrogen-doped GF to form an encapsulated hybrid struc-
tures (3D Ge-QD@NG/NGF) for high-performance flexible LIB. The
hybrid electrodes had high specific reversible capacity (1220 mAh/
g), ultrahigh-rate capability (more than 800 mAh/g at 40C), and
long cycling capability (more than 98% specific reversible capacity
retention from the second to 1000 cycles). The 3D Ge-QD@NG/NGF
yolkeshell structures not only provided internal void space to
alleviate the huge volumetric expansion of Ge during lithiation but
also provided an interconnected open channel for the easy access of
electrolyte and a high-conductive network for fast lithium ion and
electron diffusion. Moreover, the yolkeshell electrode exhibited
outstanding mechanical stability and flexibility. Compared with
that of the original flat state, only a negligible overpotential and a
<2% specific reversible capacity reduction can be observed at a
bending angle of 90
. Braun et al. demonstrated a 3D graphene/
electrochemically active material's sandwich structure for LIB with
high capacities and good rate performances [151]. Graphene was
grown via CVD on a Ni scaffold copied from opal. And a first layer of
V2O5 was then solvothermally grown onto the 3D graphene/Ni
scaffold. After the Ni scaffold was etched, another V2O5 layer was
grown and thermally treated into the inner layer of graphene,
forming a 3D sandwich nanoarchitecture electrode. The
V2O5@graphene@V2O5 cathode exhibited a gravimetric capacity
(full electrode basis) of about 230 mAh/g at 5C after 200 cycles, and
the capacity was still as high as 125 mAh/g even at 100C. They have
also fabricated a sandwich graphene@Si@graphene electrode as an
anode for LIB. After 200 chargeedischarge cycles at 0.4C, this
mesostructured anode exhibited a capacity of 2500 mAh/g.
4.2.2.2. Other batteries. Besides the aforementioned normal LIB, 3D
graphene network structures have also demonstrated great
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027 21

Fig. 12. Flexible LIBs with ultrafast charge and discharge rates based on GF networks. (a) Photograph of a freestanding flexible LTO/GF being bent (2  2 cm2). (b-c) SEM images of
the LTO/GF. (d) Discharging voltage curves of LTO/GF with different charge/discharge rates. (e) Capacities of LTO/GF charged and discharged at constant 30C and 100C rates for 500
cycles. (f) Lighting a red LED device by a full battery under bending. (g) Galvanostatic charging/discharging curves of the battery. Red and blue lines represent the as-fabricated flat
battery and the bent battery after repeatedly bending to a radius of 5 mm 20 times, respectively. (h) Cyclic performance of the battery under flat and bent states. LIBs, lithium-ion
batteries; GF, graphene foam; LTO, Li4Ti5O12; SEM, scanning electron microscope. Reproduced with permission from Ref. [149]. Copyright: 2012 National Academy of Sciences.

promise for the applications in lithiumesulfur [100,152,153] and
lithiumeoxygen [154,155] batteries and even aluminum-ion bat-
teries [156,157] because of their highly porous structures, rich
surface area, and high-conductive interconnected networks. Dai
et al. presented a rechargeable aluminum-ion battery with high-
rate capability that used an aluminum metal anode and a 3D
graphitic foam cathode (Fig. 13a, b) [156]. The flexible graphitic
foam made on a nickel foam template by CVD was developed for
the first time as a possible material for ultrafast aluminum batte-
ries, which greatly decreased the diffusion length for the inter-
calating electrolyte anions and thus facilitated fast charge and
discharge. Remarkably, the Al/graphitic foam cell could be charged
and discharged at a current density up to 5000 mA/g (75C), about
75 times higher than the Al/pyrolytic graphite cell while main-
taining a similar voltage profile and discharge capacity (~60 mAh/
g), suggesting the highly indispensable of the 3D graphitic foam
electrodes for such high-rate performance. An impressive cycling
stability with ~100% capacity retention was observed over 7500
cycles with a coulombic efficiency of 97 ± 2.3%. This was the first
time an ultrafast aluminum-ion battery has been constructed with
stability over thousands of cycles. The present Al/graphitic foam
battery can afford an energy density of ~40 Wh/kg (comparable to
leadeacid and NieMH batteries) and a high power density up to
3000 W/kg (similar to supercapacitors). Gao et al. have also
developed a 3D porous graphene film for ultrafast rechargeable
aluminum-ion batteries [157]. The graphene cathode possessed a
‘trihigh tricontinuous’ (3H3C) features of high quality, orientation,
and channeling for local structures (3H) and continuous electron-
conducting matrix, ion diffusion highway, and electroactive mass
for the whole electrode (3C), resulting in a high specific capacity of
around 120 mAh/g at ultrahigh current density of 400 A/g (charged
in 1.1 s) with 91.7% retention after 250000 cycles, which surpassed
all the previous aluminum-ion batteries in terms of rate capability
and cycle life. Owing to the flexible, continuous, and high-
22 Z. Chen et al. / Materials Today Nano 5 (2019) 100027

Fig. 13. Other kinds of batteries based on 3D porous graphene. (a) Scanning electron microscopy image showing graphitic foam with an open frame structure; scale bar, 300 mm.
Inset, photograph of graphitic foam; scale bar, 1 cm. (b) Long-term stability test of an Al/graphitic foam pouch cell over 7500 charging and discharging cycles at a current density of
4000 mA/g. (c, d) Images of fully discharged and charged rGO electrodes obtained with a 0.05 M LiI/0.25 M LiTFSI/DME electrolyte in the first cycle. Scale bar: 20 mm. (e) Discharge/
charge curves for lithiumeoxygen batteries using rGO electrodes and a 0.05 M LiI/0.25 M LiTFSI/DME electrolyte as a function of rate. (f, g) Schematic and TEM image of the structure
of nanoporous N-doped graphene layers and RuO2 particles. (h) Long cycle performance of the unstacked double-layer graphene/sulfur cathode for lithiumesulfur battery at 1, 5,
and 10C. LiTFSI/DME, lithium bis(trifluoromethyl) sulfonylimide/dimethoxyethane .Reproduced with permission from Ref. [156] (aeb), [154] (cee), [155] (feg), [100] (h). Copyright:
2015 Macmillan Publishers Limited (aeb), 2015 Science Publishing Group (cee), 2015 Wiley (feg), 2014 Macmillan Publishers Limited (h).

conductive graphene electrodes, the aluminum-ion batteries
exhibited excellent flexibility for wearable energy storage devices.
The capacity was completely retained after both 10000 times of
180
bending and following 500 battery cycles under 180
bending
state.
Grey et al. have demonstrated a highly efficient, rechargeable
lithiumeoxygen battery with extremely large capacities using a
macroporous rGO electrode and the redox mediator LiI in a dime-
thoxyethane (DME)-based electrolyte (Fig. 13cee) [154]. A
lithiumeoxygen battery was prepared using a Li metal anode, a
0.25 M lithium bis(trifluoromethyl) sulfonylimide/DME (LiTFSI/
DME) electrolyte with 0.05 M LiI additive, and a hierarchically
macroporous rGO electrodes (binder-free). The rGO frameworks
provided efficient diffusion pathways for all redox active species in
the electrolyte and hence, a reduced cell polarization and flatter
electrochemical profile. Moreover, it permitted the growth of LiOH
crystals with size of tens of micrometers, resulting in a capacity that
was much closer to the theoretical value of lithiumeoxygen bat-
teries, and excellent energy efficiency (93.2%) with a voltage gap of
only 0.2 V as well as an impressive rechargeability. Chen et al.
developed a 3D nanoporous cathode by encapsulating RuO2
nanoparticles using nitrogen-doped graphene (Fig. 13f, g) [155].
The framework of the 3D porous electrode was a high-conductive
graphene network grown on a nanoporous Ni template by CVD.
And the encapsulated RuO2 nanoparticles exhibited high catalytic
activities and ultrahigh stability. The freestanding nanoporous
graphene/RuO2-based lithiumeoxygen battery showed highly
reversible cathodic reactions for up to 100 times discharge/charge
cycles at the cutoff capacity of 2000 mAh/g and low average charge
potential of 3.7 V. The maximum rechargeable capacity at the
current density of 200 mA/g was up to 8700 mAh/g.
The large surface area and high porosity of the 3D graphene
network structures also enable ultrahigh sulfur loading for high-
performance lithiumesulfur batteries. For example, Duan et al.
reported a mechanically robust grapheneesulfur 3D porous com-
posite framework with the high sulfur weight content up to 90%,
which can be directly used as the sulfur cathode without additional
binders or conductive additives [152]. Besides acting as the high-
conductive pathway for electron and ion transport, the 3D gra-
phene framework can also function as an effective encapsulation
layer to retard the polysulfide shuttling effect, enabling a highly
robust sulfur cathode. Thus, the 3D grapheneesulfur framework
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027
cathode enabled a high-performance sulfur cathode with a record-
high capacity of 969 mAh/g when normalized by the weight of the
entire cathode at 0.1C and stable cycling endurance up to 500 times
at 1C with a capacity fading of 0.052% per cycle. Ren et al. reported a
3D hybrid graphene hierarchical network macrostructure, a CVD-
grown highly conductive GF nested with rGO aerogel (GFerGO),
as a current collector to simultaneously achieve high sulfur areal
loading (14.36 mg/cm2) and sulfur weight content (89.4 wt%) [153].
A high areal capacity of 10.3 mA h cm2 at 0.2 C rate with a good
cycling performance has been obtained. The areal capacity was
almost two times higher than that of the commercial LIBs, and the
cycling performance was even better than those reported for the
Liesulfur batteries with a much lower sulfur loading and sulfur
content. Wei et al. developed an intrinsically unstacked double-
layer graphene via template-directed CVD on MgAl-layered dou-
ble hydroxides (Fig. 13h) [100]. The obtained mesoporous graphene
structures showed a high specific surface area of 1628 m2/g and a
total pore volume of 2.0 cm3/g. The highly porous structure and the
expected high electrical conductivity (438 S/cm) derived from the
CVD-grown graphene made the as-fabricated graphene meso-
porous structures a promising cathode material for lithiumesulfur
batteries. The sulfur was homogeneously dispersed in the
unstacked double-layer graphene/sulfur nanocomposites with a
high sulfur loading of ~64 wt%. The as-fabricated lithiumesulfur
cells exhibited excellent high-rate performance because of the
high conductivity of the CVD-grown graphene layers and the
effective retention of sulfur within their mesoporous structures.
High reversible capacities of 1034 mAh/g and 734 mAh/g were
achieved at high discharge rates of 5C and 10C, respectively. Even
after 1000 cycles, high reversible capacities of 530 and 380 mAh/g
were retained at 5 and 10C, respectively. Li et al. reported a 3D
porous vanadium nitride nanoribbon/graphene hybrid structure as
the cathode of a lithiumesulfur battery [158]. The vanadium
nitride/graphene composite provided strong anchoring for poly-
sulfides and fast polysulfide conversion. The initial capacity
reached 1471 mAh/g and the capacity still retained 1252 mAh/g
after 100 cycles (a loss of only 15%), offering a potential for use in
high-energy lithiumesulfur batteries.
4.3. Energy conversion
Besides energy storage, 3D graphene network structures also
greatly improve the performances of energy conversion devices
including the fuel cell, solar cell, hydrogen evolution, and so on. The
3D graphene network structures are mainly used as the catalysts
and/or catalyst supports for chemical fuel cells, solar cells, and
hydrogen evolution. For microbial fuel cell (MFC), the large surface
area of the 3D graphene network structures is essential for bacteria
propagation. The high-conductive networks of the 3D graphene
structures play critical role in achieving fast charge transport for all
of these energy conversion devices.
4.3.1. Fuel cell/MFC
Development of high-efficient and low-cost electrocatalyst for
oxygen reduction reaction (ORR) and fuel oxidation reaction is the
key for large-scale applications of fuel cells. To date, the com-
mercial platinum (Pt)/C catalysts are the most extensively inves-
tigated catalysts because of their high catalytic activity for ORR.
However, the high cost of Pt and scarcity of Pt sources hamper the
further development of fuel cell. Besides, an insulating PTFE binder
is needed for incorporating the Pt/C powder catalysts into the real
fuel cell electrodes, which decreases the Pt utilization and the
conductivity of the electrodes. Graphene-based materials have
been demonstrated as promising catalysts and catalyst support for
chemical/electrochemical reactions due to their high conductivity,
23
large surface area, and excellent chemical/electrochemical stabil-
ity [159]. Furthermore, 3D graphene structures have been
demonstrated special advantages for use as catalysts and elec-
trodes in fuel cells because the high-conductive interconnected
graphene networks are beneficial to rapid charge transfer and ion
transfer kinetics, and the large accessible graphene surface pro-
vides strong adhesion for catalyst particles and special reaction
microenvironment. Recently, Maiyalagan et al. [160] demonstrated
the pulsed electrochemical deposition of Pt nanoparticles on CVD-
grown GF networks for use as catalytic electrodes toward meth-
anol oxidation in direct methanol fuel cells. The peak current
density of the forward anodic peaks of the GF/Pt electrodes was
approximately 1.6 mA/cm2, nearly two times the peak current
density of the carbon fiber/Pt electrodes and even higher than that
of commercial Pt/C catalysts (1.39 mA/cm2) [161]. Distinct from
previous strategies, Lim et al. synthesized monodispersed Pt
nanoparticles with ultrafine particle size (~3 nm) on GF networks
using ferritin protein nanocages as the template and subsequently
self-assembled on the GF surface [162]. The obtained GF/Pt elec-
trodes exhibited a high electrocatalytic activity for methanol
oxidation with a peak current density of 2.5 mA/cm2, which was
much higher than that of pulsed electrochemically deposited GF/Pt
and commercial Pt/C catalyst [160]. As substitute for precious
metals, non-noble metal and metal oxides are attracting interest
because of their low cost, electrochemical stability, resistance to
poisoning, and high catalytic activity. However, the low conduc-
tivity and agglomeration of these metal and metal oxide nano-
particles often restrict their electrocatalytic performance. With
this respect, Chen et al. demonstrated the electrochemical depo-
sition of Co3O4 on 3D CVD-grown GF networks to form hybrid
electrodes as both the anode for glucose oxidation and the cathode
for oxygen reduction in enzyme-free biofuel cells (Fig. 14aec)
[163]. The fuel cell was able to efficiently harvest electricity from
various sweet biofuels, for example, the glucose-powered fuel cell
offered high open circuit voltage (1.1 V, close to the theoretical
limit), high power output (2.38 mW/cm2), and long-term stability
(only 27% run-down after 30 days). Ren et al. [164] synthesized a
3D Ni/graphene aerogel through the self-assembly aggregation of
graphene accompanied with Ni nanoparticle during the hydro-
thermal reduction of GO and Ni ions. The hybrid electrodes
exhibited high electrochemical catalytic properties for ethanol
oxidation with a high peak current density of ~6 mA/cm2 in 0.1 M
ethanol and 0.1 M NaOH solution, showing great potential for
application in direct ethanol fuel cells. Müllen et al. synthesized a
Fe3O4/N-doped graphene aerogel by hydrothermal self-assembly
process, which was used as efficient cathode catalysts for ORR
(Fig. 14f) [165]. Compared with Fe3O4 nanoparticles grown on N-
Doped graphene sheets and carbon black, the Fe3O4/N-doped
graphene aerogel exhibited a pronounced electrocatalytic ORR
activity associated with a more positive ORR onset potential
(0.19 V) and higher cathodic current density (2.56 mA/cm2).
Besides acting as support for metal and metal oxide nanoparticles,
graphene sheets and 3D graphene porous structures were also
directly used as metal-free catalysts for ORR [166] and various
synthetic reactions under mild conditions [42,159,167,168]. For
example, Qu et al. demonstrated a nitrogen and boron codoped
GFs (BN-GFs) as metal-free catalyst for ORR (Fig. 14dee) [166]. The
BN-GFs with codoped nitrogen (4.5 atom %) and boron (3 atom %)
were prepared by CVD using melamine diborate as the precursor.
Electrochemical measurements of the BN-GFs electrodes showed
much higher electrocatalytic activities toward ORR than their
undoped counterparts. And the BN-GFs electrodes exhibited a very
slow attenuation with a high current retention (89%) after 20000 s,
showing a higher stability than the noble Pt catalyst (40% current
loss) toward ORR.
24 Z. Chen et al. / Materials Today Nano 5 (2019) 100027

Fig. 14. High-performance fuel cell based on 3D porous graphene. (a) Illustration of the glucose-powered fuel cell based on a 3D graphene/Co3O4 anode and cathode. (b) The
maximum power output at different concentrations of glucose, sucrose, or b-lactose or their mixture (50 mM glucose, 25 mM sucrose, and 25 mM b-lactose). (c) The device image
showing a yellow LED powered by two fuel cells in series. (d) Rotating disk electrode voltammograms of the undoped GF electrode, the B-GF electrode, the N-GF electrode, the BN-
GF electrode, and the Pt-C electrode in oxygen-saturated 0.1 M KOH solution at a rotation rate of 1600 rpm. Scan rate: 10 mV/s. (e) Current-time chronoamperometric response of
the BN-GF electrode and the Pt-C electrode at 0.25 V in O2-saturated 0.10 M KOH. (f) SEM image of Fe3O4/N-doped graphene aerogel revealing the 3D macroporous structure and
uniform distribution of Fe3O4 nanoparticles in graphene aerogel. (g-h) SEM images of graphene/PANI electrodes after 60-h incubation in MFC with S.oneidensis MR-1 cell sus-
pension. (i) Polarization curves of the two types of MFCs, the inset showed the I-V relation. GF, graphene foam; BN-GF, boron codoped GF; SEM, scanning electron microscope; PANI,
polyaniline; MFC, microbial fuel cell. Reproduced with permission from Ref. [163] (aec), [166] (dee), [165] (f), [170] (gei). Copyright: 2013 Owner Societies (aec), 2013 Owner
Societies (dee), 2012 American Chemical Society (f), 2012 American Chemical Society (gei).

Unlike the chemical fuel cells that recover energy from purified
fuels, such as hydrogen, methane, and ethanol, the MFC can convert
chemical energy in organic wastes into electricity and integrate
environmental bioremediation with power production. The MFC is
a sustainable and green energy source and represents a galvanic
cell that produces electric current by integrating: (i) bio-
electrochemical oxidation of organic matter at the anode and (ii)
abiotic reduction of electron acceptor at the cathode. The bacterial
loading capacity and extracellular electron transfer efficiency be-
tween the bacteria and the electrodes are the key points for high-
performance MFC. Three-dimensional porous graphene macro-
structures provide a large surface area for propagation of bacteria
and a high-conductive interconnected network for electron trans-
fer. Therefore, 3D porous graphene macrostructures show great
promise for use as high-performance MFC electrodes. Cui et al.
prepared a 3D porous graphene/polyurethane sponge by a simple
and scalable dipping-and-drying process [169]. The composite
sponge showed a conductivity of 0.01 S/cm and achieved a
maximum power density of 0.111 W/m2 when it was directly used
as an MFC anode. However, the conductivity of this graphene
composite sponge was still too low for high-performance MFC
because of the low quality and/or high intersheet junction contact
resistance of the sonication-derived graphene sheets. To address
this issue, a stainless steel mesh was incorporated in graphene/
polyurethane sponge as a current collector to achieve fast electron
pathways, which enabled a maximum power density of 1.57 W/m2,
14 times that of sponge without a stainless steel current collector.
Yong et al. [170] used a much more conductive CVD-grown GF as an
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027
MFC anode for higher performance (Fig. 14gei). To overcome the
highly hydrophobic feature of the graphene surface and promote
bacteria adhesion and biofilm formation, hydrophilic conducting
polyaniline (PANI) was first decorated on the surface of GF through
in situ polymerization. The charge-transfer resistance of GF/PANI-
based MFC (~100 U) was much smaller than that of the carbon
clothebased MFC (~2800 U), suggesting a faster electron transfer
rate in 3D GF/PANI anode. The maximum power density of the MFC
based on GF/PANI was 0.768 W/m2, which was about four times
higher than that of MFC based on the carbon cloth. Metal materials
also have very high conductivity and are usually used as current
collectors in the MFC [169]. However, metal anodes are strongly
susceptible to galvanic corrosion in MFCs. Nikhil et al. have
demonstrated that conformal CVD growth of graphene on the
surface of 3D porous Ni foam can act as an efficient passive layer
that retarded microbially induced galvanic corrosion of Ni foam
electrodes for an extended MFC operating period of time up to
~27:00 h [171].
4.3.2. Solar cell
A solar cell is an electrical device that converts the energy of
light directly into electricity by the photovoltaic effect. The solar
cell has been regarded as one of the most potential candidates to
replace petroleum fuels in the future due to its clean, free, and
inexhaustible features. Emerging research topics and preindustrial
technology in solar cells include dye-sensitized solar cells (DSSCs),
quantum dot solar cells (QDSCs), thin film solar cells (TFSCs),
organic/polymer solar cells, etc. Owing to its high conductivity and
high transparency, many efforts have been made to apply trans-
parent conductive graphene film as alternative to the ubiquitously
used metal oxides window electrodes for various solar cells
[172e174]. Alternately, it is also suitable to use 3D graphene
structures as back/counter electrodes and photocatalyst additives
for metal-free solar cells because of their high conductivity, large
reactive surface area, and unique electrocatalytic properties. Dai
et al. prepared an N-doped graphene porous structure by annealing
the freeze-dried GO structures in ammonia [175]. The resultant 3D
foam-like graphene structure had a high nitrogen content of 7.6%
and was used as metal-free electrocatalyst for the reduction of
triiodide to replace the Pt cathode in DSSCs (Fig. 15aec). The solar
device showed power conversion efficiency as high as 7.07%. This
value was among one of the highest efficiencies reported for DSSCs
with a metal-free carbon-based counter electrode and was com-
parable to that of DSSCs with a Pt counter electrode (7.44%) con-
structed under the same condition. Wang et al. [102] developed a
novel strategy for the synthesis of a 3D honeycomb-like graphene
structure by a simple reaction between Li2O and CO. The graphene
structures exhibited excellent catalytic performance as a counter
electrode for DSSCs with a high power conversion efficiency of 7.8%
and a high power density of 100 mW/cm2 under illumination of
AM1.5 simulated sunlight. This efficiency was 10-times higher than
that of the DSSC with a chemical exfoliated graphene-based
counter electrode (0.64%) and was even comparable to that of a
Pt-based DSSC (8%). Tang et al. [176] prepared a high-conductive
P25-based photoanode for high-performance DSSCs using CVD-
grown GF networks as conductive additive. The obtained hybrid
photoanode exhibited better dye absorption abilities and electron
transport kinetics. A high efficiency of 6.87% was obtained for the
DSSC by adding 1 wt% of GF networks in the photoanode, much
higher than that of pristine P25-based DSSC (4.96%). Furthermore,
they also used the GF networks as a counter electrode for DSSC, and
an efficiency of 5.83% was achieved, which was only a little lower
than that of DSSC with Pt as a counter electrode (6.87%) under
identical conditions.
25
Besides DSSCs, 3D graphene structures have also been used as
back/counter electrodes for other solar cells such as TFSCs [84] and
QDSCs [69]. Huang et al. fabricated a CdTe-based TFSC using CVD-
grown GF networks as back electrodes (Fig. 15deg) [84]. An over-
all power conversion efficiency of 9.1% was achieved, which was
superior to CdTe-based TFSC with back electrodes based on rGO, B-
doped graphene, and CNTs. Lee et al. synthesized a 3D foam-like
graphene structure by nucleate boiling method for use as a
counter electrode of QDSCs (Fig. 15hej), which exhibited a slightly
better overall efficiency (3.6%) than a conventional gold electrode
(3.4%) and much better than an rGO electrode (1.4%) [69].
4.3.3. H2 production
Development of high-efficient catalysts for hydrogen evolution
reaction (HER) is critical for the applications of clean hydrogen
energy. Three-dimensional Ni foam deposited with graphene layers
on its surface has been used as a conducting solid support to load
MoSx catalysts for electrocatalytic HER [177]. To grow MoSx cata-
lysts on the graphene surfaces, the graphene-protected Ni foam
was immersed in an ammonium thiomolybdate solution, followed
by annealing at various temperatures. The highly conductive 3D
graphene/Ni foam structure not only effectively increased the
catalyst loading but also decreased the resistance of the electrodes,
leading to the improvement in electrocatalytic HER efficiency. The
highest hydrogen production rate was around 13.47 mmol/g cm2 h1
(302 mL/g1 cm2 h1) at a potential of 0.2 V, which was higher
compared with the MoSx grown on various planar carbon elec-
trodes, including carbon paper, carbon cloth, and graphene mats.
Ito et al. [91] reported a nitrogen and sulfur codoped graphene
nanoporous structure, which was grown on nanoporous Ni tem-
plate by CVD. The coupling between chemical dopants and the
geometric lattice defects in 3D nanoporous graphene offered
excellent catalytic activities toward HER with low operating po-
tential. Lower CVD temperatures down to 500
C gave rise to higher
N and S concentrations and more defective graphene structures
with high surface areas of 1320 m2/g and an average pore size of
90 nm. These chemically doped nanoporous graphene showed the
best HER activities with an onset potential of 0.13 V, Tafel slope of
80.5 mV/dec, and operating potential of 0.28 V at 10 mA/cm2,
among one of the best metal-free catalysts in HER known to date.
4.4. Sensors
Individual graphene sheet has been demonstrated as ultrasen-
sitive gas sensor [178]. The exceptional band structure together
with large surface area provides graphene ultrahigh sensitivity,
where the surface absorbents including gas molecules can greatly
alter its electronic property and carrier density. Owing to their
excellent conductivity, large surface area coupled with high
porosity, the macroscopic and continuous 3D GF networks have
been used for high-sensitive detection of NH3 and NO2 at room
temperature and atmospheric pressure (Fig. 16aeb) [179]. The GF
network offered high sensitivity for gas detection in the ppm range.
Because the walls of GF were comprised on average of only few-
layer graphene films, the charge carrier transport through the GF
network was highly sensitive to the adsorption/desorption of gas
species. The high porosity of GF made it easy for gas molecules to
infiltrate uniformly into the entire surface, resulting in high sensi-
tivity and stable operation of the device. Moreover, Joule heating
can be used to expel the adsorbed gas molecules on GF, leading to
fast and fully reversible operation. Besides gas sensor, GF network
has also been used as electrodes for electrochemical sensors for
detection of dopamine [180]. The 3D porous structure of GF
ensured efficient mass transport of redox species and electrolyte to
the surface of GF electrode. And the interconnected and high-
26 Z. Chen et al. / Materials Today Nano 5 (2019) 100027

Fig. 15. High-performance solar cell based on 3D porous graphene. (a) Preparation route of the N-GF counter electrode. (b) DSSC with an N-GF counter electrode. (c) Triiodide
reduction on the N-doped graphene surface. (d) SEM cross-section image of a graphene film and top-view of the graphene film in the inset. (e) Schematic CdTe solar cell with a 3D
graphene back electrode. (f) Band structure of the graphene-based CdTe solar cell. (g) JeV characteristics of CdTe solar cell with a graphene back electrode. (h) Schematic diagram of
SFG-based quantum dot sensitized solar cells (QDSSCs). (i) Schematic and real image of SFG-based QDSSCs. (j) Performance of Au-, 2D rGOe, and SFG-based QDSSCs. DSSC, dye-
sensitized solar cell; SEM, scanning electron microscope. SFG, self-as-sem-bled foam-like graphene. Reproduced with permission from Ref. [175] (aec), [84] (deg), and [69] (hej).
Copyright: 2012 Wiley (aec), 2011 The Royal Society of Chemistry (deg), and 2013 Nature Publishing Group (hej).

conductive networks provided a fast electron pathway for rapid
and sensitive detection. As a result, the GF electrodes exhibited
remarkable sensitivity (0.619 mA/mM cm2) and lower detection
limit (25 nM at a signal-to-noise ratio [S/N] of 5.6), with linear
response up to ~25 mM. Moreover, large surface area and numerous
wrinkles and ripples of GF could provide plenty of surface and
active sites for high mass loading of electroactive materials such as
metal oxide nanostructures, metal nanoparticles, and MWCNTs for
improved sensor performance. For example, Chen et al. synthesized
Co3O4 nanowires/GF hybrid electrodes by the hydrothermal
method for non-enzymatic detection of glucose, which exhibited a
ultrahigh sensitivity of 3.39 mA/mM cm2 in the linear response
range (up to 80 mM) and a remarkable lower detection limit of
<25 nM (S/N ¼ 8.5) (Fig. 16cee) [138]. Zhang et al. deposited
MWCNTs on the surface of GF networks to form hybrid electrodes,
which was subsequently anchored with Pt nanoparticles [181]. The
composite electrode exhibited a significantly improved detection
limit to H2O2 (8.6 nM) and a linear detection range from 0.025 to
6.3 mM (Fig. 16f). Comparison of electrochemical sensor perfor-
mance of hybrid electrodes based on several electroactive materials
grown on GF networks is summarized in Table 2 [138,139,181e183].
Besides of the aforementioned chemical sensors, Gao et al. have
fabricated a strain sensor for logic identification of sophisticated
shape conversions based on highly stretchable neat graphene/CNT
binary aerogel by 3D printing method [80]. The freestanding gra-
phene/CNT binary aerogel with high electrical conductivity
(~1000 S/m after 3000 K thermal annealing) can be reversibly
stretched (positive strain) and compressed (negative strain). For a
binary aerogel with a designed strain from þ100% to 20%, the
resistance gently increased (þ10% at þ100% strain) under stretch-
ing and steeply decreased (80% at 14% strain) under compress-
ing, due to the corresponding stretching-collapsing structural
evolution of the interconnected polygon cells. The resistance
change pattern of the binary aerogel kept nearly identical in the
cyclic deformation for at least 100 times. Therefore, this graphene/
CNT aerogel can act as a new generation of strain sensor to express
three logic digits and has been attached onto the junctions of a
snake-like robot as a strain sensor array to monitor its movement
and configurations.
4.5. Environmental management
Environmental protection is an increasing urgency for higher
quality of human life. Water contamination by oil spills, organic
solvent, dyes, and heavy metals is one of the most serious envi-
ronmental problems. It is imperative to develop novel materials
that can effectively absorb and remove these contaminations from
water. The materials for adsorption must have high porosity, large
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027 27

Fig. 16. High-performance chemical sensors based on 3D GF networks. (a) Corresponding adsorption and desorption response of GF sensor where Joule heating of the sample was
operated during the desorption step. (b) Normalized resistance change vs. time for different concentrations of NH3 in air. The adsorption step was performed at room temperature,
while Joule heating to ~400 K was used during desorption. (c) Amperometric response of the GF/Co3O4 composite electrode (holding at 0.58 V) on addition of glucose to increasing
concentrations. (d) Average dose response curve (amperometric current response vs. glucose concentration) obtained from three different GF/Co3O4 sensors, with a linear fitting at a
lower concentration range and an exponential fitting at a higher concentration range. The error bars indicated the standard deviations. (e) Amperometric response of GF/Co3O4
sensors to 25 nM glucose. An exponential fitting with a time constant of ~3.7 s was shown. (f) The amperometric response of the GF/MWCNTs/Pt composite electrodes to H2O2.
Inset: the lowest H2O2 concentration detected by the corresponding composite electrodes. GF, graphene foam; MWCNTs, multiwall carbon nanotubes. Reproduced with permission
from Ref. [179] (aeb), [138] (cee), and [181] (f). Copyright: 2011 Nature Publishing Group (aeb), 2012 American Chemical Society (cee), and 2012 Wiley (f).

Table 2
Comparison of electrochemical sensor performance of several GF-based electrodes.

Electrode Analyte Detection limit (nM) Linear detection range (mM) Sensitivity (mA mM1 cm2) References

GF Dopamine 25 Up to 25 0.619 [180]

GF/Co3O4 Glucose 25 Up to 80 3.39 [138]
GF/MWCNTs/Pt H2O2 8.6 0.025e6.3 e [181]
GF/Pt H2O2 125 0.167e7.486 e [181]
GF/MnO2 H2O2 270 0.38e13.46 e [181]
GF/MWCNTs Dopamine 20 2e64 0.47 [183]
GF/MWCNTs/horseradish peroxidase H2O2 1000 10e1000 0.138
GF/Mn3O4 Glucose 10000 100e8000 0.36 [182]
H2O2 1000 2e6500 1.03
GF/ZnO [Fe(CN)6]3þ 10 Up to 800 7  105 [139]
Dopamine 1000 Up to 2 0.015

GF, graphene foam; MWCNTs, multiwall carbon nanotubes.

surface area, low density, and good environmental friendliness, and used natural materials such as expanded perlite and zeolites,
for absorption of organic contamination, superhydrophobicity and microporous polymers, active carbon, nanowire membranes, CNT
superoleophilicity are also favorable. Recently, 3D porous graphene sponge, and expanded graphite (Table 3)
and graphene-based hybrid structures have been demonstrated as [41,45,48,50,60,71,94,184e188]. For example, Qu et al. prepared a
high-efficient recyclable absorption materials with better adsorp- nitrogen-doped 3D graphene framework by hydrothermal reaction
tion capacity for various water contaminations than the commonly of GO and pyrrole solution. Owing to its ultralow density of 2.1 mg/
28 Z. Chen et al. / Materials Today Nano 5 (2019) 100027

Table 3
Comparison of contamination sorption capacities of carbon-based sorbents.

Sorbents Contamination Absorption capacity References

N-doped graphene frameworks Liquid organics 200e600 g/g [48]

Graphene/CNT aerogel Liquid organics 215e743 g/g [188]
GF/CNT Liquid organics 80e130 g/g [187]
Graphene/polypyrrole foam Liquid organics 37e108 g/g [184]
rGO foam Liquid organics 10e37 g/g [71]
Spongy graphene Liquid organics 20e86 g/g [186]
Carbon nanofiber aerogels Liquid organics 40e115 g/g [190]
CNT sponge Liquid organics 80e180 g/g [191]
Seashell-derived GF Liquid organics 200e250 g/g [103]
Graphene sponge Liquid organics 75e154 g/g [50]
Dye 11.5e184 mg/g [50]
Graphene-based hydrogel Liquid organics 28e40 g/g [60]
Dye 150e650 mg/g [60]
GO/DNA hydrogel Dye 960 mg/g [41]
Graphene/a-FeOOH hydrogel Liquid organics 13e27 g/g [45]
Heavy metal 139e374 mg/g [45]
Graphene macrostructure Heavy metal 434e3820 mg/g [94]
GO aerogel Heavy metal 19.1 mg/g [185]
Graphene-MoS2 aerogel Heavy metal 1245 mg/g [189]

CNT, carbon nanotube; GF, graphene foam; GO, graphene oxide.

cm3 and large surface area of 280 m2/g, the as-prepared graphene
framework exhibited an excellent adsorption capacity for various
classes of oil and organic solvents, with ultrahigh adsorb amounts
up to 200 to 600 times its own weight, which was much higher
than other typical carbonaceous sorbents [48]. Sun et al. [188]
synthesized an ultra-flyweight graphene/CNT aerogel by freeze-
drying aqueous solutions of CNTs and giant GO sheets (Fig. 17a).
The robust graphene/CNT aerogel with a ultralow density of
0.75 mg/cm3 exhibited highly hydrophobic (the contact angle was
~132.9
) and had a large surface area of 272 m2/g. As a result, the
hybrid aerogels processed ultrahigh absorption capacity for various
solvents and oils, with 215e743 times of their own weights
dependent on the liquid density. Chen et al. grew 3D graphene/CNT
hybrid foam by two-step CVD method [187]. The hybrid foam was
superhydrophobic with a large contact angle of 152.3
and showed
a large adsorption capacity up to 80e130 times of its own weight
for adsorption of various oil and organic solvents. The hydrophobic
nature of the seashell-derived 3D GF by CVD also exhibited excel-
lent adsorption performance for a wide range of organic liquids up
to 200e250 times of its own weight [103]. Moreover, owing to the
high elasticity and excellent thermal stability of these 3D graphene-
based structures, the absorbed liquids can be readily released by
mechanical extrusion or heating or can be completely burned off
from the 3D structures in air without destroying the porous
structures. By this way, the 3D graphene structures can be reused
multiple times without significant loss in adsorption capacity,
making the graphene structures ideal candidates for practical ap-
plications in absorption removal of liquid organic contaminations.
Besides the liquid organic contaminations, the graphene-based 3D
structures also exhibit high efficiency in absorption of dye and
heavy metal. For example, Xu et al. [41] synthesized a 3D GO/DNA
hydrogel by self-assembly process with DNA as a cross-link agent.
The as-prepared hydrogel was used as high effective dye sorbents,
and the total dye-loading capacity for safranine O was estimated to
be 960 mg/g. The high dye-loading ability of the hydrogel was
partially resulted from the strong electrostatic interactions be-
tween positively charged safranine O and negatively charged GO as
well as DNA. Meanwhile, the highly porous structure and large
surface area of the hydrogel increased the contact opportunity and
affinity of dye molecules on GO sheets. Cheng et al. fabricated a
graphene sponge by hydrothermal treatment of GO with the
assistance of thiourea [50]. The graphene sponge showed a tunable
pore structure and surface properties, resulting in high adsorption
ability for various water contaminations. Large amount of methy-
lene blue (184 mg/g) and rhodamine B (72.5 mg/g) can be absorbed
by the graphene sponge. And the rhodamine B molecules can be
easily desorbed from the graphene sponge in methanol or ethanol,
which suggested the highly repeatable use of graphene sponge for
removing dye from water (Fig. 17bee). Gao et al. fabricated a 3D
graphene hydrogel using Cu nanoparticles as a reduction agent,
which exhibited high absorption capacity for different dyes ranged
from 150 to 650 mg/g [60]. Li et al. [94] developed a CVD method for
synthesis of high-density 3D graphene macroscopic structures,
which were used as electrolytic electrodes to remove various heavy
metal ions (Fig. 17feg). The robust 3D structure, high conductivity
(12 S/cm), and large specific surface area (560 m2/g) enabled ul-
trahigh electrical adsorption capacities of 434, 882, 1683, and
3820 mg/g for Cd2þ, Pb2þ, Ni2þ, and Cu2þ, respectively, from
aqueous solutions and fast desorption speed. Cong et al. [45] syn-
thesized a 3D graphene/a-FeOOH hydrogel by reduction of GO
sheets with ferrous ions. The hybrid hydrogel has been demon-
strated as a promising candidate for removal of heavy metal pol-
lutants, with maximum adsorption capacities of 139.2 and
373.8 mg/g for Cr(VI) and Pb(II), respectively. Zhang et al. have
fabricated a graphene-MoS2 aerogel via a one-pot hydrothermal
method, which showed a quick sorption rate and high sorption
capacity for a wide variety of contaminants, including organic
solvents, organic dyes, and also toxic heavy metals ions [189]. The
sorption capacity toward Hg2þ was up to 1245 mg/g and can be
optimized by simply changing the loading amount of MoS2.
4.6. Biomaterial
Owing to their ultrahigh mechanical properties, good chemical
stability, and excellent biocompatibility, carbon nanomaterials such
as CNT thin films and graphene sheets have been demonstrated as
novel cell-instructive materials for tissue engineering [192e194].
However, for clinical application of tissue engineering and regen-
erative medicine, a 3D scaffold is required to provide 3D cell growth
microenvironments and appropriate synergistic cell guidance cues
[195]. The GF networks with 3D porous structures have been
demonstrated as a novel scaffold and culture substrate for prolif-
eration and differentiation of stem cells [196,197]. Cheng et al. re-
ported the first utilization of GF as a novel scaffold for neural stem
cell (NSC) in vitro (Fig. 18aed) [197]. It has been found that the high
specific surface area of GF could provide a large surface area for cell
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027 29

Fig. 17. Sorption capacities of 3D porous graphene-based sorbents. (a) Absorption process of toluene (stained with Sudan Black B) on water by the graphene/CNT aerogel within 5 s.
(bee) The adsorption and desorption of rhodamine B in graphene sponge. A graphene sponge in rhodamine B solution (b) at the beginning and (c) for 180 min. The same graphene
sponge adsorbed with rhodamine B in ethanol for (d) 2 min and (e) 10 min. (f) Schematic illustrations of the electrolytic deposition on 3D graphene structures for removing heavy
metal ions. (g) Typical adsorption capacity versus time for the various heavy metals' ions. CNT, carbon nanotube. Reproduced with permission from Ref. [188] (a), [50] (bee), and
[94] (feg). Copyright: 2013 Wiley (a), 2012 The Royal Society of Chemistry (bee), and 2013 Nature Publishing Group (feg).
30 Z. Chen et al. / Materials Today Nano 5 (2019) 100027

attachment and growth, and the macroporous structure of GF
ensured efficient mass transport of nutrition for NSC metabolic
demands, which should facilitate active cell proliferation with
significantly higher Ki67 expression than that of 2D graphene films.
Meanwhile, phenotypic analysis indicated that GF networks can
enhance the NSC differentiation toward astrocytes and especially
neurons. Moreover, the high-conductive GF networks exhibited a
high efficiency in mediation of electrical stimulation for differen-
tiated NSCs. Sung et al. used the GF networks as culture substrates
for human mesenchymal stem cell (hMSC) [196]. Similar to the case
of NSC, the 3D GF networks could also support the attachment and
viability of hMSCs and induced spontaneous osteogenic differen-
tiation without the need for extrinsic biochemical manipulation,
which held great promise for advanced application of GF in tissue
engineering and regenerative medicine. Moreover, 3D printing
graphene (3DG) structures have also demonstrated the potential as
electrically conducting scaffolds for tissue regenerative engineering
applications using in vitro and in vivo biocompatibility studies
(Fig. 18e) [76]. The resulting 3DG structures were mechanically
robust and flexible with high electrical conductivities of
>800 S m1. In vitro experiments in simple growth medium without
neurogenic stimuli revealed that 3DG can support hMSC adhesion,
viability, proliferation, and neurogenic differentiation with signifi-
cant upregulation of glial and neuronal genes. This coincided with
hMSCs adopting highly elongated morphologies with features
similar to axons and presynaptic terminals. In vivo experiments
indicated that 3DG had promising biocompatibility over the course
of at least 30 days. Surgical tests using a human cadaver nerve
model also illustrated that 3DG had exceptional handling charac-
teristics and can be intraoperatively manipulated and applied to
fine surgical procedures. With this unique set of properties, com-
bined with ease of fabrication, 3DG could be applied toward the
design and fabrication of a wide range of functional electronic,
biological, and bioelectronic medical and non-medical devices.
4.7. Thermal management
The room temperature thermal conductivity of monolayer gra-
phene exceeds 5000 W/m K, making it an excellent material for
thermal management [6,198]. Three-dimensional graphene
network structures with isotropic and high-conductive thermal
pathway hold great promise for use in thermal interfacial material
and phase change materials. Pettes et al. [199] synthesized GF and
ultrathin graphite foam by CVD, which exhibited a high thermal
conductivity up to 1.7 W/m K, with the solid thermal conductivity
of the graphene constitutes up to 1600 W/m K at about 150 K. Lin
et al. [200] reported the thermal diffusivity study of suspended GF
using transient electrothermal technique. It was found that the
intrinsic thermal diffusivity of the suspended GF can reach
1.16e2.22  104 m2/s, and the corresponding intrinsic thermal
conductivity of solid graphene was 182e349 W/m K. Yang et al.
demonstrated that 3D flexible and interconnected GF networks can
use as a high-performance thermal interfacial material, which
exhibited an ultralow thermal interfacial resistance at SieAl inter-
face (0.04 cm2 K/W), one order of magnitude lower than conven-
tional thermal grease and thermal paste-based thermal interfacial
material (Fig. 19aec) [201]. Teo et al. fabricated a high-density 3D-
foam by simply compressing the CVD-grown GF network with an
applied force for high-performance nanothermal interface material
[202]. The high-density foam structures revealed their high cross-
plane thermal conductivity (62e86 W/m K) and excellent surface
conformity, which are essential for thermal management. An
exceptional performance as thermal interface material with a
drastic decrease of chip temperature by DT of 4424
C has been

Fig. 18. Three-dimensional porous graphene for biomedical applications. (a-b) Representative fluorescence images of differentiated NSCs on the surface of 3D-GF network under
differentiation conditions; the cells were immunostained with Tuj-1 for neuron (green, a), glial fibrillary acidic protein (GFAP) for astrocyte (red, a and b), O4 for oligodendrocyte
(green, b), and 40 ,6-diamidino-2-phenylindole (DAPI) for nuclei (blue, a and b). (c) Cell viability assay of NSCs on 3D-GFs after 5 days of culture as determined by live/dead assay, live
cells were stained green and dead cells were red, white arrow pointed to the dead cell. The lower right inset depicted the percentage of live cell on 2D graphene films and 3D-GFs.
(d) Fluorescence images of NSCs proliferated on 3D-GFs for 5 days, immunostaining markers were nestin (green) for neural stem cells and DAPI (blue) for nuclei. (e) 3D printable
graphene inks were produced through simple combination and mixing of the elastomer solution with the dispersion of graphene powder in a graded solvent followed by volume
reduction and thickening, a process that can be scaled up to many liters at once if desired. User-defined architectures 3D printed from graphene ink have a variety of potential
applications, including those relating to biomedical and bioelectronics, as well as tissue and organ engineering. NSCs, neural stem cells; GF, graphene foam; Reproduced with
permission from Ref. [197] (aed), [76] (e). Copyright: 2013 Nature Publishing Group (aed), 2015 American Chemical Society (e).
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027 31

Fig. 19. Thermal management applications of various 3D porous graphene structures. (a) Thermal interface testing of GF-based thermal interfacial material. (b) Thermographic
images of the copper blocks under steady-state cooling with and without GF. (c) Plots of the temperature drop across the interface with and without GF: without GF, the tem-
perature drop was 12.2
C; with GF, the drop fell to almost 1.2
C (the heat flow without and with GF are 120 and 150 kW/m2, respectively). (d) Pictures of graphene aerogel,
octadecanoic acid, and their composite. (e) Thermal images of the graphene aerogel and the composite at the cooling time of 20 s. (f) Temperature response of graphene aerogel and
the composite during the cooling time. (g) A schematic of solar thermal conversion difference between ordinary graphene foam and hierarchical graphene foam. (h) Temperature
distribution and a photo of the steam generation unit under solar illumination of 5 kW/m2. GF, graphene foam. Reproduced with permission from Ref. [201] (aec), [203] (def), and
[204] (geh). Copyright: 2013 Elsevier (aef), 2017 WILEY (geh).

achieved. Zhong et al. [203] synthesized a graphene aerogel/octa-
decanoic acid composite for use as phase change materials
(Fig. 19def). The graphene aerogel was prepared by a convenient
one-step hydrothermal method, which offered a large number of
interconnected open pores and large surface area for impregnation
of octadecanoic acid. The thermal conductivity of the composite
was about 2.635 W/m K at a graphene loading fraction of 20 vol%,
which was about 14 times that of octadecanoic acid. The composite
presented a high heat storage capacity of 181.8 J/g, which was very
close to that of pure octadecanoic acid (186.1 J/g). A hierarchical GF
has been synthesized via a facile one-step plasma-enhanced CVD
on Ni foam template for an efficient solar thermal conversion
medium (Fig. 19g, h) [204]. It consisted of vertical graphene
nanoplates array on the 3D porous GF skeleton, which provided a
much larger heat exchange area, resulting in a dramatic enhance-
ment of broadband and omnidirectional absorption of sunlight.
Therefore, the solar thermal conversion efficiency was dramatically
enhanced by the hierarchical GF (z93.4%), which was much su-
perior to that of traditional GFs and other carbon-based
solar thermal materials. In addition, it was used as a light
absorber and efficient heater in a solar-driven seawater desalina-
tion system, and the solar-vapor conversion efficiency exceeded
90% with excellent durability, recycling performance, and anticor-
rosion property.
32 Z. Chen et al. / Materials Today Nano 5 (2019) 100027
5. Conclusions and outlooks
With a relatively short history, 3D graphene network structures
have greatly extended the research area of graphene, exhibiting a
wide variety of new functionalities and exciting potential applica-
tions. The unique network structure, ultrahigh porosity, large spe-
cific surface area, high electrical/thermal conductivities, and
outstanding mechanical flexibility of the 3D graphene structures
and their composites enable many promising applications,
including high-conductive polymer composites, elastic and flexible
conductors, high-performance electrode materials for energy
storage and conversion, high-capacity absorption materials, high-
conductive thermal interface materials, high-sensitive chemical
and electrochemical sensors, and multifunctional biomedical
materials.
5.1. Remained challenges
Based on the chemical exfoliated and CVD-grown graphene,
several approaches, including self-assembly of chemically derived
graphene sheets during reduction or with the assist of cross-linking
agents, template-directed assembly of graphene sheets, gas
expansion of graphene films, 3D printing, and template-directed
CVD growth on various 3D porous metal/insulator substrates,
have been developed for the synthesis of 3D graphene structures.
Among them, the approaches based on chemical exfoliated gra-
phene are most promising for scale-up and low-cost production of
3D graphene structures due to the ease and mass preparation and
processing of chemically derived graphene. However, the network
and pore structures of these 3D graphene structures are difficult to
control, especially for the self-assembly methods. The structural
properties and performances of the obtained 3D graphene struc-
tures are strongly dependent on the quality, size and concentration
of the GO precursor, the type of the reducing agents and cross-link
agents, the reaction temperature and time, and the pH value of the
GO solution. Besides, using the self-assembly method, mainly
irregular macroporous graphene structures can be obtained. When
templates with regular structures are introduced in the graphene
self-assembly process, it is possible to fabricate 3D graphene
structures in ordered arrangement. Although the template-directed
assembly methods usually need complicated operation and sacri-
ficial template, the direct freeze-drying assembly method with ice
crystals as templates is quite simple and is possible to form ordered
graphene structures by careful control of the formation of ice
crystals. However, making the pore structure uniform within the
whole freeze-dried sample is a challenge because of the tempera-
ture gradient in freeze process, especially for the scale-up fabrica-
tion. As mentioned previously, the chemically derived graphene
sheets have achieved great success in self-assembly and/or inte-
gration with other nanomaterials into various 3D macroscopic
network structures. However, these integrated graphene materials
and structures show poor electrical conductivity, owing to severe
structural defects in graphene sheets and their high intersheet
junction contact resistance. Alternatively, using template-directed
CVD methods, 3D graphene network structures with high con-
ductivity can be synthesized, in which the graphene is seamlessly
interconnected into a 3D flexible network. The high quality of the
graphene sheets and their perfect connection in three dimensions
give the 3D structures outstanding electrical and thermal conduc-
tivity that are superior to those fabricated from chemically derived
graphene sheets. By controlling the CVD conditions and using
different kinds of porous template substrates, 3D graphene with
different pore structure and morphology can be synthesized.
However, the CVD methods are more difficult for scale-up fabri-
cation compared with the chemically derived methods because of
the high-temperature condition, sacrificial template, and multiple
transfer steps.
5.2. Perspectives
Therefore, although many efforts have been devoted and
advanced progress have been achieved for the fabrication and ap-
plications of 3D graphene structures, many challenges still remain
for their further development and commercialization. First, all the
synthesis methods mentioned previously require further de-
velopments for low-cost and large-scale preparations of high-
quality 3D graphene structures. With respect to the synthesis
methods based on chemically derived graphene, the quality,
thickness, and size distribution of the GO sheets need further
optimization. The graphene synthesis by other exfoliation methods
such as electrochemical exfoliation, intercalation compound exfo-
liation, and liquid-phase ultrasonic exfoliation could be used for
fabrication of 3D graphene structures, which may possess higher
quality, less defects, and oxygen functional groups than those
synthesized by the chemical exfoliation method. For the template-
directed assembly methods, more efforts should devote in low-cost
fabrication and controlled assembly of the templates. Besides, the
assembly mechanism of the chemically derived graphene sheets
requires more clear understanding for better control of the network
and pore structures. Regarding the template-directed CVD growth
methods, the scale-up fabrication at low cost is the most urgent
issue. Although large-area GF in A4 size has been fabricated, it is
still far from enough for commercial applications. Larger CVD
furnace and continuous line operations in growth and transfer
process may greatly improve the efficiency and reduce the cost. A
continuous fluid bed CVD technology should be suitable for scale-
up fabrication of 3D porous graphene from metal or insulator
particle templates. Developing new templates with ordered pore
structures and different pore sizes at a low cost is still an attractive
topic in the research of 3D graphene structures. Based on the new
templates, 3D graphene networks with ordered pore structures and
controlled pore size can be fabricated for more macroscopic
applications.
Moreover, the structures and properties of 3D graphene require
further optimization for specific applications. For polymer com-
posites and thermal management, higher electrical/thermal con-
ductivity of the 3D graphene structures is most welcomed.
Therefore, graphene with higher quality and better reduction
method should be developed, and a seamless assembly of indi-
vidual graphene sheet into a high-conductive interconnected
network is still highly desired. Welding individual macroscopic
graphene assemblies via electrical Joule heating or electron beam
radiation could be candidate methods for their seamless connec-
tion [205,206]. The CVD conditions should be controlled more
precisely for higher quality of 3D graphene structures. For energy
storage and conversion, hierarchical combination of different pores
(i.e. micropores, mesopores, and macropores) is crucial for
improved electrode performances. However, most of the reported
3D graphene structures only possess macropores, which result in
relative low volume energy density of the devices. Therefore,
construction of hierarchical porous 3D graphene structures,
together with the integration of electroactive materials into their
void space, can obtain high-density electrodes for supercapacitors
and batteries with high energy density. In addition, heteroatom
doping of the 3D graphene structures should be further investi-
gated to promote the electrochemical activity and catalysis for
high-performance energy storage and conversion devices. For ab-
sorption materials, lower density, larger specific surface area, and
higher pore volume are required. Therefore, strategies for pre-
venting restack of graphene sheets and controlling of the wall
 Z. Chen et al. / Materials Today Nano 5 (2019) 100027
thickness are desirable. For the sensor, higher conductivity, larger
specific surface area, and thinner wall of the 3D graphene struc-
tures are also crucial for high sensitivity. Besides, the surface
modification of the 3D graphene structures should increase the
selectivity of the sensors. For the biomedical materials, the pore
morphology and pore size of the 3D graphene structures should be
specially designed for proliferation and guidance of specific cells.
The mechanical property of the 3D graphene structures should also
be improved for applications in tissue engineering. Therefore, more
innovative efforts will require for addressing these key challenges
and further developments of the 3D graphene structures for further
applications. Besides graphene, a broad class of other 2D materials
should provide more opportunities and possibilities for construct-
ing novel 3D network structures [207e209]. Moreover, owing to
the large varieties of new 2D materials with diverse characteristics,
it will be interesting to combine them with each other and/or with
graphene to form 3D hybrid structures with multifunctional
properties for wide range of applications.
Declaration of interests
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
The authors thank the support from National Program for
Thousand Young Talents of China, National Key R&D Program of
China (No. 2016YFA0200101), National Science Foundation of China
(Nos. 51325205, 51290273, and 5152109), and the Strategic Priority
Research Program of Chinese Academy of Sciences (No.
XDB30000000).
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