Materials Research Letters

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Holey graphene: a unique structural derivative of

graphene

Yi Lin, Yunlong Liao, Zhongfang Chen & John W. Connell

To cite this article: Yi Lin, Yunlong Liao, Zhongfang Chen & John W. Connell (2017): Holey
graphene: a unique structural derivative of graphene, Materials Research Letters, DOI:
10.1080/21663831.2016.1271047

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MATER. RES. LETT., 2017
http://dx.doi.org/10.1080/21663831.2016.1271047

Holey graphene: a unique structural derivative of graphene

Yi Lina,b , Yunlong Liaoa,c , Zhongfang Chenc and John W. Connelld
a National Institute of Aerospace, Hampton, VA, USA; b Department of Applied Science, The College of William and Mary, Williamsburg, VA, USA;
c Department of Chemistry, Institute for Functional Nanomaterials, University of Puerto Rico, San Juan, Puerto Rico; d Advanced Materials and
Processing Branch, NASA Langley Research Center, Hampton, VA, USA

ABSTRACT ARTICLE HISTORY

Holey graphene (hG), also called graphene nanomesh, is a structural derivative of graphene. hG is Received 13 October 2016
formed by removing a large number of atoms from the graphitic plane to produce holes distributed Accepted 6 December 2016
on and through the atomic thickness of the graphene sheets. These holes, sometimes with abundant KEYWORDS
functional groups around their edges, impart properties that are uncommon to intact graphene but Holey graphene; graphene
advantageous toward various applications. In this review, strategies to prepare hG and the related nanomeshes; porous
applications that take advantage of the unique structural motif of these materials are discussed. graphene; synthesis and
Prospects are then given for this emerging class of graphene derivatives. applications; energy storage

IMPACT STATEMENT
Holey graphene is a novel class of graphene derivative that has in-plane porosity. It outperforms
intact graphene in many applications such as nanoelectronics, sensors, energy storage, and mem-
branes.

1. Introduction
sheets [4,5]. The highest quality sheets come from
An ideal graphene sheet is a perfect two-dimensional mechanical exfoliation (the ‘Scotch tape’ method), which
graphitic crystal consisting of only one layer of carbon can generate large area sheets with very low defect density
atoms. Since its first isolation in 2004 [1], graphene has [1]. However, this method is not scalable as it provides
attracted applications in the fields of electronics, sensors, only a few sheets on supported substrates. The most scal-
composites, and energy storage due to its high surface able method for applications, such as composites and
area, high electrical and thermal conductivity, excellent energy storage, is oxidation and exfoliation of graphite to
mechanical strength, thermal and chemical stability, and generate graphene oxide (GO), which can be reduced to
the ability to be modified to introduce diverse chemical restore its graphitic structure [6]. The graphene thus pro-
functionalities [2,3]. duced, called reduced graphene oxide (rGO), has defects,
In the last decade, many methods have been estab- but can be prepared routinely in gram quantities in lab-
lished to prepare monolayer or few-layered graphene oratories, and has recently been industrialized to ton

CONTACT Yi Lin [email protected] National Institute of Aerospace, Hampton, VA 23666, USA; Department of Applied Science, The College
of William and Mary, Williamsburg, VA 23185, USA
This work was authored as part of the Contributor’s official duties as an Employee of the United States Government and is therefore a work of the United States Government. In accordance
with 17 U.S.C. 105, no copyright protection is available for such works under U.S. Law. This is an Open Access article that has been identified as being free of known restrictions under
copyright law, including all related and neighboring rights (https://creativecommons.org/publicdomain/mark/1.0/). You can copy, modify, distribute and perform the work, even for
commercial purposes, all without asking permission.
2 Y. LIN ET AL.

quantities [7]. Other methods, such as chemical vapor • Can a graphene sheet retain its mechanical integrity
deposition (CVD) growth [8] and liquid exfoliation of when large (nanometers or larger) defects or holes are
graphite [9], have also been industrialized and pro- introduced?
vided graphene materials with qualities and quantities in • How would the electronic properties of graphene
between the above two extremes and give specific prop- change when quantum confinement is induced by the
erty combinations required for some applications [10]. sculpturing of the conjugated structure?
While mechanically exfoliated graphene sheets are
usually of high atomic order, as-produced graphene Answering these questions was a major driving force
sheets from many other methods always contain defects in early hG research, which primarily focused on high-
from atomic to nanoscale. At first glance, it would seem precision and high-fidelity methods to create holes on
undesirable to have defects on graphene sheets, since intact graphene sheets. These methods include both
defects would be detrimental to mechanical strength low-throughput approaches such as nanoscopic elec-
and electrical conductivity. However, due to quantum tron beam drilling, and high-throughput methods such
confinement effects, structural defects at the nanoscale as nanolithography or templated growth. In the high-
impart unique physical and chemical properties to throughput methods, highly ordered arrays of holes with
nanosized objects, thereby affording desirable proper- well-controlled shapes could be formed on graphene sur-
ties for some applications [11–13]. For example, the faces. Although these high-precision and high-fidelity
presence of defects may allow more facile attachment methods are only applicable to substrate-supported
of functional groups, which may affect other proper- graphene, they can produce materials for morphological
ties such as processing characteristics or interaction studies as well as electronic measurements and appli-
with other materials including polymer or biological cations. In particular, hGs with highly ordered hole
agents, making these functionalized graphene materials arrays are often viewed as interconnected graphene
more beneficial in polymeric composites and biological nanoribbons [14,15]. Unlike perfect graphene sheets
applications [3]. with zero band gap, graphene nanoribbons are semi-
This review discusses a unique category of defec- conductors with high electron mobility, making them
tive graphene material called ‘holey graphene’ (hG, also one of the ideal choices for graphene-based field-effect
called ‘graphene meshes’ or ‘graphene nanomeshes’). For transistor (FET) devices [21,22]. Scalable fabrication
hG, nanometer-sized or even larger (‘mesoscale’) holes of high-quality, narrow-width graphene nanoribbons
are intentionally introduced to afford significant gains for has been a challenge [5]. The high-fidelity prepara-
various applications. For example, the creation of a large tions of hG as nanoribbon-mimics exhibited excellent
number of holes can result in quantum confinement of performance and provided new alternatives in FET
the remaining graphitic structure, which leads to signif- applications.
icant changes to electronic properties of the nanosheets
[14,15]. For sensing applications, the abundant hole-edge 2.1.1. Electron or ion-beam bombardment
functional groups provide many more active sites and To produce holes through a thin layer of material in
can increase the sensitivity or response toward targeted the macroscopic world, the use of mechanical force is
chemical or biological species [16]. In energy storage a straightforward choice. One approach to obtain holes
applications, the presence of holes may allow facile cross- through graphene sheets was achieved by high-energy
plane ion transport, enabling high-charge-/discharge- bombardment with electrons or ions. For example,
rate devices [17–19]. Herein, various strategies to prepare the electron beam in a transmission electron micro-
hG are systematically presented, followed by a discussion scope (TEM) was used to drill nanometer-sized holes
on several representative applications that are enabled by in graphene sheets, while the entire process was mon-
the structural motifs of hG. Finally, some prospects for itored via real-time imaging. In one of the first efforts,
this emerging class of graphene structural derivatives are Fischbein and Drndic suspended mechanically exfoli-
summarized. ated multilayer graphene sheets over a hole in an SiNx
membrane, and condensed the imaging electron beam
to the nanometer level [20]. The energy of the electron
2. Preparation of holey graphene beam was sufficient to ablate through the graphene layers,
forming pores of circular shapes (Figure 1). By control-
2.1. High-precision and high-fidelity methods
ling the position and/or movement of the electron beam,
The initial curiosity toward intentionally introducing pores of different shapes (circular or line-shaped) and
structural vacancies on graphene surfaces evolved from arrays of pores were prepared at a rate of a few seconds
two considerations [20]: per hole. For defect-free graphene, the threshold electron
 MATER. RES. LETT. 3

through the holes [25–27]. More details will be discussed

in Section 3.3.

2.1.2. Nanolithographic methods

Compared to electron beam drilling, nanolithographic
etching is a high-throughput method to produce hG
with periodic arrays of holes and narrow hole-size
distributions [28]. A typical nanolithographic etching
process consists of several common steps:

(1) Graphene sheets are deposited or synthesized on a

substrate
(2) A porous template or mask is prepared to cover the
top surface of the graphene sheets
(3) An etching process is conducted
(4) The template or mask is removed to yield hG
products
Figure 1. TEM images of a suspended graphene sheet (a) before
and (b) after a nanopore is made by electron beam ablation. The compositions of the porous templates or masks
(c) Higher magnification image of the nanopore. (d) Multiple varied, including block copolymers, polystyrene (PS)
nanopores made in close proximity to each other. Scale bars are
nanospheres, anodic aluminum oxide (AAO) [29,30],
50, 50, 2, and 10 nm, respectively. Reproduced from Ref. [20] with
permission from AIP Publishing LLC. or patterned photoresist layers [31–33]. These templates
are required to be inert towards graphene and to only
contribute morphologically during the etching process.
This technique was first independently reported in
beam energy needed for hole ablation was ∼ 80 keV, with 2010 by Bai et al. [14] and Kim et al. [15] who synthe-
the carbon displacement cross-section rapidly rising with sized hG (‘graphene nanomeshes’) with highly ordered
increasing energy [23]. However, the presence of defects, mesh-like structures using block copolymer lithography,
doped atoms, and contaminations significantly reduced which is a multi-step nanolithographic method using a
the ablation energy threshold. block copolymer as the template (Figure 2). Both groups
High-energy ion beams can also ablate through the used poly(styrene-block-methyl methacrylate) [P(S-b-
graphene layers. In the report by Standop et al. [24], a MMA)], a thin film that exhibits hexagonally packed
graphene monolayer supported on an Ir(111) substrate cylindrical poly(methyl methacrylate) (PMMA) domains
was subjected to 5 keV Xe+ irradiation at room tempera- in the PS matrix. After coating the graphene with a sacri-
ture. Interestingly, with an off-normal incident angle of ficial SiOx layer followed by the block copolymer, PMMA
75°, each incident ion left a track of a few nanometer- domains were removed via UV exposure, and the tem-
sized holes along the impacting direction. In an ‘inter- plate was developed using glacial acetic acid. A reactive-
face channeling’ model, it was proposed that the incident ion etch (RIE) process was then used followed by an oxy-
ions might have penetrated through the top graphene gen plasma etch to drill through the SiOx layer, and then
layer, and reflected between the metallic substrate and the underlying graphene sheet. Removing the SiOx layer
the graphene sheet, resulting in multiple hole openings resulted in hG with highly ordered hexagonally packed
on the sheet. By controlling the irradiation energy and holes inherited from the block copolymer. It is possi-
flux, graphene nanomesh with well-spaced holes was cre- ble to tune the periodicity of the hexagonal packing by
ated with the hole-distribution periodicity regulated by using different molecular weights of the block copolymer.
the incident irradiation angle and the graphene–substrate At the same periodicity, using the same block copoly-
distance. mer, over-etching resulted in larger holes and smaller
The above electron and ion beam of drilling processes ‘neck widths’, i.e. the widths of the graphene structure
are highly localized with high precision. Obviously, it is between adjacent holes (eg ∼ 9–15 nm at 39 nm period-
prohibitively time-consuming if a large array of holes icity). The concept of the neck width is important for the
is to be drilled with such techniques. Although these hG materials from nanolithographic methods because
methods are not scalable, they enabled some interest- their primary application is for FET devices in which
ing sensing experiments in which ionic current block- hGs mimic the behavior of graphene nanoribbons. The
age was detected while passing molecules, such as DNA, widths of graphene nanoribbons are directly related to
4 Y. LIN ET AL.

along with a protection layer of PMMA to etch large

area Si/SiO2 substrate-supported rGO with O2 plasma.
The hole dimensions and neck widths of the hG were
largely determined by those in the AAO template [29,36].
More structural tunability was achieved by sputtering Pt
onto AAO to create porous Pt masks of various neck
widths, which were then used as direct templates for hG
formation [37].
Monodisperse colloidal nanoparticles were also used
as templates for hG preparation. As shown in Figure
3, Sinitskii and Tour [38] spread a monolayer of sil-
ica nanoparticles of a given diameter onto graphene
that was first covered with a protective silica layer. The
stack was subjected to RIE to partially etch the silica
nanoparticles to a desired diameter, partially exposing
the graphene/protection layer underneath. Subsequently,
another protection layer (Au) was evaporated onto the
stack, followed by removal of the silica nanoparticles and
a second RIE step to carve holes in the graphene. All pro-
tection layers were then removed to afford hG. The key to
achieving highly ordered hole structures in nanosphere
lithography is to use highly monodisperse nanoparti-
cles. Colloidal PS nanoparticles with well-established
preparation procedures were also excellent choices as
lithographic templates for hG preparation [39–41]. The
nanosphere lithography yielded hGs with larger hole
diameters ( > 100 nm) so this method was complemen-
tary to the block copolymer method. With excellent elec-
tronic properties, the FET devices based on hG from
Figure 2. Schematic depiction of the fabrication of nanoperfo-
rated, highly oriented pyrolitic graphene (HOPG), or hG, using nanosphere lithography were used as chemiresistor sen-
block copolymer lithography and the corresponding top-down sors that exhibited superior response to both electron-
scanning electron microscopy (SEM) images of (a) vertically ori- donating and electron-withdrawing gaseous species such
ented PMMA cylinders in a block copolymer thin film obtained by as NO2 and NH3 [39].
thermal annealing, (b) residual PS honeycomb template obtained Conventional photolithographic methods were
after selective PMMA removal with UV irradiation, (c) etched struc-
tures after O2 followed by CHF3 + O2 plasma RIE resulting in the employed to prepare large area ‘graphene meshes’ with
etching of the random copolymer mat and the oxide buffer layer, periodicity on the order of tens of micrometers [31].
respectively, and (d) nanoperforated HOPG resulting from the final E-beam lithography was used to prepare meshes with
O2 plasma RIE and the removal of the oxide buffer by HF solution. hole widths of a few micrometers [42]. However, such
Scale bars = 200 nm. Reproduced from Ref. [15] with permission graphene meshes are prepared from thin films, not indi-
from American Chemical Society.
vidual graphene sheets, and are not a graphene struc-
tural derivative but modified films. An exception was a
their electronic properties. Similarly, the neck width is recent report which demonstrated that the use of inter-
one of the crucial factors for the hG-based FET device ferometric lithography could reduce the neck width of
performances. the photoresist to 70 nm [33]. With 80 s of O2 plasma
Instead of using a block copolymer, Liang et al. etching, the neck widths of the exceptionally large area
[34] used nanoimprint templates to physically impose graphene mesh could reach as narrow as 10 nm, a dimen-
periodic hole arrays onto the PS-based resist coating, sion relevant to the structural modification of individ-
followed by similar RIE etching procedures to produce ual graphene sheets. The method was used to prepare
substrate-supported hG with highly ordered holes. wafer-scale samples over 1 × 1 cm2 with a periodicity of
AAO has vertically aligned hexagonal arrays of cylin- 150–200 nm, which exhibited reasonable FET character-
drical nanochannels, and has been widely used for the istics that were comparable to hG samples from other
template formation of various one-dimensional nanos- nanolithographic techniques (Table 1). A slight draw-
tructures [35]. Zeng et al. [29] utilized AAO as a mask back was that the residual photoresist could not be fully
 MATER. RES. LETT. 5

Figure 3. Nanosphere lithography for hG. Reproduced from Ref. [38] with permission from American Chemical Society.
Table 1. Comparison of dimensions and electronic properties of hGs fabricated by different techniques.
Fabrication technique
Block copolymer Block copolymer Nanoimprint AAO templating Nanosphere Nanosphere Interferometric
Properties lithography [14] lithography [15] lithography [34] [37] lithography [38] lithography [43] lithography [33]
Graphene type SL/ML SL SL SL NR SL SL
Sheet coverage (μm2 ) NR 106 4 NR NR NR 108
Minimum neck width (nm) 5 18 7 15 20 65 10
ON/OFF ratioa 100 39 80 10 10 2 35
Mobilitya (cm2 /V s) NR >1 1000 NR NR 31 80
Band gapa (meV) 100 102 NR NR NR 0 30
Channel width (μm) 3 NR 2 5.8 1.5 1 2
Channel length (μm) 2.3 NR 2 2 20 2 2000
Source: Reproduced from Ref. [33] with permission from Nature Publishing Group.
Note: SL: monolayer; ML: multi-layered; NR: not reported.
a ON/OFF ratios, mobilities, and band gaps are all room temperature values.

removed, leaving ∼ 15–20 nm coatings on the product. growth of graphene. The templates served as the inert
Nevertheless, the Raman spectra of the graphene struc- islands blocking the otherwise continuous graphene for-
tures were readily detected. The locations with 10 nm mation, creating well-defined patterns.
neck width exhibited enhanced D-band attributed to the In one of the first demonstrations, Safron et al.
increased edge-to-surface atomic ratios. [44] patterned aluminum oxide (Al2 O3 ) via e-beam
and block copolymer lithography as the inert templates
2.1.3. Templated growth (or ‘barriers’) on Cu foil. Various shapes and patterns
Bottom-up growth of graphene using CVD approaches of barriers were fabricated, and graphene was subse-
with gaseous carbon precursors has been extensively quently grown via CVD on the exposed Cu at 1000°C.
studied in recent years [3,8]. In a typical CVD growth The oxide barriers were then removed, leaving well-
process, a gaseous carbon feedstock, such as methane, defined patterned graphene. Block copolymer lithogra-
is introduced into a heated furnace and decomposes on phy allowed the deposition of a hexagonal array of Al2 O3
the surface of a supporting smooth metallic (typically nanoparticles of 16 nm in diameter with a periodicity
Cu or Ni) substrate that has extremely low carbon sol- of 41 nm. Remarkably, the holes after graphene growth
ubility, thereby allowing the two-dimensional growth of were only ∼ 1 nm larger in diameter than the nanopar-
graphene crystals. In the nanolithography approaches ticle templates (neck width ∼ 24 nm), suggesting near-
for hG discussed in the previous section, graphene is atomic precision of the barrier function at the given
first grown or deposited onto a substrate covered with growth conditions. The nucleation density of graphene
the nanotemplates, and then selectively etched. In the on the nanoparticle-patterned Cu was lower than unim-
templated growth of hG, the nanotemplates are first peded growth on bare Cu, but the shape of the crystal-
deposited onto an active substrate, followed by CVD lites remained hexagonal. Multiple domains seamlessly
6 Y. LIN ET AL.

GO or rGO from the highly oxidative synthesis con-

ditions usually serve as the main seeding sites for the
hole growth to form hG. It should also be noted that
most scalable methods that are used to process GO into
hG are also applicable to substrate-supported graphene
sheets, although the conditions must be adjusted to avoid
over-oxidation.

2.2.1. Liquid-phase oxidation

Figure 4. Nanosphere-templated hG growth. Reproduced from Liquid-phase oxidation methods using conventional wet
Ref. [43] with permission from Nature Publishing Group. chemistry are popular in hG synthesis. In many examples,
the direct products from liquid-phase oxidation meth-
zipped together to form a large-area, continuous high- ods were holey graphene oxide (hGO) nanosheets, the
quality hG film. Compared to hG from top-down (ie highly oxidized and water-soluble form of hG. hGO can
using intact graphene as the starting material) lithog- be reduced to more electrically conductive hG via reduc-
raphy methods, the Raman spectra of the CVD-grown tion methods applicable to GO. The comparison of hGO
hG exhibited much lower D-band intensity, suggesting vs. hG is highly analogous to that of GO vs. rGO.
well-defined hole edges where the barriers terminated In Hummer’s method in which graphite is oxidized
growth. Similar findings were reported by Wang et al. and exfoliated by acidified KMnO4 [4–6], the reaction
[43], who used a closely packed colloidal PS nanoparticle mixture is typically heated to 40–70°C for a few hours.
monolayer to pattern SiO2 islands that served as the tem- Alternatively, using microwave irradiation with acidified
plates/barriers for CVD growth of hG with neck widths KMnO4 produced GO in as little as 30 s [46]. Interest-
of 65–75 nm (Figure 4). This bottom-up, nanosphere- ingly, only slightly longer exposure (40 s) resulted in con-
templated growth method is analogous to the top-down trolled over-oxidation and yielded hGO. The presence
nanosphere lithography for hG formation discussed in of both strong mixed acids (H2 SO4 :HNO3 = 4:1) and
the previous section (Figure 3) [38]. KMnO4 oxidants was critical to the hGO formation. The
Using AAO as the template, Jung et al. [37] sputtered mixed acids introduced nitronium ions, which attacked
a thin Au layer and transferred it onto an SiO2 wafer for both defect and graphitic carbons to create defects on the
graphene growth. The morphology of the AAO channels graphite, while KMnO4 preferentially reacted with exist-
led to hG films with neck widths as small as 19 nm. In ing defects facilitating hole formation. Consequently, the
a related gram-scale bottom-up growth method, highly use of only mixed acids without KMnO4 resulted in small
porous MgO crystalline platelets were used as the growth graphene pieces [46]. However, with GO as the start-
template for graphene [45]. However, graphene growth ing material, KMnO4 alone was sufficient to form hGO
was not planar because it followed the contours of the with microwave energy [47]. In a related report, liquid
porous MgO templates. Therefore, these products were exfoliated graphene (from organic solvent sonication of
not exactly hG, but more precisely a type of porous graphite [9]), which has fewer defects than GO, was used
graphene with continuous graphitic structures. as the starting material for hG via the use of room tem-
perature KMnO4 solution, followed by treatment with
hot HCl [48]. The oxidation extent was less because of
2.2. Scalable methods
the lack of a strong oxidizing acid; the hG product had
For many non-electronic applications such as compos- few defects, and remained in a non-oxidized form with
ites and energy storage, large quantities of active mate- relatively low oxygen content.
rials are needed. The high-precision methods for hG Concentrated HNO3 was another reagent used for
synthesis discussed in the previous section do not usu- hG/hGO synthesis. In fact, the first successful large-
ally provide enough material for such purposes. To pre- scale hGO syntheses were by Kung and coworkers, who
pare bulk quantities of hG, the first step is to obtain used 1 h bath sonication to process an aqueous mix-
enough graphene starting material. As discussed in the ture of GO and concentrated HNO3 , leading to hGO
Introduction, one of the most convenient and scalable with wide hole-size distributions [17,49]. Increasing the
methods to prepare graphene is via GO nanosheets amount of HNO3 resulted in larger holes with a higher
produced by liquid-phase oxidation and exfoliation of extent of oxidation. In comparison to GO, hGO had more
graphite. The majority of the scalable hG preparation carbonyl and carboxylate functional groups. The high
methods reported thus far started with either GO or water solubility of hGO made it readily processable, like
its reduced form (rGO). The abundant defect sites in the parent GO. For example, by following the typical
 MATER. RES. LETT. 7

excess KMnO4 at the end of the oxidation reaction and is

generally considered ineffective at oxidizing the graphitic
surface. However, Xu et al. demonstrated that diluted
H2 O2 oxidized GO in aqueous solutions forming hG, but
only under hydrothermal conditions [19,52]. For exam-
ple, at 180°C for 6 h, the GO sheets transformed into
an interconnected hydrogel network of hG sheets via
self-assembly (Figure 6) [19]. After reduction and freeze-
drying steps, foam-like hG monoliths were obtained. The
hG foams were lightweight and highly compressible, and
exhibited high surface area and excellent electrical con-
ductivity. At a lower hydrothermal reaction temperature
(100°C for 4 h) where a hydrogel was not formed, water-
soluble hGO was found to be the product [52]. The hGO
solutions were subsequently processed into hydrogels or
papers for energy storage applications [19,52].
Figure 5. Schematic drawing (not to scale) of the introduction of Alternatively, Au nanoparticles catalyzed the H2 O2
in-plane pores into GO and the subsequent filtration into an HGO oxidation of rGO into hG via UV photolysis [53]. It
paper. The thermal reduction of GO sheets with in-plane poros- was proposed that the Au nanoparticles catalyzed both
ity and removal of water molecules from the interlayers result
in a three-dimensional network with interconnecting graphitic
the decomposition of H2 O2 into · OH (hydroxyl radi-
domains that retain high electrical conductivity and structural cal) and the oxidation of rGO by · OH (more info in
integrity and disordered porous graphene regions that provide Section 2.2.4). Hole-edge functionalities, especially car-
interplane diffusion channels (rHGO). Li ions can diffuse through- boxylic acid moieties, made some hG products excellent
out the structure rapidly through the in-plane pores and inter- candidates to detect trace H2 O2 , with their sensitivity
plane channels. The interlayer spacing between graphene sheets
comparable to the widely adopted biosensing approach
is greatly exaggerated. The digital image shows a coin cell-size
rHGO paper. Reproduced from Ref. [49] with permission from using horseradish peroxidase (HRP) [51]. Interestingly,
American Chemical Society. HRP, a common oxidative enzyme molecule, in the pres-
ence of H2 O2 also catalyzed the oxidation of GO to form
holes on graphene sheets after a few days of incubation
method of preparing ‘GO paper’ [50], hGO was vac- [54]. However, the same procedure was ineffective toward
uum filtered to form a free-standing membrane (‘HGO rGO, presumably due to conformational restrictions that
paper’) that was reduced into ‘rHGO paper’ (ie hG paper) induced insufficient activity of the enzyme after binding
(Figure 5). to the less hydrophilic graphitic surfaces of rGO.
Chemically reduced GO was also oxidatively etched by
refluxing in concentrated HNO3 for a prolonged period 2.2.2. Gaseous-phase etching
of time (4–11 h) [51]. The resultant hGs had pore sizes As-prepared graphene sheets, especially thermally
of 10–40 nm (4 h reflux) or > 40 nm (9 h reflux); both reduced GO (t-rGO) from rapid heating of GO to achieve
had high pore densities. However, 11 h of reflux resulted simultaneous reduction and exfoliation [55], contain
in over-oxidation and cleaved the rGO sheets into small abundant intrinsic point defects. These point defects can
pieces. Controlled oxidation removed the defect carbons originate from the parent GO due to the oxidative synthe-
and formed holes on rGO sheets, but the resulted hG sis conditions, or may be formed during the rapid heat-
products had much lower oxygen content than typical ing due to the quick release of gaseous byproducts such
GO and hGO. Interestingly, the products still had small as CO2 . Recently, several groups, including our team,
enough zeta-potentials (−36 to −46 mV) to be stable in built upon this aspect of the thermal exfoliation pro-
aqueous solution, and were readily soluble in water and cess to produce hG using controlled partial air oxidation
processable using aqueous methodologies. The solubility [18,56–60]. These processes were typically carried out in
was most likely rendered by the abundant hole-edge- air without solvents or other chemical agents, making
attached, oxygen-containing functional groups formed them the most facile methods for scalable hG production
with the holes. using GO or rGO as the starting material.
Milder oxidation reagents were also used for hG/hGO In one example of gaseous phase etching, a com-
synthesis, but they would require more demanding con- mercially obtained t-rGO powder was subjected to a
ditions, or the use of catalysts. In a typical Hummer’s single-step air oxidation near its weight-loss threshold
method for GO synthesis, H2 O2 is often used to remove ( ∼ 400–500°C) (Figure 7) [18,56]. Both temperature and
8 Y. LIN ET AL.

Figure 6. Preparation and structural characterization of hG foams (HGF). (a) Schematic illustration of the preparation process of HGFs
and HGF films. (b) A photograph showing a free-standing HGF. (c) SEM image of interior microstructures of HGFs. Scale bar = 1 μm. (d)
TEM image of hG sheets in HGFs. Scale bar = 10 nm. (e) TEM image of non-hG sheets in GFs for comparison. Scale bar = 10 nm. (f) A
photograph showing HGFs before and after mechanical compression with the flexibility of the compressed HGF film shown in the inset.
(g) Cross-sectional SEM image of the compressed HGF film. Scale bar = 1 μm. Reproduced from Ref. [19] with permission from Nature
Publishing Group.

heating duration were varied, and hG was formed at a of the hG products increased slightly, while the fraction
temperature as low as 390°C with a heating duration as of mesopores increased significantly. Further structural
short as 1 h [56]. At the more benign end of synthesis characterizations revealed that both the increased pop-
conditions (ie lower temperature and/or shorter heating ulation of oxygen-containing functional groups located
duration), defect carbons were selectively oxidized and around the hole edges and the increased mesopore frac-
gasified, forming holes with diameters of a few nanome- tion were likely the main causes for the observed capac-
ters on the graphene sheets. Interestingly, a further itance improvement. It was proposed that, after removal
increase in temperature and heating duration did not sig- of defective carbon during initial heating, further thermal
nificantly increase the hole size, but the electrochemical oxidation started to occur on graphitic carbons, result-
double layer capacitance of the products exhibited dra- ing in the formation of hole-edge functional groups and
matic improvement (approximately twofold). Despite the mesopores that were critical for electrochemical energy
presence of abundant holes, the D/G ratios in the Raman storage [56].
spectra of hG products remained similar to the starting Earlier efforts at rapid thermal exfoliation of GO were
t-rGO. The Brunauer–Emmett–Teller (BET) surface area purposely carried out in an inert atmosphere to avoid
 MATER. RES. LETT. 9

Figure 7. (a) Schematic of the scalable synthesis of the hG sheets, (b) digital photo of the as-synthesized hG powder in bulk, and (c)
Raman spectra comparison for hG obtained at 480°C/3 h and the starting graphene (t-rGO). Reproduced from Ref. [18] with permission
from American Chemical Society.

the formation of defects [55]. Such thermally exfoli- the oxygen in the air aided the mechanical punctua-
ated graphene material is intrinsically a ‘holey’ graphene tion from rapid expansion of gaseous products, arising
material, although in most cases the holes are in the size from oxidation of defect site functional groups, to form
domain of point defects (ie only a few atoms missing). nanometer-sized or even larger holes on graphene sheets.
By carrying out the thermal exfoliation of GO in air, Note that mostly point defects were formed upon rapid
Chang and coworkers successfully obtained hG materials heating in inert atmosphere. In Chang et al.’s experi-
with through-thickness holes (Figure 8) [57–59]. Here, ments, it was also demonstrated that a high heating rate

Figure 8. Schematic illustration for the ultra-rapid heating of GO powder to obtain and collect fluffy hG products with much increased
volume. Reproduced from Ref. [57] with permission from Elsevier.
10 Y. LIN ET AL.

was critical in the hole formation. Although slow heating the three-dimensionally interconnected pores than the
in air also resulted in exfoliated and reduced graphene, two-dimensional holes that are similarly present in other
few or no holes were present in the products. A lower typical hG materials.
heating temperature of 300°C was sufficient to intro- In the first reported experiments on a-MEGO in
duce holes while preserving abundant oxygen functional 2011 (Figure 9) [64], MEGO was first impregnated with
groups that are beneficial for electrochemical energy stor- a concentrated (7 M) KOH solution. The dried mix-
age. Higher temperatures with a high heating rate also ture was then treated at 800°C for 1 h under argon,
produced hG, but the oxygen functional groups were followed by washing to remove the excess base. A
mostly removed. final high-temperature-annealing step resulted in reduc-
The strategy of direct thermal exfoliation in air for hG ing the oxygen functional group content in a-MEGO
production could be pushed one step back in the GO materials. In comparison, many as-prepared hG mate-
production process to the stage where graphite was effec- rials from the liquid-phase or gaseous-phase oxidative
tively oxidized (eg using NaClO3 and fuming HNO3 ) but etching processes contain abundant oxygen functional
not yet exfoliated into GO (usually achieved in the pres- groups if no annealing step is applied. Nevertheless, the
ence of acidic KMnO4 ). Rapidly heating graphite oxide in a-MEGO products exhibited pore sizes ranging from
air at 300°C for 30 min also resulted in the formation of < 1 to 10 nm and BET surface area values, as high
hG [60]. Compared to graphite oxide, these hG materials as 3100 m2 /g. The theoretical surface area of graphene
exhibited increased surface area and mesopore popula- is only 2630 m2 /g. The ultra-large surface area was
tion, restoration of the graphitic network, and reduced attributed to the highly interconnected micropores and
oxidation extent. The X-ray photoelectron spectroscopy mesopores generated during the KOH etching process.
(XPS) data suggested that these materials had concen- Similar KOH-activation processes were also successfully
trations of oxygen-containing functional groups that are applied to t-rGO powder [64], GO films [65], and even
comparable to those in hG produced by other partial air ‘crumpled’ GO [66]. Activated graphene from ‘crumpled’
oxidation methods discussed above. GO not only exhibited micropores and mesopores that
Gaseous etching techniques were also applied to are typical for other a-MEGO materials, but also con-
substrate-supported graphene nanosheets. For example, tained macropores as a result of the aerosol spray dry-
Han and coworkers found that steam was a mild enough ing process that introduced the ‘crumpled’ morphology.
etchant to introduce in-plane pores on GO sheets sup- Their hierarchical pore structure makes these materials
ported on SiO2 /Si substrates or copper TEM grids [16]. excellent candidates for electrochemical energy storage.
The reaction was carried out in a sealed vessel at 200°C, Rather than heating at high temperature, KOH etch-
and pores of 2–40 nm were found. Air oxidation of ing of GO was conducted at ambient conditions with
substrate-supported GO could even proceed under room 30 h of ball-milling using a planetary mill [67–69]. Three-
temperature with UV light irradiation [61]. Oxygen-rich dimensional porous structures were also found in the
regions on the GO sheets were found to be the most final hG products, which exhibited somewhat lower
susceptible to further oxidation to form holes. BET surface area values ( ∼ 800 m2 /g) than typical a-
MEGO materials. Room temperature etching with aque-
2.2.3. Chemical activation ous NaOH solution was successful with silica-coated GO
Activated carbon (AC) is a high-surface-area material [70]. The treatment with NaOH not only removed the sil-
that has been industrialized and is commonly used ica coating, but also simultaneously caused perforation of
as an adsorbent and as an electrode [62,63]. A com- the graphene sheet.
mon method to produce AC is to chemically treat a
carbon stock with certain corrosive chemicals such as 2.2.4. Guided etching with catalytic or reactive
potassium hydroxide (KOH) followed by carbonization. nanoparticles
Ruoff and coworkers adopted a similar strategy and Many methodologies have been developed to deposit
used KOH to treat microwave-exfoliated GO (MEGO), inorganic (eg metal or metal oxide) nanoparticles onto
a type of reduced GO from a rapid microwave heat- the large lateral surface of graphene sheets [71]. The con-
ing process, and generated a high-porosity activated- ductive and high-surface-area graphene substrate often
graphene material dubbed ‘a-MEGO’ [64]. Activated enhances the performance of the nanoparticles, and
MEGO graphene sheets contain in-plane pores that are the resultant nanoparticle–graphene hybrids outperform
through the sheet thickness, a key feature of hG materi- the individual components in various applications such
als that are surveyed in this review. However, it should as catalysis, sensing, and energy storage. An interest-
be noted that the surface area values and electrochemi- ing application of the nanoparticle–graphene hybrids
cal properties of a-MEGO seem to be dictated more by was their usage as precursors for hG, as discussed in
 MATER. RES. LETT. 11

Figure 9. (A) Schematic showing the microwave exfoliation/reduction of GO and the following chemical activation of MEGO with KOH
that creates pores while retaining high electrical conductivity. (B) Low magnification SEM image of a three-dimensional a-MEGO piece.
(C) High-resolution SEM image of a different sample region that demonstrates the porous morphology. (D) Annular dark-field scanning
transmission electron microscopy image of the same area as (C), acquired simultaneously. As seen, a-MEGO contains micro- and meso-
pores with a distribution of sizes between ∼ 1 and ∼ 10 nm. (E) High-resolution phase contrast electron micrograph of the thin edge of
an a-MEGO chunk, taken at 80 kV. There is a variation in focus across the image because of the sloped nature of the sample and changes
in sample thickness. The image shows the presence of a dense network of nanometer scale pores surrounded by highly curved, pre-
dominantly single-layer carbon. (F) Exit wave reconstructed high-resolution transmission electron microscopy image from the edge of
a-MEGO. The in-plane carbon atoms are clearly resolved, and a variety of n-membered carbon rings can be seen. Substantial curvature of
the single-carbon sheets is visible, with the in-plane crystallinity being preserved. Reproduced from Ref. [64] with permission from The
American Association for the Advancement of Science.

this section. The well-dispersed nanoparticles on the route) or light irradiation (photochemical route).
graphene surface served as guiding sites for the chemical During etching, the nanoparticles catalytically pro-
etching reactions, in which the nanoparticles participated mote or chemically induce the gasification of car-
either as catalysts or as active reactants. This method bon at the contact area between the nanoparticles
can be viewed as the scale-up version of the nanosphere and graphene surface, leaving behind holes that are
nanolithography discussed in Section 2.1.2, even though through the graphene sheet thickness.
the shape control of holes and the regularity of hole arrays (3) The nanoparticles are removed to yield hG as the
were not as consistent. Another major difference was that final product.
the nanospheres in the lithographic methods function as
masks, but not catalysts/reactants. Although metal-catalyzed oxidative etching of graphite
A typical procedure to prepare hG via guided etching dates back to the 1970s [73,74], it was only recently
can be described as follows (guided catalytic etching is adapted for etching two-dimensional graphene sheets
shown in Figure 10 [72]): [75] and later for hG synthesis [72]. In 2012, Lin
et al. [72] reported the catalytic oxidative etching
(1) Active inorganic nanoparticles are deposited onto of graphene (Figure 10), where an Ag nanoparti-
the graphene surface to form a nanoparticle– cle–decorated graphene hybrid material was heated to
graphene hybrid. 300°C in air, a temperature much lower than the ther-
(2) The hybrid is subject to the etching reaction by mal decomposition threshold of graphene without Ag.
a provided form of energy such as heat (thermal Most newly formed holes on the graphene sheets were
12 Y. LIN ET AL.

Figure 10. A typical catalytic oxidative etching process to prepare hG. Reproduced from Ref. [72] with permission from The Royal Society
of Chemistry.

associated with Ag nanoparticles, suggesting the car- Ag was further confirmed by the XPS results, which
bon atoms that were in contact with Ag were removed showed that the Ag nanoparticles maintained their zero
during the etching (Figure 11). The catalytic role of valence state after the reaction. The Ag nanoparticles

Figure 11. Several representative electron microscopy images of an Ag-graphene sample subjected to air oxidation at 300°C for 3 h: (a)
a lower magnification SEM image showing both holes and tracks, SEM images showing areas enriched with (b) lower aspect ratio holes
and (c) high-aspect ratio holes (ie tracks), (d) a TEM image at higher magnification showing the morphology of a hole. Reproduced from
Ref. [72] with permission from The Royal Society of Chemistry.
 MATER. RES. LETT. 13

were conveniently removed via acid wash or reflux to In another report, Akhavan deposited GO sheets on
yield hG. By changing the size of the Ag nanoparticles, the tips of ZnO nanorod arrays that served as photocat-
the hG hole sizes could be tuned in the range of about alyst and etching sites for the GO [77]. The vertically
five to tens of nm. Despite the ‘defective’ appearance of aligned ZnO nanorods were less than 1 μm in length
these hG sheets with high densities of large holes, elec- and 140 nm in diameter, and they led to hG with hole
tron diffraction, Raman, XPS, and electron conductiv- sizes of ∼ 200 nm. The same authors found that TiO2
ity measurements, all indicated that these hG products nanoparticles were also effective in photochemical etch-
retained the two-dimensional graphitic structure as well ing of GO into hG [78].
as a chemical composition similar to that of the parent Alternatively, the catalytic etching of graphene could
graphene. be carried out in a reductive atmosphere. H2 etching
Other noble metal nanoparticles such as Au and Pt could also induce partial carbon gasification by form-
also acted as catalysts for hG formation via thermal oxi- ing CH4 (in comparison to the CO/CO2 products from
dation in air [72,76]. In a photocatalytic oxidation route, etching in air/O2 ). For example, Liu et al. [79] success-
as mentioned in Section 2.2.1, Radich and Kamat [53] fully etched CVD-grown graphene into nanomeshes in
used Au nanoparticles in a solution phase to catalytically 5% H2 at 500°C using Cu nanoparticles. There were
oxidize rGO under UV illumination. It was proposed several prior reports on nanoparticle-induced reductive
that the Au nanoparticles first catalyzed the oxidation of etching of graphene in H2 , which resulted in chirality-
the added H2 O2 to yield hydroxyl radicals. These sub- guided patterns instead of circular holes [80,81]. One
sequently reacted, again catalyzed by Au, with rGO to might speculate that it was the reductive environment
form hG that was rich in hydroxyl functional groups that resulted in the chirality guidance, but there was
(Figure 12). In contrast to most of the other examples in another observation that the Ag-catalyzed etching of
this section, in this case the Au nanoparticles were not graphene in a controlled O2 environment also followed
directly anchored on the graphene sheets but used as a the graphene chirality [82]. Two common characteris-
homogeneous catalyst in the solution process. tics of the experimental conditions in these reports were

Figure 12. Proposed mechanism for the photoinduced reaction between RGO (ie rGO), AuNPs (ie Au nanoparticles), and H2 O2 . A sus-
pension of RGO, AuNPs, and H2 O2 is prepared as shown at t = 0. Upon irradiation, AuNPs catalyze photolytic production of OH• as well
as OH• attack on RGO. Competitive decomposition of H2 O2 to O2 leads to bubble nucleation and detachment from the RGO surface, to
which we attribute the observed wrinkling of the RGO sheets. Extended irradiation leads to migration of AuNPs and creation of nanopores
at various places along the RGO sheets through diffusion and/or adsorption/desorption. Reproduced from Ref. [53] with permission from
American Chemical Society.
14 Y. LIN ET AL.

the use of high-quality graphene starting material (typ- decomposed to induce N-doping on graphene, while
ically from mechanical exfoliation) and prolonged etch- FeCl3 presumably converted into Fe2 O3 that induced
ing time, which were likely among the major causes for local etching of the graphene sheets in situ [85,86]. In
the observed highly ordered patterned etching. In the most of these examples [83–86], since an inert atmo-
previous example, extended thermal exposure of Ag- sphere was used during hole formation without addi-
decorated graphene in air did result in long etched chan- tional oxidative or reductive agents, the nanoparticles
nels or trenches on graphene sheets (Figure 11(c)), but must have chemically participated in the etching reac-
the morphology was more irregular, perhaps due to the tions as reagents instead of catalysts.
defective nature of the graphene used (t-rGO) [72]. In an
earlier example, rapid heating of Ag-decorated HOPG to
3. Applications of holey graphene
650°C also resulted in uneven catalytic trenching [75].
There are several examples of hG syntheses where Target applications for hGs from high-precision produc-
the graphene surface-anchored nanoparticles acted as the tion methods such as nanolithography and templated
etching reactants instead of as catalysts. In the report by growth are mainly in nanoelectronics; for example, FETs
Fan et al. [47], a solution mixture of GO and KMnO4 and FET-based sensor devices. While these applications
was subjected to microwave irradiation to form GO with have been briefly mentioned in the earlier sections, more
surface porosity induced by high-valence Mn etching. details can also be found in other reviews [28,87]. In this
The ‘porous GO’ (ie hGO) was subsequently reduced section, a few other key applications that take advan-
with hydrazine and washed with acid to afford hG. Lv tage of the structural motifs of hGs, especially those from
et al. [83] achieved similar etching chemistry by freeze- scalable preparation methods, are highlighted. While the
drying a GO–KMnO4 solution mixture and annealing it pristine graphene is useful in all of these applications, the
to 800°C in Ar, resulting in hG with holes of 40–100 nm performance of hGs is enhanced either by the presence of
formed around Mn3 O4 nanoparticles. Zhao et al. [84] holes, hole-edge functional groups, or both.
prepared nitrogen-doped (N-doped) hG in the form
of a lightweight foam using Fe-containing nanoparti-
3.1. Electrodes for supercapacitors and batteries
cles (Figure 13). They started with GO and polymer-
ized pyrrole onto the nanosheet surface to form a gel. Carbon nanomaterials, especially graphene, are attractive
After impregnating with an FeCl3 solution, the gel was candidates for advanced electrode materials in energy
heated in Ar to 850°C. At this temperature, polypyrrole storage devices such as supercapacitors and batteries
because of their excellent electrical conductivity and high
surface area. However, restacking graphene sheets in
their solid state significantly limits the surface area acces-
sible by the electrolyte ions, making the actual device per-
formance inferior to theoretical performance. A common
strategy to increase accessible surface area of graphene is
to introduce ‘pores’ between the nanosheets to enhance
ion access. A solid-state graphene with this architecture is
usually called ‘porous graphene’ and is a subject of inter-
est for energy storage applications [87,88]. Although the
holes on hG sheet can be considered two-dimensional
pores, the concept of hG is fundamentally different. In
hG, the ‘pores’ are large graphitic structural defects per-
tinent to the graphitic sheet structure, while in porous
graphene, the pores refer to the empty spaces between the
individual graphene sheets. In essence, hG is a graphene
structural derivative, while porous graphene is a type of
graphene assembly.
Figure 13. The fabrication of N-doped hG foam (N-GMF). Holey graphene materials have several advantages for
(a) Pyrrole (Py) monomer dispersed in a GO suspension. (b) various energy storage applications. First, the through-
Three-dimensional polypyrrole/graphene (Py/G) obtained after
plane ion transport is highly facilitated by the in-plane
hydrothermal treatment. (c) N-GMF with intercalated Fe2 O3
nanoparticles. (d) N-GMF after being washed with HCl. Repro- pores, making the ionic conduction path less tortu-
duced from Ref. [84] with permission from The Royal Society of ous compared to that in a typical electrode consist-
Chemistry. ing of stacked graphene sheets. This enables a higher
 MATER. RES. LETT. 15

ionic transport rate, and also a higher volumetric perfor- generally exhibited enhanced specific capacitance and
mance. Second, atoms at or near the hole edges are more rate performance compared to those made with pristine
active, similar to those at defect sites. In particular, there graphene because of the advantages discussed above.
are often abundant oxygen-containing functional groups Making binder-free electrodes would remove unnec-
attached to the hole edges in as-prepared hG materi- essary weight and volume in the final devices. For
als. Compared to graphene with no holes, hG usually nanocarbon materials such as graphene, wet filtration
has a higher intrinsic capacitance because the functional of a homogeneous dispersion of the active material is
groups impart additional Faradaic storage pathways and commonly used to achieve this goal. This process has
better electrode wetting [56]. also been applied to hG. For example, hG from an air
Conventionally, supercapacitor or battery electrodes oxidation process was readily dispersed in organic sol-
are made by mixing the active material, and some con- vents such as N-methylpyrolidone via bath sonication.
ductive carbon powder with a polymer binder in a solvent The dispersions were then filtered to form membranes
(usually with a high boiling point). The slurry is coated (also called ‘film’ or ‘paper’) that could be directly used as
on a conductive substrate followed by drying. Holey supercapacitor electrodes. The presence of holes on hG
graphene-based supercapacitors thus prepared [57,58] facilitated the removal of solvent during wet filtration,

Figure 14. (a) Digital photos of h-Graphene (ie hG) and graphene filtration films. The graphene film cracked during the drying process. (b)
Mechanical tensile test result for the h-Graphene film. (c) Cross-sectional SEM images for h-Graphene (left) and graphene films (right) at
equivalent areal mass densities of 0.31 mg/cm2 . Cross-sectional SEM images at identical magnifications for h-Graphene (d) and graphene
films (e). Reproduced from Ref. [18] with permission from American Chemical Society.
16 Y. LIN ET AL.

resulting in robust and dense films with high pack- contributions, which can dominate over the typical elec-
ing densities (ρ = 1.2 g/cm3 ) (Figure 14) [18]. In com- trical double layer capacitance from hG. For example,
parison, the nanosheet packing density of the pristine incorporation of Ni(OH)2 into hG electrodes improved
graphene (t-rGO) from the same filtration procedure was the capacitance more than sixfold (1860.6 vs. 251.4 F/g at
much less (0.2 g/cm3 ). Although the gravimetric capaci- 5 mV/s in 6 M KOH).
tance (Cm ) of hG was only slightly larger than that of the As discussed in Section 2.3.3, activated graphenes
pristine graphene in an ionic liquid electrolyte, the higher (ie a-MEGO and similar materials) are holey/porous
packing density resulted in a much higher volumetric graphenes with both in-plane and complex intercon-
capacitance (CV = Cm × ρ). nected pore structures with ultrahigh surface areas. As
Homogeneous aqueous dispersions of hGO are also a result, activated-graphene-based electrodes exhibited
excellent precursors for binder-free hG electrodes. As Xu excellent specific capacitance and rate performance as
et al. [52] reported, hGO was reduced to hG in the disper- electrodes for supercapacitors with both organic and
sion, which was subsequently filtered to form hG paper ionic liquid electrolytes [64–66]. Compaction signifi-
(Figure 15). Holey graphene paper (HGP) electrodes cantly improved the electrode packing density and, thus,
thus prepared exhibited excellent capacitance both gravi- the volumetric capacitance [90]. Binder-free activated-
metrically and volumetrically (209 F/g and 234 F/cm3 graphene electrodes were prepared by filtration of an
at 1 A/g, respectively), with superior rate performance aqueous mixture of GO and KOH followed by a typical
(157 F/g at 20 A/g). activation process (eg 800°C/1 h in Ar) [65]. These elec-
Various physical pore generation techniques for trodes retained high surface area (2400 m2 /g) and exhib-
porous graphene assemblies, such as foam formation or ited excellent capacitance (120 F/g at 10 A/g). They also
spacer insertion, can also be applied to hG, resulting in exhibited high in-plane electrical conductivity resulting
porous hG with truly three-dimensional porous struc- in ultralow equivalent series resistance (R = 0.1 ) for
tures providing additional advantages toward energy the supercapacitor device, and thus high power den-
storage [19,52,84]. Hydrogels from self-assembly of hGO sity (Pm = V 2 /4mR, where V is the operation voltage
in aqueous dispersion either during [19] or after prepa- window and m is the total electrode mass).
ration [52] were freeze-dried to form a highly porous Ionic liquid electrolyte-based supercapacitors have a
hG foam framework that was used as high-performance much wider operational voltage window than aqueous
binder-free electrodes. The Cm value of the hG foam electrolytes (3.5 vs. 1 V), resulting in higher energy den-
directly from hydrothermal reaction reached 310 F/g at sity (E = ½ CV 2 ) values. The typical drawback to ionic
1 A/g in 6 M KOH, and retained an outstanding 237 F/g at liquids is that the electrolyte molecules are much bulkier
100 A/g [19]. In comparison, non-holey graphene foam which usually leads to lower capacitance and rate perfor-
exhibited 208 and 131 F/g at 1 and 100 A/g, respectively. mances. It was shown computationally, though, that the
Holey graphene foams were readily compressed into holes with nanoscale–mesoscale diameters in hG could
thin films (eg from 1 cm to 140 μm, ρ = 0.7 g/cm3 ) that allow near impedance-free physical transport through
exhibited high volumetric performance [19]. In addition, the graphene plane of such large-sized molecules [18].
the capacitance values only decreased by ∼ 12% when Experimentally, various hG-based electrodes generally
the areal density of hG foam electrodes increased from 1 performed well in ionic liquids [18,19,58,91].
to 10 mg/cm2 (comparable to commercial electrode mass Holey graphene electrodes are similarly useful as elec-
loading), suggesting excellent ion transport despite the trodes for other energy storage devices such as lithium-
large electrode thickness. ion batteries (LIB) where holes and hole-edge functional
Inserting nanoscale spacers between graphene sheets groups render the same set of advantages. In one of the
is another common strategy to introduce three- first demonstrations, Kung and co-workers incorporated
dimensionally porous structures into an hG electrode Si nanoparticles into hG paper and tested the composite
architecture to further improve in-plane ion access. Ide- as the LIB electrode [17]. It was found that the binder-free
ally, these spacers would have extra functions, such as Si-hG composite electrode exhibited reversible capaci-
electrical conductivity or pseudocapacitance. For exam- ties of 3200 mAh/g at 1 A/g and 1100 mAh/g (or 34%)
ple, while binder-free hG electrodes exhibited greatly even at a rate as high as 8 A/g (Figure 16). The capac-
enhanced capacitance values compared to untreated ity of a Si-graphene electrode without in-plane pores
graphene (263 vs. 185 F/g at 5 mV/s in 6 M KOH), the diminished 90% with the same rate increase. With-
incorporation of highly conductive carbon nanotubes out the high capacity Si component, binder-free hG
into the hG electrode provided additional improvement paper electrodes exhibited somewhat lower capacities as
(294 F/g) [89]. Transition metal oxide nanoparticles as expected (eg 178 mAh/g at 2 A/g), but still outperformed
spacers afford pseudocapacitance due to Faraday reaction GP without in-plane pores at the same current rate
 MATER. RES. LETT. 17

Figure 15. Preparation and electrochemical characterizations of hG paper (HGP) and graphene paper (GP)-based supercapacitors in
1.0 M H2 SO4 aqueous electrolyte. (a) Photographs of aqueous dispersions of hGO and hG. (b) Photograph of a free-standing flexible HGP
with a thickness of ∼ 9 μm. (c) SEM image of the cross-section of the HGP. (d) Schematic illustration of ion diffusion pathways across the
GP and HGP. (e) Cyclic voltammetry (CV) curves at a scan rate of 200 mV/s. Galvanostatic charge/discharge curves at a current density of
1 A/g (f) and 20 A/g (g). (h) Specific capacitances vs. current densities. (i) Nyquist plots. Reproduced from Ref. [52] with permission from
American Chemical Society.

(66 mAh/g) [49]. Similar high-rate and stable-cycling Holey graphene electrodes were also shown to be
performances were also observed in LIB with hG useful for high-rate and reversible storage of Na+ , for
electrodes prepared using conventional slurry-based which capacities of 220 and 85 mAh/g were achieved
methods [67]. at 0.03 and 10 A/g, respectively. The batteries retained
18 Y. LIN ET AL.

Figure 16. Electrochemical characterization of ∼ 5 μm thick Si–hG paper anodes. (a) Specific delithiation capacity (solid) and coulombic
efficiency (open) of Si–hG between 0.02 and 1.5 V at 1 and 8 A/g (C/3 and 2.6 C based on a theoretical capacity of 3052 mAh/g), and
between 0.1 and 0.55 V at 4 A/g (1.3 C). (b) Fifth-cycle charge/discharge curves of Si–hG at 1, 4, and 8 A/g. Reproduced from Ref. [17] with
permission from John Wiley and Sons. A C-rate of 1C is defined to provide the full battery capacity at a 1-h discharge; 0.5C or C/2 is a 2-h
discharge and 0.2C or C/5 is a 5-h discharge [92].

70% of performance after 500 cycles at 0.1 A/g [59]. N-rich compounds such as pyrrole [84], urea [96],
In the same report, hG annealed at a higher temper- melamine [68], or ammonium hydroxide [69], some-
ature (1100°C rather than 300°C in Ar) exhibited a times followed by high-temperature annealing [68]. For
much lower storage capacity, presumably due to a much example, Yu et al. [96] prepared N-doped hG by first
lower content of hole-edge-attached oxygen-containing sonicating GO in concentrated nitric acid to prepare
functional groups [59]. hGO, which was then hydrothermally reacted with urea
at 180°C for 18 h to achieve simultaneous N-doping and
reduction. The resultant N-doped hG had a high N con-
3.2. N-Doped hG for catalysis and energy storage
tent of 8.6 at% with a surface area of 784 m2 /g and
The hole-edge-attached oxygen-containing functional exhibited excellent properties in both hydrazine oxida-
groups of typical hG materials exhibited some catalytic tion reaction and ORR.
activities, but improvements are needed for practical Despite the variations of the synthetic methods and
use. Recently, graphene heteroatomically doped with the resultant N-contents, most ORR characteristics for
elements such as N (the most common), B, P, or S N-hG from different methods were quite similar: low
have emerged as excellent metal-free replacements for onset potential, high limiting current density, durability
costly noble metal catalytic systems [93]. Unlike undoped against methanol intoxication, and excellent cyclability.
graphene, N-doped graphene possesses extra electroneg- An example for these general ORR characteristics is given
ativity near the doping sites increasing its catalytic activ- in Figure 17. Except for the slightly higher onset poten-
ity towards such reactions as oxygen reduction reac- tial, N-doped hG outperformed the state-of-the-art Pt-C
tion (ORR) and oxygen evolution reaction (OER). Both catalysts in most other ORR characteristics.
ORR and OER are of great importance in oxygen-related N,S-co-doped hG exhibited even better ORR perfor-
energy storage technologies, such as fuel cells and metal- mance than N-doped hG, suggesting the potential of
air batteries, and are currently one of the focused research further enhancement with secondary dopants [84]. It
and development areas [94]. Compared to graphene, the should be noted that ORR/OER bi-functional proper-
more abundant edge sites in hG could allow for more ties that would be extremely useful in energy storage can
effective localized doping. In addition, the presence of be achieved by certain co-doping techniques [97]. Holey
holes permits the effective transport of reactants that may graphene with manganese oxide (MnOx ) nanoparticles
interact with the heteroatomically doped active sites near decorated at their holes, directly from MnOx -induced
the holes, a synergism that may result in highly active high-temperature catalytic etching of GO, also exhibited
catalytic materials. excellent ORR performance without any heteroatomic
Various preparation strategies have been reported doping [83].
for N-doped hG. In some cases, holes were generated N-doped graphene is also known to improve the ion
first followed by doping, while in others N-doping was adsorption energy of the nanosheets thereby decreasing
achieved first followed by hole generation. N-doping the energy barriers for ion diffusion in supercapacitors
methods also vary and include gas-phase doping with and LIBs, resulting in higher capacity and rate perfor-
ammonia gas [95], microwave treatment with ammo- mance as well as cycling stability. Xu et al. [95] obtained
nium hydroxide [46], and hydrothermal reactions with N-doped hG by annealing hG in a flowing ammonia
 MATER. RES. LETT. 19

Figure 17. (a) Rotating disk electrode voltammograms of the reduced graphene, reduced holey graphene, nitrogen-doped holey
graphene (NHG), and 20 wt% Pt–C electrodes in an O2 -saturated, 0.1 M KOH solution at a rotation rate of 1600 rpm. Scan rate: 10 mV/s;
(b) rotating ring-disk electrode voltammogram of the NHG electrode in an O2 -saturated, 0.1 M KOH aqueous solution at a scan rate of
10 mV/s at 1600 rpm; (c) current–time chronoamperometric response for ORR at the NHG electrode and the 20 wt% Pt–C electrode upon
introduction of 1 M methanol after about 300 s at −0.25 V; (d) chronoamperometric response of the NHG electrode and the 20 wt% Pt–C
electrode at −0.25 V in an O2 -saturated 0.1 M KOH aqueous solution. Reproduced from Ref. [96] with permission from The Royal Society
of Chemistry.

atmosphere at 500°C for 5 h. Despite the relatively low 5 C (or ∼ 4 A/g), the capacity was retained at 400 mAh/g
N content ( ∼ 1%), the lithium storage characteristics of for over 1000 cycles. Alternatively, N-doping was intro-
N-doped hG electrodes were much improved compared duced into the hG hydrogel via in situ polymeriza-
to either neat hG without N-doping or N-doped pris- tion of pyrrole followed by annealing [99]. Interestingly,
tine graphene without holes. In particular, the first dis- the slow solvent evaporation after pyrrole incorpora-
charge/charge capacities were as high as 3056/990 mAh/g tion caused the hydrogel to shrink, resulting in an N-
at 0.1 A/g. Despite the initial drop during the first few doped hG monolith with a density of 1.1 g/cm3 and
cycles (likely due to the delayed electrode wetting pro- an excellent volumetric performance as an LIB anode
cess), the battery was cycled 6000 times and retained ( > 1000 mAh/cm3 for over 1200 cycles at 0.1 mA/cm2 ).
a discharge capacity of 554 mAh/g at a high rate of Other combinations of hole-generation/N-doping/pore-
5 A/g (Figure 18). Much like the hG foam electrodes dis- forming strategies are also available. For example, Jiang
cussed in Section 3.1, N-doped hG can also be made and Jiang [100] reported the annealing of a mixture of
into foam-like electrodes that are highly beneficial for hGO, melamine (as the N source), and silica nanopar-
Li-ion transport and storage. For example, the hG foam ticles (as the pore template), followed by removal of the
from hydrothermal etching in H2 O2 discussed in the template. Ji et al. [101] used CVD-grown graphene on Ni
previous section could be N-doped to 3.4% via ther- foam as the substrate and infiltrated a mixture of GO and
mal treatment in an ammonia atmosphere [98]. The LIB KOH, followed by the chemical activation process (see
with the N-doped-hG-based anode had a high capacity Section 2.3.3) and the removal of KOH and Ni. LIB with
of 2847 mAh/g in the first cycle at 0.1 C (or ∼ 75 mA/g) anodes made from both types of porous N-doped hG
and a reversible capacity of ∼ 1150 mAh/g in subse- architectures exhibited high capacities and excellent rate
quent cycles with near 100% Columbic efficiency. At capabilities.
20 Y. LIN ET AL.

Figure 18. LIB performance of neat graphene (G), hG, n-doped graphene (N-G), and N-doped hG (N-hG) measured in the voltage range
of 0.02–2.5 V. (a) Initial discharge–charge curves at 0.1 A/g, (b) rate capability, (c) discharge–charge curves of N-hG at various current den-
sities, (d) capacity retention vs. various current densities, and (e) cycling performance at 5 A/g. Reproduced from Ref. [95] with permission
from John Wiley and Sons.

3.3. Membranes Currently, most of these concepts and experiments

have been focused on graphene sheets with single layers.
Single-layer graphene with in-plane pores, an example
For DNA sequencing, the ultrathin nature of single-layer
of hG, has been proposed for various membrane appli-
graphene would provide the highest resolution and sensi-
cations such as gas separation [102], water purification
tivity. For gas separation, high precision of the hole mor-
[103–105], and biosensing [106]. The initial theoretical
phology on an ultrathin platform would also be required.
predictions and experimental results have been promis-
In water purification, thinner membranes would pro-
ing. For example, in the case of biosensing (discussed in
vide higher water flux, although stringent control of
Section 2.1.1), a direct application for the first experi-
pore size and structure would be required. However, it
ments on electron beam hole drilling on a graphene sheet
could be technically challenging to utilize single-layer
was to use the resultant nanopore to detect the translo-
graphene, especially for large-scale applications such as
cation event of biomolecules such as DNA [25–27]. As
water purification due to concerns in the scalability,
these large molecules gradually passed through the hole,
mechanical stability under high flow rates and pressure,
the disturbance (ie blockage) in the solution ionic current
ion blockage, membrane fouling, etc. [109].
could be detected and analyzed (Figure 19) [106]. High-
Holey graphene materials from scalable preparation
resolution sequencing of DNA could be possible because
methods have shortcomings in the lack of structural
of the ultrathin nature of graphene sheets [106–108].
 MATER. RES. LETT. 21

Figure 19. Four new concepts using graphene nanostructures for DNA sequencing. (a) Detection of changes in the ionic current through
a nanopore in a graphene membrane due to the passage of a DNA molecule. (b) Modulations of a tunneling current through a nanogap
between two graphene electrodes due to the presence of a DNA molecule. (c) Variations in the in-plane current through a graphene
nanoribbon due to traversal of a DNA molecule. (d) Changes in a graphene current due to the physisorption of DNA bases onto the
graphene. Reproduced from Ref. [106] with permission from Nature Publishing Group.

precision/fidelity in the hole sizes, shapes, and distribu- only enhanced proton conductivity, but also much atten-
tions. However, if this precision is not strictly required, uated methanol permeation (Table 2). The performance
such hG materials could be used for membrane appli- was superior to that of state-of-the-art Nafion mem-
cations. An example was the design of a functionalized branes, leading to enhanced DMFC operation with much
hGO paper to selectively conduct protons while blocking improved electrochemical performance and power den-
methanol penetration [110]. This characteristic is criti- sity. It was hypothesized that the hydrophilic sulfonate
cal for direct methanol fuel cell (DMFC) systems, where groups adsorbed on hG sheets are the key to facilitate the
high-proton conduction is desirable but low-methanol proton exchange but simultaneously reduce the methanol
permeation is required to prevent reduction in power diffusion channel size.
density, increased fuel utilization, and catalytic poison- The above example underlines the potential signifi-
ing. However, the in-plane holes within the hGO paper cance of manipulating hole-edge chemistry to achieve
were found to allow the permeation of both protons a unique function in hG. Notably, it was also pro-
and methanol. Interestingly, an organic sulfonate sur- posed that hole-edge functionalization could signifi-
factant, sodium dodecylbenzenesulfonate (SDBS), incor- cantly enhance the selectivity or sensitivity of the molec-
porated via room temperature incubation in aqueous ular translocation of single-layer graphene with in-plane
solution, led to an SDBS-hGO paper that exhibited not pores [108,111].

Table 2. Comparison of ion-exchange capacity (measured at 65°C), proton conductivity (measured at

65°C), and methanol permeability for the various GO/hGO membranes in comparison to the benchmark
®
Nafion 112 membrane.
Ion-exchange Proton conductivity Methanol permeability
Membrane Thickness capacity (meq/g) (mS/cm) (×106 cm2 /s)
GO paper 31.2 ± 0.5 0.50 ± 0.01 54.2 ± 0.5 0.24 ± 0.01
hGO paper 32.4 ± 0.3 0.77 ± 0.01 68.4 ± 0.6 14.55 ± 0.14
SDBS-GO paper 31.7 ± 0.5 1.07 ± 0.02 68.5 ± 0.5 0.44 ± 0.01
SDBS-hGO paper 31.1 ± 0.6 1.84 ± 0.03 91.8 ± 0.9 3.54 ± 0.04
®
Nafion 112 53.2 ± 0.5 0.94 ± 0.02 95.1 ± 1.0 4.75 ± 0.05
Source: Reproduced from Ref. [110] with permission from The Royal Society of Chemistry.
22 Y. LIN ET AL.

3.4. Mechanical applications maximum strain value used in the above work was only
0.5%, in subsequent work by the same group the authors
Intuitively, hG is a highly ‘defective’ graphene deriva-
increased the strain to achieve fracture [113]. With MD
tive and should have an inferior mechanical performance
simulations, it was found that the fracture strain of hG
to that of the parent graphene. However, Lin et al. [72]
with sub-5 nm holes exhibited an initial decrease with
found that a hG polymer composite made by melt pro-
porosity, but continued to increase significantly to ∼ 20%
cessing exhibited better strength and modulus compared
when the porosity reached as high as 80%. Although
to one made with the same loading of pristine graphene
the elastic modulus and fracture toughness decreased
without in-plane porosity. Several contributing factors
with porosity, both parameters still maintained very high
were proposed. First, the graphitic crystallinity of hG was
values ( > 5 GPa and > 0.5 J/m2 , respectively).
preserved after hole generation, as evidenced by elec-
More striking computational results were shown by
tron diffraction and Raman studies. Second, with the
Zhu et al. [114] who used a bottom-up, coarse-grained
same loading weight, there were, in fact, more sheets
(CG) simulation approach to hypothesize that hG with
used as fillers due to their lower mass density per sheet.
∼ 50 nm holes could be highly compliant (ie have a neg-
Third, hG might be considered microscopic ‘nets’ that
ligible stiffness) up to 20% strain (Figure 20). The ini-
made them highly flexible. Last, but not least, the hole
tial highly compliant deformation of the hG sheet was
structures may allow polymer penetration through the
entirely geometric, similar to the ‘graphene net’ concept
graphene sheets, thus enhancing the polymer–filler inter-
proposed by Lin et al [72]. Zhu et al. further proposed
actions [72]. It would be expected that the appropriate
that this compliance could make hG-based bioelectronic
hole-edge functionalization could further improve such
devices accommodate large deformations of biological
interactions.
tissues with little effect on the device performance.
For naturally porous materials such as bones, the
elastic modulus scales with the square of the density
(ie reduces with porosity). Using molecular statics and
molecular dynamics (MD) simulations, it was deduced 4. Summary and outlook
that the modulus of hG with ideal unpassivated circular Despite the presence of arrays of holes through the
holes is reduced with the increase in hole density [112], atomic thicknesses of the two-dimensional nanosheets,
consistent with the intuitive concept of hG being ‘defec- hG retained many excellent properties from the par-
tive’ graphene. However, as the same authors reported ent intact graphene, such as high electrical and ther-
[112], hG hole-morphology shape change (such as to mal conductivity, large surface area, high mechanical
elliptical-shaped ones) could lead to deviations from the strength, high thermal and chemical stability, and versa-
above scaling law, while hole passivation (ie functional- tile chemistry. Furthermore, the unique structural motif
ization) would improve the elastic modulus. While the of this new class of graphene derivative makes it much

Figure 20. (a) CG model for the patterned hG. (b)–(g) Snapshots of the deformed hG under various applied tensile strains. The arrow
in (b) indicates the direction of applied tensile load. (h) Resultant force in the hG as a function of applied elongation. The light green
shaded region (‘Stage I’) highlights the extremely compliant region of the hG while the light blue shaded region (‘Stage II’) highlights the
highly compliant region with an effective stiffness of about 15.8 N/m. Here, LG = 351 nm, WG = 199 nm, LC = 50 nm, and WR = 2 nm.
Reproduced from Ref. [114] with permission from AIP Publishing LLC.
 MATER. RES. LETT. 23

more advantageous than its parent counterpart in various the preparation/processing procedure, the physical and
applications by enabling (1) facile through-plane mass chemical properties of hG such as hole size and dis-
transport, (2) facile functionalization at or near the hole tribution, functional group content and doping extent,
edges, and (3) modified electronic properties. defect density, and surface area could all significantly
In this review, various preparation approaches, char- vary, resulting in drastically different material perfor-
acterization methods, and applications of hG, a deriva- mance even in the same application.
tive of graphene, are discussed. The hole morphology, Finally, it is anticipated that some of the hole-
distribution, and chemistry of hG could significantly generation strategies could be applied to other two-
impact the material properties and the corresponding dimensional nanomaterials. In fact, both catalytic etching
applications. In the preparation, high-precision or high- of hexagonal boron nitride [115] and oxidative etching of
fidelity methods such as electron beam irradiation, nano- molybdenum disulfide [116] have recently been reported.
lithography, and template growth, are used to prepare Similar hole-enabled advantages can thus be envisioned
substrate-supported hG with precise hole locations or for these novel holey two-dimensional materials beyond
hole morphologies/distributions. The source of graphene graphene, for applications in electronics, energy conver-
in these approaches is typically mechanical cleavage of sion and storage, and catalysis, where material properties
graphite or CVD growth, and the resultant hG mate- different from those of graphene are required.
rials are often useful for device-level applications such
as sensors and nanoelectronics. Bulk preparation meth-
Acknowledgements
ods typically involve liquid- or gaseous-phase etching
of GO-based materials, sometimes in the presence of Y.L. and J.W.C. also thank Prof. Liangbing Hu (University of
catalysts. Although hG materials can be routinely pre- Maryland, College Park) and Prof. Liming Dai (Case Western
Reserve University) for fruitful collaborations.
pared in gram quantities, the precision in the hole loca-
tion and morphology is much less controllable with the
bulk approaches. However, many applications such as Disclosure statement
energy storage or catalysis do not require precise hole
sizes and morphologies. The presence of arrays of holes No potential conflict of interest was reported by the
with abundant oxygen-containing hole-edge functional authors.
groups and/or enhanced reactivity, due to heteroatomic
doping near the hole edges, is sufficient to give sig- Funding
nificant advantages of these scalable hG materials over
Y.L. and J.W.C. acknowledge the support by the Internal
conventional intact graphene materials in these types of
Research and Development (IRAD) program from NASA Lan-
applications. gley Research Center. Z.C. acknowledges the support by NSF
Despite the ongoing achievements discussed herein, [grant number EPS-1002410] and U.S. Department of Defense
many challenges remain for hG materials. For exam- [grant number W911NF-15-1-0650].
ple, although nearly perfectly structured hG sheets could
be produced using the high-fidelity approaches, compli-
References
cated steps, high costs, low yields, as well as contam-
ination arising from the templates are still significant [1] Novoselov KS, Geim AK, Morozov SV, et al. Electric
field effect in atomically thin carbon films. Science.
obstacles. Moreover, little work has been reported on
2004;306:666–669.
the presumably facile functionalization at the hole edges. [2] Geim AK. Graphene: status and prospects. Science.
Although precision in hole characteristics is usually not 2009;324:1530–1534.
required for hG from bulk preparation, gaining control [3] Ferrari AC, Bonaccorso F, Fal’ko V, et al. Science
of the hole-edge chemistry would be highly beneficial and technology roadmap for graphene, related two-
to most of the desirable applications. Tuning hole-edge dimensional crystals, and hybrid systems. Nanoscale.
2015;7:4598–4810.
functionalities for substrate-supported hG could also be [4] Zhu Y, Murali S, Cai W, et al. Graphene and graphene
useful to applications such as sensors. oxide: synthesis, properties, and applications. Adv Mater.
Care must be taken when comparing various hG 2010;22:3906–3924.
materials from different preparation methods, especially [5] Zhu Y, James DK, Tour JM. New routes to graphene,
those from scalable techniques. Most hG materials do graphene oxide and their related applications. Adv
Mater. 2012;24:4924–4955.
share the same key advantages of the holey structure,
[6] Stankovich S, Dikin DA, Dommett GHB, et al. Graphene
such as the benefit from the hole-enabled through-plane -based composite materials. Nature. 2006;442:282–286.
transport and the hole-edge functional groups. How- [7] Ren W, Cheng H-M. The global growth of graphene. Nat
ever, depending upon the starting graphene material and Nanotechnol. 2014;9:726–730.
24 Y. LIN ET AL.

[8] Li XS, Cai W, An J, et al. Large-area synthesis of high- [29] Zeng Z, Huang X, Yin Z, et al. Fabrication of graphene
quality and uniform graphene films on copper foils. nanomesh by using an anodic aluminum oxide mem-
Science. 2009;324:1312–1314. brane as a template. Adv Mater. 2012;24:4138–4142.
[9] Hernandez Y, Nicolosi V, Lotya M, et al. High-yield [30] Liu X, Liu N, Liu M, et al. Graphene nanomesh photode-
production of graphene by liquid-phase exfoliation of tector with effective charge tunnelling from quantum
graphite. Nat Nanotechnol. 2008;3:563–568. dots. Nanoscale. 2015;7:4242–4249.
[10] Scott A. Graphene’s global race to market. Chem Eng [31] Zhang Q, Wan X, Xing F, et al. Solution-processable
News. 2016;94:28–33. graphene mesh transparent electrodes for organic solar
[11] Schmidt-Mende L, MacManus-Driscoll JL. Zno— cells. Nano Res. 2013;6:478–484.
nanostructures, defects, and devices. Mater Today. [32] Ding J, Du K, Wathuthanthri I, et al. Transfer pattern-
2007;10:40–48. ing of large-area graphene nanomesh via holographic
[12] Charlier JC. Defects in carbon nanotubes. Acc Chem lithography and plasma etching. J Vac Sci Technol B.
Res. 2002;35:1063–1069. 2014;32:06FF01.
[13] Terrones H, Lv R, Terrones M, et al. The role of defects [33] Kazemi A, He X, Alaie S, et al. Large-area semicon-
and doping in 2D graphene sheets and 1D nanoribbons. ducting graphene nanomesh tailored by interferometric
Rep Prog Phys. 2012;75:062501. lithography. Sci Rep. 2015;5:11463.
[14] Bai J, Zhong X, Jiang S, et al. Graphene nanomesh. Nat [34] Liang X, Jung Y-S, Wu S, et al. Formation of bandgap and
Nanotechnol. 2010;5:190–194. subbands in graphene nanomeshes with sub-10 nm rib-
[15] Kim M, Safron NS, Han E, et al. Fabrication and charac- bon width fabricated via nanoimprint lithography. Nano
terization of large-area, semiconducting nanoperforated Lett. 2010;10:2454–2460.
graphene materials. Nano Lett. 2010;10:1125–1131. [35] Lee W, Park S-J. Porous anodic aluminum oxide:
[16] Han TH, Huang Y-K, Tan ATL, et al. Steam etched anodization and templated synthesis of functional
porous graphene oxide network for chemical sensing. J nanostructures. Chem Rev. 2014;114:7487–7556.
Am Chem Soc. 2011;133:15264–15267. [36] Tada K, Kosugi N, Sakuramoto K, et al. Electron-spin-
[17] Zhao X, Hayner CM, Kung MC, et al. In-plane based phenomena arising from pore edges of graphene
vacancy-enabled high-power Si-graphene composite nanomeshes. J Supercond Nov Magn. 2013;26:1037–1043.
electrode for lithium-ion batteries. Adv Energy Mater. [37] Jung I, Jang HY, Park S. Direct growth of graphene
2011;1:1079–1084. nanomesh using a Au nano-network as a metal cat-
[18] Han X, Funk MR, Shen F, et al. Scalable holey alyst via chemical vapor deposition. Appl Phys Lett.
graphene synthesis and dense electrode fabrication 2013;103:023105.
toward high-performance ultracapacitors. ACS Nano. [38] Sinitskii A, Tour JM. Patterning graphene through
2014;8:8255–8265. the self-assembled templates: toward periodic two-
[19] Xu Y, Lin Z, Zhong X, et al. Holey graphene frame- dimensional graphene nanostructures with semicon-
works for highly efficient capacitive energy storage. Nat ductor properties. J Am Chem Soc. 2010;132:14730–14732.
Commun. 2014;5:4554. [39] Paul RK, Badhulika S, Saucedo NM, et al. Graphene
[20] Fischbein MD, Drndic M. Electron beam nanosculpt- nanomesh as highly sensitive chemiresistor gas sensor.
ing of suspended graphene sheets. Appl Phys Lett. Anal Chem. 2012;84:8171–8178.
2008;93:113107. [40] Esfandiar A, Kybert NJ, Dattoli EN, et al. DNA-
[21] Son YW, Cohen ML, Louie SG. Energy gaps in graphene decorated graphene nanomesh for detection of chemical
nanoribbons. Phys Rev Lett. 2006;97:216803. vapors. Appl Phys Lett. 2013;103:183110.
[22] Kosynkin DV, Higginbotham AL, Sinitskii A, et al. [41] Mangadlao JD, de Leon ACC, Felipe MJL, et al. Electro-
Longitudinal unzipping of carbon nanotubes to form chemical fabrication of graphene nanomesh via colloidal
graphene nanoribbons. Nature. 2009;458:872–876. templating. Chem Commun. 2015;51:7629–7632.
[23] Song B, Schneider GF, Xu Q, et al. Atomic-scale electron- [42] Li C, Yang X, Ding S, et al. Field emission proper-
beam sculpting of near-defect-free graphene nanostruc- ties of triode-type graphene mesh emitter arrays. IEEE
tures. Nano Lett. 2011;11:2247–2250. Electron Dev Lett. 2014;35:786–788.
[24] Standop S, Lehtinen O, Herbig C, et al. Ion impacts on [43] Wang M, Fu L, Gan L, et al. CVD growth of large
graphene/Ir(111): interface channeling, vacancy funnels, area smooth-edged graphene nanomesh by nanosphere
and a nanomesh. Nano Lett. 2013;13:1948–1955. lithography. Sci Rep. 2013;3:1238.
[25] Merchant CA, Healy K, Wanunu M, et al. DNA [44] Safron NS, Kim M, Gopalan P, et al. Barrier-guided
translocation through graphene nanopores. Nano Lett. growth of micro- and nano-structured graphene. Adv
2010;10:2915–2921. Mater. 2012;24:1041–1045.
[26] Schneider GF, Kowalczyk SW, Calado VE, et al. DNA [45] Ning G, Fan Z, Wang G, et al. Gram-scale synthesis of
translocation through graphene nanopores. Nano Lett. nanomesh graphene with high surface area and its appli-
2010;10:3163–3167. cation in supercapacitor electrodes. Chem Commun.
[27] Traversi F, Raillon C, Benameur SM, et al. Detecting 2011;47:5976–5978.
the translocation of DNA through a nanopore using [46] Patel M, Feng W, Savaram K, et al. Microwave enabled
graphene nanoribbons. Nat Nanotechnol. 2013;8:939–945. one-pot, one-step fabrication and nitrogen doping of
[28] Yang J, Ma M, Li L, et al. Graphene nanomesh: new holey graphene oxide for catalytic applications. Small.
versatile materials. Nanoscale. 2014;6:13301–13313. 2015;11:3358–3368.
 MATER. RES. LETT. 25

[47] Fan Z, Zhao Q, Li T, et al. Easy synthesis of porous [65] Zhang LL, Zhao X, Stoller MD, et al. Highly conduc-
graphene nanosheets and their use in supercapacitors. tive and porous activated reduced graphene oxide films
Carbon. 2012;50:1699–1703. for high-power supercapacitors. Nano Lett. 2012;12:
[48] Chen S, Duan J, Jaroniec M, et al. Hierarchically 1806–1812.
porous graphene-based hybrid electrodes with excel- [66] Kim TY, Jung G, Yoo S, et al. Activated graphene-based
lent electrochemical performance. J Mater Chem A. carbons as supercapacitor electrodes with macro- and
2013;1:9409–9413. mesopores. ACS Nano. 2013;7:6899–6905.
[49] Zhao X, Hayner CM, Kung MC, et al. Flexible holey [67] Jiang Z, Pei B, Manthiram A. Randomly stacked
graphene paper electrodes with enhanced rate capability holey graphene anodes for lithium ion batteries with
for energy storage applications. ACS Nano. 2011;5:8739– enhanced electrochemical performance. J Mater Chem
8749. A. 2013;1:7775–7781.
[50] Dikin DA, Stankovich S, Zimney EJ, et al. Preparation [68] Jiang Z-j, Jiang Z, Chen W. The role of holes in improv-
and characterization of graphene oxide paper. Nature. ing the performance of nitrogen-doped holey graphene
2007;448:457–460. as an active electrode material for supercapacitor and
[51] Wang X, Jiao L, Sheng K, et al. Solution-processable oxygen reduction reaction. J Power Sources. 2014;251:
graphene nanomeshes with controlled pore structures. 55–65.
Sci Rep. 2013;3:1996. [69] Jiang Z, Jiang Z-j, Tian X, et al. Amine-functionalized
[52] Xu Y, Chen C-Y, Zhao Z, et al. Solution process- holey graphene as a highly active metal-free catalyst
able holey graphene oxide and its derived macrostruc- for the oxygen reduction reaction. J Mater Chem A.
tures for high-performance supercapacitors. Nano Lett. 2014;2:441–450.
2015;15:4605–4610. [70] Jhajharia SK, Selvaraj K. Non-templated ambient nanop-
[53] Radich JG, Kamat PV. Making graphene holey. gold- erforation of graphene: a novel scalable process and its
nanoparticle-mediated hydroxyl radical attack on exploitation for energy and environmental applications.
reduced graphene oxide. ACS Nano. 2013;7:5546–5557. Nanoscale. 2015;7:19705–19713.
[54] Kotchey GP, Allen BL, Vedala H, et al. The enzy- [71] Yin PT, Shah S, Chhowalla M, et al. Design, synthesis,
matic oxidation of graphene oxide. ACS Nano. 2011;5: and characterization of graphene-nanoparticle hybrid
2098–2108. materials for bioapplications. Chem Rev. 2015;115:
[55] Schniepp HC, Li J-L, McAllister MJ, et al. Functionalized 2483–2531.
single graphene sheets derived from splitting graphite [72] Lin Y, Watson KA, Kim J-W, et al. Bulk preparation
oxide. J Phys Chem B. 2006;110:8535–8539. of holey graphene via controlled catalytic oxidation.
[56] Lin Y, Han X, Campbell CJ, et al. Holey graphene Nanoscale. 2013;5:7814–7824.
nanomanufacturing: structure, composition, and elec- [73] Baker RTK, Harris PS. Controlled atmosphere electron-
trochemical properties. Adv Funct Mater. 2015;25: microscopy studies of graphite gasification. I. Catalytic
2920–2927. influence of zinc. Carbon. 1973;11:25–31.
[57] Peng Y-Y, Liu Y-M, Chang J-K, et al. A facile approach [74] Harris PS, Feates FS, Reuben BG. Controlled atmosphere
to produce holey graphene and its application in super- electron microscopy studies of graphite gasification. 4.
capacitors. Carbon. 2015;81:347–356. Catalysis of graphite—O2 reaction by silver. Carbon.
[58] Yang C-H, Huang P-L, Luo X-F, et al. Holey graphene 1974;12:189–197.
nanosheets with surface functional groups as high- [75] Severin N, Kirstein S, Sokolov IM, et al. Rapid trench
performance supercapacitors in ionic-liquid electrolyte. channeling of graphenes with catalytic silver nanoparti-
ChemSusChem. 2015;8:1779–1786. cles. Nano Lett. 2009;9:457–461.
[59] Luo X-F, Yang C-H, Chang J-K. Correlations between [76] Gethers ML, Thomas JC, Jiang S, et al. Holey graphene
electrochemical Na+ storage properties and physio- as a weed barrier for molecules. ACS Nano. 2015;9:
chemical characteristics of holey graphene nanosheets. 10909–10915.
J Mater Chem A. 2015;3:17282–17289. [77] Akhavan O. Graphene nanomesh by ZnO nanorod pho-
[60] Xing Z, Tian J, Liu Q, et al. Holey graphene nanosheets: tocatalysts. ACS Nano. 2010;4:4174–4180.
large-scale rapid preparation and their application [78] Akhavan O, Ghaderi E. Graphene nanomesh promises
toward highly-effective water cleaning. Nanoscale. 2014; extremely efficient in vivo photothermal therapy. Small.
6:11659–11663. 2013;9:3593–3601.
[61] Koinuma M, Ogata C, Kamei Y, et al. Photochemical [79] Liu J, Cai H, Yu X, et al. Fabrication of graphene
engineering of graphene oxide nanosheets. J Phys Chem nanomesh and improved chemical enhancement for
C. 2012;116:19822–19827. Raman spectroscopy. J Phys Chem C. 2012;116:
[62] Shannon MA, Bohn PW, Elimelech M, et al. Science and 15741–15746.
technology for water purification in the coming decades. [80] Datta SS, Strachan DR, Khamis SM, et al. Crystal-
Nature. 2008;452:301–310. lographic etching of few-layer graphene. Nano Lett.
[63] Frackowiak E, Beguin F. Carbon materials for the elec- 2008;8:1912–1915.
trochemical storage of energy in capacitors. Carbon. [81] Ci L, Xu Z, Wang L, et al. Controlled nanocutting of
2001;39:937–950. graphene. Nano Res. 2008;1:116–122.
[64] Zhu Y, Murali S, Stoller MD, et al. Carbon-based super- [82] Booth TJ, Pizzocchero F, Anderson H, et al. Discrete
capacitors produced by activation of graphene. Science. dynamics of nanoparticle channelling in suspended
2011;332:1537–1541. graphene. Nano Lett. 2011;11:2689–2692.
26 Y. LIN ET AL.

[83] Lv X, Lv W, Wei W, et al. A hybrid of holey graphene and [100] Jiang Z-J, Jiang Z. Fabrication of nitrogen-doped holey
Mn3 O4 and its oxygen reduction reaction performance. graphene hollow microspheres and their use as an active
Chem Commun. 2015;51:3911–3914. electrode material for lithium ion batteries. ACS Appl
[84] Zhao Y, Hu C, Song L, et al. Functional graphene Mater Interfaces. 2014;6:19082–19091.
nanomesh foam. Energy Environ Sci. 2014;7:1913–1918. [101] Ji J, Liu J, Lai L, et al. In situ activation of nitrogen-doped
[85] Palaniselvam T, Aiyappa HB, Kurungot S. An effi- graphene anchored on graphite foam for a high-capacity
cient oxygen reduction electrocatalyst from graphene anode. ACS Nano. 2015;9:8609–8616.
by simultaneously generating pores and nitrogen doped [102] Koenig SP, Wang L, Pellegrino J, et al. Selective molecu-
active sites. J Mater Chem. 2012;22:23799–23805. lar sieving through porous graphene. Nat Nanotechnol.
[86] Wang H, Zhi L, Liu K, et al. Thin-sheet carbon nanomesh 2012;7:728–732.
with an excellent electrocapacitive performance. Adv [103] Cohen-Tanugi D, Grossman JC. Water desalination
Funct Mater. 2015;25:5420–5427. across nanoporous graphene. Nano Lett. 2012;12:
[87] Jiang L, Fan Z. Design of advanced porous graphene 3602–3608.
materials: from graphene nanomesh to 3D architectures. [104] O’Hern SC, Jang D, Bose S, et al. Nanofiltration across
Nanoscale. 2014;6:1922–1945. defect-sealed nanoporous monolayer graphene. Nano
[88] Han S, Wu D, Li S, et al. Porous graphene materials for Lett. 2015;15:3254–3260.
advanced electrochemical energy storage and conver- [105] Surwade SP, Smirnov SN, Vlassiouk IV, et al. Water
sion devices. Adv Mater. 2014;26:849–864. desalination using nanoporous single-layer graphene.
[89] Jiang L, Sheng L, Long C, et al. Densely packed graphene Nat Nanotechnol. 2015;10:459–464.
nanomesh-carbon nanotube hybrid film for ultra-high [106] Heerema SJ, Dekker C. Graphene nanodevices for
volumetric performance supercapacitors. Nano Energy. DNA sequencing. Nat Nanotechnol. 2016;11:127–
2015;11:471–480. 136.
[90] Murali S, Quarles N, Zhang LL, et al. Volumetric capac- [107] Wells DB, Belkin M, Comer J, et al. Assessing graphene
itance of compressed activated microwave-expanded nanopores for sequencing DNA. Nano Lett. 2012;12:
graphite oxide (a-MEGO) electrodes. Nano Energy. 4117–4123.
2013;2:764–768. [108] Paulechka E, Wassenaar TA, Kroenlein K, et al.
[91] Tsai W-Y, Lin R, Murali S, et al. Outstanding perfor- Nucleobase-functionalized graphene nanoribbons for
mance of activated graphene based supercapacitors in accurate high-speed sequencing. Nanoscale. 2016;8:
ionic liquid electrolyte from −50 to 80°C. Nano Energy. 1861–1867.
2013;2:403–411. [109] Sun C, Wen B, Bai B. Recent advances in nanoporous
[92] http://batteryuniversity.com/learn/article/what_is_ graphene membrane for gas separation and water purifi-
the_c_rate cation. Sci Bull. 2015;60:1807–1823.
[93] Dai L, Xue Y, Qu L, et al. Metal-free catalyst for oxygen [110] Jiang Z, Shi Y, Jiang Z-J, et al. High performance of a free-
reduction reaction. Chem Rev. 2015;115:4823–4892. standing sulfonic acid functionalized holey graphene
[94] Shui J, Wang M, Du F, et al. N-doped carbon nanomate- oxide paper as a proton conducting polymer electrolyte
rials are durable catalysts for oxygen reduction reaction for air-breathing direct methanol fuel cells. J Mater
in acidic fuel cells. Sci Adv. 2015;1:e1400129. Chem A. 2014;2:6494–6503.
[95] Xu J, Lin Y, Connell JW, et al. Nitrogen-doped holey [111] Sint K, Wang B, Krai P. Selective ion passage through
graphene as an anode for lithium-ion batteries with high functionalized graphene nanopores. J Am Chem Soc.
volumetric energy density and long cycle life. Small. 2008;130:16448–16449.
2015;11:6179–6185. [112] Carpenter C, Christmann AM, Hu L, et al. Elastic
[96] Yu D, Wei L, Jiang W, et al. Nitrogen doped holey properties of graphene nanomeshes. Appl Phys Lett.
graphene as an efficient metal-free multifunctional elec- 2014;104:141911.
trochemical catalyst for hydrazine oxidation and oxygen [113] Hu L, Wyant S, Muniz AR, et al. Mechanical behav-
reduction. Nanoscale. 2013;5:3457–3464. ior and fracture of graphene nanomeshes. J Appl Phys.
[97] Zhang J, Zhao Z, Xia Z, et al. A metal-free bifunc- 2015;117:024302.
tional electrocatalyst for oxygen reduction and oxygen [114] Zhu S, Huang Y, Li T. Extremely compliant and
evolution reactions. Nat Nanotechnol. 2015;10:444–452. highly stretchable patterned graphene. Appl Phys Lett.
[98] Sun J, Wang L, Song R, et al. Nitrogen-doped holey 2014;104:173103.
graphene foams for high-performance lithium storage. [115] Liao Y, Tu K, Han X, et al. Oxidative etching of hexagonal
RSC Adv. 2015;5:91114–91119. boron nitride toward nanosheets with defined edges and
[99] Wang X, Lv L, Cheng Z, et al. High-density mono- holes. Sci Rep. 2015;5:14510.
lith of N-doped holey graphene for ultrahigh volu- [116] Ionescu R, George A, Ruiz I, et al. Oxygen etching
metric capacity of Li-ion batteries. Adv Energy Mater. of thick MoS2 films. Chem Commun. 2014;50:11226–
2016;6:1502100. 11229.