Communication

Cellular Networks www.advmat.de

A Plesiohedral Cellular Network of Graphene Bubbles

for Ultralight, Strong, and Superelastic Materials
Seon Ju Yeo, Min Jun Oh, Hyun Min Jun, Minhwan Lee, Jung Gun Bae, Yeseul Kim,
Kyung Jin Park, Seungwoo Lee, Daeyeon Lee, Byung Mook Weon, Won Bo Lee,
Seok Joon Kwon,* and Pil J. Yoo*

The design of functional materials relies

Advanced materials with low density and high strength impose transforma- on the judicious selection and elaborate
tive impacts in the construction, aerospace, and automobile industries. assembly of building units (BUs) aiming
These materials can be realized by assembling well-designed modular at particular applications. Given that the
building units (BUs) into interconnected structures. This study uses a assembly of BUs spans multiple scales from
the molecular to macroscopic scale, a tai-
hierarchical design strategy to demonstrate a new class of carbon-based,
lored strategy is required to implement the
ultralight, strong, and even superelastic closed-cellular network structures. desired functionalities at different scales.[1]
Here, the BUs are prepared by a multiscale design approach starting from To achieve lightweight yet mechanically
the controlled synthesis of functionalized graphene oxide nanosheets strong and resilient functionality, which is
at the molecular- and nanoscale, leading to the microfluidic fabrication imperative for the development of advanced
materials for construction, aerospace, and
of spherical solid-shelled bubbles at the microscale. Then, bubbles are
automobiles,[2–4] the obvious starting point
strategically assembled into centimeter-scale 3D structures. Subsequently, is to develop mechanically stable and strong
these structures are transformed into self-interconnected and structurally BUs. The conventional approach targeting a
reinforced closed-cellular network structures with plesiohedral cellular units reduced density has concentrated on the fab-
through post-treatment, resulting in the generation of 3D graphene lattices rication of metals and ceramic lattice struc-
with rhombic dodecahedral honeycomb structure at the centimeter-scale. tures using template-directed synthesis.[5–7]
Unfortunately, these methods often require
The 3D graphene suprastructure concurrently exhibits the Young’s modulus
postprocessing and are still far from real-
above 300 kPa while retaining a light density of 7.7 mg cm−3 and sustaining izing cost- and time-effective process.
the elasticity against up to 87% of the compressive strain benefiting from Besides, the fabricated lattice structures
efficient stress dissipation through the complete space-filling closed-cel- are prone to the imposed stress and have
lular network. The method of fabricating the 3D graphene closed-cellular reduced structural recoverability. As a result,
it is highly desirable to further improve the
structure opens a new pathway for designing lightweight, strong, and
mechanical strength and adaptability as well
superelastic materials. as lightweight properties while maintaining
processability and scalability.

Dr. S. J. Yeo, Dr. S. J. Kwon Y. Kim, K. J. Park, Prof. S. Lee, Prof. B. M. Weon, Prof. P. J. Yoo
Nanophotonics Research Center SKKU Advanced Institute of Nanotechnology (SAINT)
Korea Institute of Science and Technology (KIST) Sungkyunkwan University (SKKU)
Seoul 02792, Republic of Korea Suwon 16419, Republic of Korea
E-mail: cheme@kist.re.kr Prof. D. Lee
M. J. Oh, H. M. Jun, Prof. S. Lee, Prof. P. J. Yoo Department of Chemical and Biomolecular Engineering
School of Chemical Engineering University of Pennsylvania
Sungkyunkwan University (SKKU) Philadelphia, PA 19104, USA
Suwon 16419, Republic of Korea Prof. B. M. Weon
E-mail: pjyoo@skku.edu School of Advanced Materials Science and Engineering
M. Lee, J. G. Bae, Prof. W. B. Lee Sungkyunkwan University (SKKU)
School of Chemical and Biological Engineering Suwon 16419, Republic of Korea
Institute of Chemical Processes
Seoul National University
Seoul 08826, Republic of Korea
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.201802997.

DOI: 10.1002/adma.201802997

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Figure 1. Multiscale design of GO-based microbubble assembly. a) GO, lightly- or heavily-alkylated GOs (L-GO or H-GO) molecular BUs, which are
organized into b) micro-scale spherical solid-shelled bubbles (composed of H-GO nanoplatelets (NPs)) via a microfluidic process. c) The spherical
microbubbles are further assembled into a macro-scale 3D FCC array d) followed by chemical and structural transformation into 3D RDH structures
of rGO. The transformed 3D lattice structures form centimeter-scale plesiohedral closed-cellular structures (CCSs).

Given a BU that is lighter than yet as strong as metal, a well-
designed bottom-up approach can provide a relatively simple
way of fabricating a structured material satisfying the required
mechanical strength. Some of the potential BUs demonstrating
this property are graphene and its related materials such as
graphene oxide (GO) or reduced GO (rGO) on account of their dis-
tinguished advantages including accessibility to functionalization,
strong mechanical stiffness, high elasticity, and cost-effectiveness
in preparation.[8] In particular, structurally regulated 3D porous
graphene-related materials enable the realization of func-
tionally improved materials in terms of reduced density, high
surface area, reinforced stiffness, and elasticity.[9–21] These
materials are mostly prepared from random integration of GO
or graphene nanosheets by means of hydro/solvothermal pro-
cesses,[9,16] direct freeze-drying,[13,14,19] and sol–gel reactions.[11]
Due to random stacking in the course of integration, however,
pores lack structural ordering. A template-directed chemical
vapor deposition (CVD)[10,12] or 3D printing method[17,18,20,21]
for the formation of 3D graphene networks could alleviate the
processing difficulties in assembling graphene-related mate-
rials into regular 3D networks. However, multistage, time-con-
suming, and low-yield procedures are inevitable, and most of
the materials prepared by 3D printing still lack the uniformity
in their unit cell morphologies, which hinders further applica-
bility. To overcome these hurdles, there is a need for well-defined
and adaptable strategies that utilize designer BUs of graphene-
related materials and their assembly at multiple scales.
In this study, we demonstrate a new class of hierarchically struc-
tured material composed of functionalized GOs and their reduced
phase. To cover a wide range of scales in the design hierarchy, GOs
were carefully modified in the form of alkylated GO nanosheets
with designated physicochemical and mechanical properties
(Figure 1a) to serve as nanoscale BUs with a nanosheet form
(≈500 nm width, also see the expanded panels of Figure 1b). Next,
nanosheets were microfluidically treated to form microscale solid-
shelled bubbles (≈100 µm diameter, Figure 1b) with excellent size
uniformity and sphericity. Then, the bubbles were assembled into
2D or 3D structures (centimeter-scale, Figure 1c) and finally trans-
formed into well-defined self-interconnected network structures
(Figure 1d) via thermal reduction. Notably, as a consequence of
self-interconnection between adjacent domains of microbubbles,
the resulting structures were complete space-filling closed-cel-
lular foam with rhombic dodecahedral honeycomb (RDH) lattice,
which can ideally serve as lightweight, strong, and highly adaptable
structured material by virtue of remarkable structural advantages
over multiple scales. As a result, unprecedented performances
of structured carbonaceous materials are achieved with a high
Young’s modulus above 300 kPa and ultralow density as low as
7.7 mg cm−3, while securing the superelasticity with intact struc-
tural recovery even after applying a compressive strain up to 87%.
For the realization of hierarchically structured materials, it
is essential to prepare GO-related BUs taking into account the
molecular aspect of mechanical properties. Mono- or bilayer GO
nanosheets have been known to possess a high Young’s modulus
of about 200 GPa.[22] Therefore, the stacked GO platelets are likely
to preserve the characteristics of a high elastic modulus. Mean-
while, the mechanical properties of the GO platelets can also be
tailored by chemical modification of GO nanosheets. For this
purpose, GO nanosheets (average width ≈500 nm, see Figure S1,
Supporting Information) were alkylated via the amide bond for-
mation of carboxylic acid and ring opening amination of epoxide
groups on the surface of GO using carbodiimide cross-linking
chemistry[23] and the degree of alkylation can be readily controlled
by varying the reaction time to produce lightly- (i.e., L-GO) or
heavily alkylated GO (i.e., H-GO) (see the detailed characterization
in Figure S2, Table S1, and Section S1, Supporting Information).
In order to understand the effect of alkylation on the mechan-
ical properties of GO nanosheets or nanoplatelets, we employed
molecular dynamics (MD) simulation. For the simulations of
individual GO nanosheet, 5.65 × 6.59 nm2 areas of GO, L-GO,
and H-GO structures were tested while ignoring defects (see
detailed methods in Supporting Information). For L-GO and
H-GO, alkylamine chains are allowed to adsorb onto the GO
surface (Figure 2a). We intuited the experimentally deter-
mined degree of alkylation to define the configurations of L-GO
(i.e., 26.4%) and H-GO (i.e., 86.1%) (detailed in Section S1,
Supporting Information). As a result of the MD simulation in
which a single nanosheet of GO, L-GO, and H-GO was elon-
gated at equilibrium in the in-plane direction, the three types
of GO nanosheets exhibit nearly constant Young’s modulus
(E) around 200 GPa, which is mainly due to the in-plane strain
being intervened by the planar GO backbone (Figure 2c).

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Figure 2. Mechanical properties of GO, L-GO, and H-GO BUs. a) Calculated molecular structures of GO, L-GO, and H-GO BUs at equilibrium obtained
using MD simulation. b) Calculated morphology of the overlapped layers of (upper) L-GO and (lower) H-GO NPs. Note that H-GO NPs exhibit deflection,
which is derived by free energy minimization in the course of aggregation. c,d) Calculated mechanical properties (i.e., Young’s modulus (E)) of (c) one layer
and (d) multiple-stacked layers of GO, L-GO, and H-GO BUs obtained using MD simulations. For Ei, GOi, L-GOi, and H-GOi, i denotes 1 for x- and 2 for
y-directions, respectively. Eavg means an arithmetic average of E1 and E2. The insets of (c) and (d) show stress–strain curves of single layer and stacked layers
of GO, L-GO, and H-GO BUs. e) Nanoindentation results for E of thin films composed of GO, L-GO, and H-GO BUs. The inset shows the comparison of
the MD simulation and experimental results with respect to internal porosity (φ) and layer-to-layer distance (d-spacing, cf. d0 denotes d-spacing of GO).

Notably, the alteration of mechanical properties according
to the degree of alkylation becomes prominent when the
nanosheets are assembled into a stacked form of platelets. First,
we allowed a number of L-GO or H-GO nanosheets, and GO
nanosheets with the pre-defined configurations to be placed in
3D simulation boxes with the NPT ensemble. The nanosheets
were further allowed to interact with each other for a long time
to investigate the stacking behavior. As shown in Figure 2b,
both L-GO and H-GO platelets exhibited a stacked morphology.
Intriguingly, the H-GO platelets exhibited a deflected mor-
phology in the stacked structure, which could result from the
greater number density of alkyl chains on the surface. Alkyl
chains on GO nanosheets impose short-range repulsive poten-
tial that not only hinders proximal contact but induces the
deflection of a GO platelet to minimize the total free energy by
introducing additional excluded volume around an individual
nanosheet, resulting in a difference in the internal porosity.
Using stacked configurations of GO, L-GO, and H-GO plate-
lets, we further tested the mechanical properties. As provided
in Figure 2d, it is evident that E of the stacked morphology
decreases with increasing surface density of alkyl chains. The
stacked systems of GO, L-GO, and H-GO platelets indeed
showed a notable reduction in E (Figure 2e). It should also be
noted that the modulus reduction is an order of magnitude dif-
ferent when comparing H-GO and GO (i.e., 1.18 vs 10.3 GPa,
Figure S3, Supporting Information). This reduction in the
modulus can be translated into different internal porosities (φ)
with values of φ = 0.550, φ = 0.692, and φ = 0.766 for the stacked
morphologies of GO, L-GO, and H-GO platelets, respectively
(inset of Figure 2e and Section S2, Supporting Information).[24]
From the calculated porosity, we extracted the equilibrium
spacing, dS, between the nearest platelets by assuming a simple
1D relationship of φ = ds/Ds, where DSdS + hf and hf denotes
the thickness of the single platelet. As shown in the inset of
Figure 2e, the calculated values of DS relative to that of the
stacked morphology of GO platelets showed good agreement
with the experimentally observed spacings obtained from X-ray
diffraction (Figure S2g, Supporting Information). The stacked
morphology of GOs and alkylated GOs with tunable mechan-
ical properties would successfully act as BUs at the nanoscale.
We then constructed structures at the next level of the hier-
archy, namely, the microscale, by employing a microfluidic
process to fabricate solid-shelled spherical bubbles.[25,26] In par-
ticular, to secure the stability of dispersed phase of alkylated GOs
and accordingly to enhance the compatibility with the micro-
fluidic process, H-GO platelets are chosen for the synthesis of
microsolid bubbles. On the other hand, GO and L-GO platelets
are excluded for the bubble synthesis due to their immisci-
bility or partial miscibility in toluene, which eventually results
in bubble bursting or deformation. The stability of GO solu-
tions in organic solvent depending on the degree of alkylation
(H-GO and L-GO) is compared in Figure S4 in the Supporting
Information. In the process, H-GO platelets are dispersed in an
oil (O, toluene) phase and are sandwiched between a gaseous

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Figure 3. Microscale solid-shelled spherical bubbles. a,b) Optical microscopy (OM) image and schematic illustration of the assembled H-GO NPs
via the microfluidic process, resulting in the formation of ultrastable spherical microbubbles. c) SEM image of the microscale spherical H-GO-shelled
bubbles. d) Measurement of shell thickness of the bubble. e) X-ray nanotomography images of the spherical microbubbles showing the thin-shelled
morphology: (left) 3D reconstructed image and (right) 2D cross-sectional images sliced at different positions. f) Bright- and g) dark-field OM images
of the spherical microbubbles. h) The calculated color hue of thin-shelled bubbles resulting from interference reflectance.

N2 phase (G, inner), and poly(vinyl alcohol)-dispersed aqueous
(W, outer) phase, finally forming gas-in-oil-in-water (G/O/W)
compound bubbles with controlled size and shell thickness in a
glass capillary microfluidic device (Figure 3a).
Due to buoyancy, the collected spherical bubbles are
suspended at the air–water interface. From the shell, toluene
evaporates, and the shell is gradually hardened, which results in
the generation of microscale spherical solid bubbles (Figure 3b).
Notably, the size of the encapsulated bubbles is virtually invar-
iant throughout the solvent evaporation process (Figure S5, Sup-
porting Information). The final morphology of the solid-shelled
bubbles at the fully dried state is a spherical bubble with a radius
of 50 ± 0.2 µm and a shell thickness of 100 nm (Figure 3c,d and
Figure S6, Supporting Information). Spherically isotropic thin
shell morphology is demonstrated by detailed imaging based
on X-ray nanotomography (Figure 3e and Figure S7, Supporting
Information; Movie S1, Supporting Information). As the BUs
at the microscale, spherical bubbles also possess additional
geometric stiffness due to its convexity.[27] As a result of shape
uniformity and intactness of the solid-shelled microbubbles,
some interesting optical properties are observed, such as inter-
ference reflectance (Figure 3f,g).[28] Microscale bubbles with thin
solid-shells can exhibit a colorful reflectance pattern (Figure S8,
Supporting Information, calculated colors from standard red-
green-blue matching in Figure 3h), which can be observed in the
designated solid angle, Ω, of the detector of a microscope (i.e.,
Ω = 2π(1 − cos θ), where θ is the instrumental observation angle
(θ = 8.75°)). It is also notable that the microbubble would exhibit
different reflectances by different polar positions due to different
portions of the inner layer (Figure S9, Supporting Information).

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We further proceeded to construct macroscale (centimeter-
scale) 2D and 3D structures for the demonstration of tar-
geting practical applications. The microfluidic synthetic toolkit
ensures the continuous production of uniform and stable bub-
bles with a high yield (≈1 million ea. 10 min–1) and a wide sur-
face coverage larger than 2 × 2 cm2 when assembled into a 2D
structure (inset picture in Figure 4a). Once H-GO spherical
microbubbles are suspended on the air–water interface, they
spontaneously form a 2D-assembled structure via buoyancy
and capillary attraction among the bubbles. The 2D assembly
can be directly transferred without impinging the structural
order of a hexagonally close-packed (HCP) array over a long
range (i.e., ≈1 cm), onto the target substrate to form integrated
hierarchical structures (Figure 4a). The transferred HCP array
of the bubbles is then transformed into an interconnected 2D
honeycomb lattice while preserving structural order via chem-
ical reduction of H-GO bubbles (Figure 4b,c and Figure S10,
Supporting Information).
The formation of a 2D closed-cellular structure (CCS)
encourages the construction of a centimeter-scale 3D CCS
based on the 3D assembly of H-GO spherical microbubbles.
Using a continuous packing procedure driven by the buoyancy-
assisted assembly of the H-GO spherical bubbles, we could
prepare a centimeter-scale close-packed 3D assembly of H-GO
microbubbles (Figure S11, Supporting Information). Theo-
retically, the 3D assembly of the spherical microbubbles would
generate a face-centered cubic (FCC) structure. Subsequently,
via 3D Voronoi tessellation, the FCC structure will be trans-
formed into one of the only five complete space-filling convex
polytopes (i.e., plesiohedra), an RDH lattice, which will serve
as the 3D CCS. The RDH lattice is clearly distinguished from
the inverse FCC structure (i.e., 3D inverse opal structure) in
that it is composed of regular convex polyhedral cellular units
with uniform wall thickness (Figure S12, Supporting Informa-
tion) . Indeed, as shown in Figure 4e of X-ray microtomography
imaging, the 3D-assembled structure of H-GO after thermal
reduction is fully interconnected to form the 3D CCS with
complete space-filling RDHs. As apparent in Figure 4f, inter-
connected polytopes with well-defined edges and vertices of
are manifested. Notably, the morphology of the cellular structure
revealed from the cross-sectional scanning electron microscopy
(SEM) images is substantially close to the polygonal geometry of
the ideal 3D RDH lattice. It should be noted that this geometry
is the first-ever experimental realization of closed-cellular solid
foam with regular 3D space-filling convex polyhedral cells.
By virtue of the formation of the plesiohedral complete
space-filling 3D CCS over the centimeter-scale, we can expect
such ultra-lightness at a theoretical density (ρ) as low as
3.6–7.2 mg cm−3 given an average edge length of 50 µm and a wall
thickness in a range of 50–100 nm (Section S3 and Figure S13,
Supporting Information). The density can be tuned by manipu-
lating the size and shell thickness of microbubbles. Intriguingly,
despite the substantial volumetric shrinkage upon reduction
(Figure S14, Supporting Information), the internal structures
remain intact, resulting in the formation of lightweight mate-
rials consisting of a graphene-based CCS (Figure 4d). Fur-
thermore, because of the restored nature of graphene after
reduction (Figures S15 and S16, Supporting Information) as
well as structural benefit from hierarchically designed cellular
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structures, it is also expected that the 3D CCS will have strong
mechanical properties with outstanding elasticity.
To assess their strength, we experimentally measured the
elastic modulus of 3D CCS using displacement-controlled
compression on a universal testing machine. As compared
to a simple 3D assembly of H-GO microbubbles (not yet ther-
mally reduced) showing linear deformation tendency, three
characteristic regimes of deformation were obtained in the
stress–strain curve of the 3D RDH structures (Figure 4g): i) a
nearly linear elastic region that can be associated with bending
of the cell walls and stretching of the faces (0% < strain <10%),
ii) a successive linear region with lower slope, corresponding
to elastic collapse (10% < strain < 60%), and iii) a gradual
increasing regime of stress at strains > 60%, which is defined as
a densification stage. After transforming 3D FCC structures of
spherical H-GO-shelled microbubbles into 3D RDH lattice struc-
tures, E increased from 20 to 400 kPa at an equivalent density
(Table S2, Supporting Information). Theoretically, for an ideal
3D RDH lattice without structural defects and/or loss, the effec-
tive Young’s modulus is expected to reach at 0.58–1.15 MPa (with
a wall thickness variation in the range of 50–100 nm, Section S3,
Supporting Information). The observed modulus is smaller than
the theoretical expectation, which can be attributed to mass loss
during the reduction and the inclusion of irregularities.
In particular, it should be noted that structural transformation
into self-interconnected CCS through thermal reduction derived
the structural superelasticity and full recovery characteristics as
shown in the loading–unloading hysteresis of the 3D graphene
CCS (blue line in Figure 4g). Indeed, as shown in Figure 4h,
compression tests involving the 3D graphene CCS showed full
recovery from strains exceeding 87% (Figure S17 and Movie S2,
Supporting Information). The compressive superelasticity was
also demonstrated in the repeated stress–strain curves observed
in the cycle test of 3D graphene CCS (Figure S18, Supporting
Information). The structures showed reproducible structural
integrity after 100 loading–unloading cycles (maximum com-
pressive strain ≈ 80%). We also observed that the initial mechan-
ical property (modulus) decreased but saturated shortly in the
course of the cycle test, which indicates that the structure has
reliable durability under repeated external mechanical stress. In
contrast to randomly structured graphene foams or aerogels,[9–12]
we contribute the superelasticity of our 3D CCS to the efficient
stress dissipation process through the complete space-filling
closed-cellular network of 3D hierarchically ordered structures,
spanned from nanoscale H-GO platelets to macroscale 3D RDH
lattice structures. In particular, the 3D CCS of regular polyhedral
cells and nearly monolithic interconnected structures can effec-
tively dissipate the compressive strain over the space to maintain
the integrity of the entire structure, which is another advantage
harnessed by complete space-filling network architectures.[29]
Finally, we systematically compared ρ versus E data of the
fabricated 3D CCS with other advanced porous or cellular 3D
carbon-based structures in an Ashby plot focusing on ultralight
materials (ρ < 10 mg cm−3) as shown in Figure 4i.[9,12–14,16–21,30–35]
First, the data follow a linear trend of E ~ ρ (Section S4, Sup-
porting Information), which strongly suggests that the fab-
ricated cellular structure is the closed one.[36] In addition, as
apparent from the plot, it is obvious that the fabricated 3D CCS
outperforms conventional carbon-based lightweight materials
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Figure 4. Centimeter-scale 2D and 3D assembly of microbubbles. a) OM image of 2D hexagonal close-packed (HCP) array of spherical microbub-
bles (image in the inset shows the ≈2 cm diameter of the assembly). b,c) OM images of (b) the 2D HCP and (c) 2D honeycomb lattice composed of
H-GO-shelled microbubbles. The insets show 2D fast Fourier transform images. The 2D HCP and 2D honeycomb lattice structures exhibit identical
topologies, as revealed in the skeletal lattice images (second row of (b) and (c)) and lattice edge length distributions (third row of (b) and (c)). d) A
digital photograph of the centimeter-scale 3D CCS of GO microbubbles placed on a green foxtail (after reduction). e) 3D reconstructed X-ray micro­
tomography images of the 3D assembly of thermally reduced H-GO-shelled microbubbles. f) SEM image of the 3D RDH structure. The inset shows a
cross-sectional image of an ideal RDH structure, which agrees well with the experimentally obtained SEM images (locally highlighted in yellow lines).
g) Stress–strain curves of the 3D RDH structure (ρ = 4.66 mg cm–3) and 3D assembly of H-GO-shelled microbubbles (ρ = 11.7 mg cm–3). h) Consecu-
tive digital photographs showing the compressibility of the 3D RDH structure. i) An Ashby plot for the 3D RDH structures compared to carbon-based
3D porous structures (open- and closed-cellular) and 3D-printed structures.

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in terms of the mechanical property. Overall, the mechanical
strength of our 3D CCS is at the most advanced level among
carbon-based open/CCSs ever reported at an equivalent den-
sity. In particular, as compared to aerographite,[12] the fabricated
3D CCS exhibited one order of magnitude greater E by density
(i.e., along E ~ ρ , blue dotted line in Figure 4i). Ultimately, the
3D graphene CCS based on hierarchically architected GO BUs
successfully serves as a state-of-the-art, carbon-based, ultralight,
mechanically strong, and even superelastically resilient func-
tional material that is expected to be widely applied.
In summary, we demonstrated a new class of 3D CCS com-
prising rGO nanosheets, which concurrently exhibited ultra-
lightness and high mechanical strength as well as superelastic
behavior. The resulting materials contain hierarchical cellular
architectures spanning seven orders of magnitude from a few
nanometers (i.e., the design of GO nanosheets), micrometers (i.e.,
generation of microbubbles using functionalized GO nanosheets
by a microfluidic technique), to a few centimeters (i.e., directed
assembly into 2D and 3D structures). Eventually, the 3D assem-
bled structures are transformed into self-interconnected CCS
with complete space-filling plesiohedra (convex polyhedra) by
thermal reduction, resulting in scalable 3D RDH graphene struc-
tures at the macroscale. These approaches can be easily extended
to a variety of BUs with diverse shapes and compositions for the
enhancement of other properties such as electronic and optical
properties and used to elucidate the relationship between mate-
rial properties and structural characteristics.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
S.J.Y. and M.J.O. contributed equally to this work. This work was
supported by Samsung Research Funding Center for Samsung
Electronics under Project Number SRFC-MA1602-02 and the institutional
research program of the Korea Institute of Science and Technology
(KIST) (2E28070).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
closed-cellular structures, graphene, lightweight materials, microsolid
bubbles, plesiohedra
Received: May 9, 2018
Revised: July 16, 2018
Published online: August 29, 2018
[1] Y. H. Kim, H. Kang, S. Park, A. R. Park, Y. M. Lee, D. K. Rhee,
S. Han, H. Chang, D. Y. Ryu, P. J. Yoo, Adv. Mater. 2014, 26, 7998.
[2] G. S. Cole, A. M. Sherman, Mater. Charact. 1995, 35, 3.
[3] J. C. Williams, E. A. Starke, Acta Mater. 2003, 51, 5775.
Adv. Mater. 2018, 30, 1802997 1802997 (7 of 7)
www.advmat.de
[4] F. C. Campbell, Lightweight Materials: Understanding the Basics, ASM
International, Materials Park, OH, USA 2012.
[5] T. A. Schaedler, A. J. Jacobsen, A. Torrents, A. E. Sorensen, J. Lian,
J. R. Greer, L. Valdevit, W. B. Carter, Science 2011, 334, 962.
[6] X. Zheng, H. Lee, T. H. Weisgraber, M. Shusteff, J. DeOtte,
E. B. Duoss, J. D. Kuntz, M. M. Biener, Q. Ge, J. A. Jackson,
S. O. Kucheyev, N. X. Fang, C. M. Spadaccini, Science 2014, 344, 1373.
[7] L. R. Meza, S. Das, J. R. Greer, Science 2014, 345, 1322.
[8] Y. Zhu, S. Murali, W. Cai, X. Li, J. W. Suk, J. R. Potts, R. S. Ruoff, Adv.
Mater. 2010, 22, 3906.
[9] Y. Xu, K. Sheng, C. Li, G. Shi, ACS Nano 2010, 4, 4324.
[10] Z. Chen, W. Ren, L. Gao, B. Liu, S. Pei, H.-M. Cheng, Nat. Mater.
2011, 10, 424.
[11] X. Zhang, Z. Sui, B. Xu, S. Yue, Y. Luo, W. Zhan, B. Liu, J. Mater.
Chem. 2011, 21, 6494.
[12] M. Mecklenburg, A. Schuchardt, Y. K. Mishra, S. Kaps, R. Adelung,
A. Lotnyk, L. Kienle, K. Schulte, Adv. Mater. 2012, 24, 3486.
[13] L. Qiu, J. Z. Liu, S. L. Y. Chang, Y. Wu, D. Li, Nat. Commun. 2012,
3, 1241.
[14] H. Sun, Z. Xu, C. Gao, Adv. Mater. 2013, 25, 2554.
[15] J. Li, J. Li, H. Meng, S. Xie, B. Zhang, L. Li, H. Ma, J. Zhang, M. Yu,
J. Mater. Chem. A 2014, 2, 2934.
[16] Y. Wu, N. Yi, L. Huang, T. Zhang, S. Fang, H. Chang, N. Li, J. Oh,
J. A. Lee, M. Kozlov, A. C. Chipara, H. Terrones, P. Xiao, G. Long,
Y. Huang, F. Zhang, L. Zhang, X. Lepró, C. Haines, M. D. Lima,
N. P. Lopez, L. P. Rajukumar, A. L. Elias, S. Feng, S. J. Kim,
N. T. Narayanan, P. M. Ajayan, M. Terrones, A. Aliev, P. Chu,
Z. Zhang, R. H. Baughman, Y. Chen, Nat. Commun. 2015, 6, 6141.
[17] E. García-Tuñon, S. Barg, J. Franco, R. Bell, S. Eslava, E. D’Elia,
R. C. Maher, F. Guitian, E. Saiz, Adv. Mater. 2015, 27, 1688.
[18] C. Zhu, T. Y.-J. Han, E. B. Duoss, A. M. Golobic, J. D. Kuntz,
C. M. Spadaccini, M. A. Worsley, Nat. Commun. 2015, 6, 6962.
[19] N. Ni, S. Barg, E. Garcia-Tunon, F. M. Perez, M. Miranda, C. Lu,
C. Mattevi, E. Saiz, Sci. Rep. 2015, 5, 13712.
[20] Q. Zhang, F. Zhang, S. P. Medarametla, H. Li, C. Zhou, D. Lin,
Small 2016, 12, 1702.
[21] Z. Qin, G. S. Jung, M. J. Kang, M. J. Buehler, Sci. Adv. 2017, 3,
e1601536.
[22] J. W. Suk, R. D. Piner, J. An, R. S. Ruoff, ACS Nano 2010, 4, 6557.
[23] H. Kim, R. Namgung, K. Singha, I. K. Oh, W. J. Kim, Bioconjugate
Chem. 2011, 22, 2558.
[24] H. Fan, C. Hartshorn, T. Buchheit, D. Tallant, R. Assink, R. Simpson,
D. J. Kissel, D. J. Lacks, S. Torquato, C. J. Brinker, Nat. Mater. 2007,
6, 418.
[25] T. Brugarolas, F. Tu, D. Lee, Soft Matter 2013, 9, 9046.
[26] S. J. Yeo, K. J. Park, K. Guo, P. J. Yoo, S. Lee, Adv. Mater. 2016, 28,
5268.
[27] L. D. Landau, E. M. Lifshitz, Theory of Elasticity, 3rd ed., Pergamon,
New York 1986.
[28] K. Higashiguchi, J. Imai, K. Matsuda, Langmuir 2016, 32, 4945.
[29] J. B. Berger, H. N. G. Wadley, R. M. McMeeking, Nature 2017, 543,
533.
[30] M. A. Worsley, S. O. Kucheyev, J. H. Satcher, A. V. Hamza,
T. F. Baumann, Appl. Phys. Lett. 2009, 94, 073115.
[31] K. H. Kim, Y. Oh, M. F. Islam, Nat. Nanotechnol. 2012, 7, 562.
[32] Y. Li, J. Chen, L. Huang, C. Li, J. D. Hong, G. Shi, Adv. Mater. 2014,
26, 4789.
[33] S. Barg, F. M. Perez, N. Ni, P. do Vale Pereira, R. C. Maher,
E. Garcia-Tuñon, S. Eslava, S. Agnoli, C. Mattevi, E. Saiz, Nat.
Commun. 2014, 5, 4328.
[34] B. Zhang, J. Zhang, X. Sang, C. Liu, T. Luo, L. Peng, B. Han, X. Tan,
X. Ma, D. Wang, N. Zhao, Sci. Rep. 2016, 6, 25830.
[35] X. Zhao, W. Yao, W. Gao, H. Chen, C. Gao, Adv. Mater. 2017, 29, 1701482.
[36] L. J. Gibson, M. F. Ashby, Cellular Solids: Structure & Properties,
Cambridge University Press, Cambridge, UK 1997.
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