Progress Report

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Nanoscale Assembly of 2D Materials for Energy

and Environmental Applications
Gyoung Hwa Jeong, Suchithra Padmajan Sasikala, Taeyeong Yun, Gil Yong Lee,
Won Jun Lee,* and Sang Ouk Kim*

2004,[5,6] and was followed by a new era of

Rational design of 2D materials is crucial for the realization of their pro- atomically thin materials, such as transi-
found implications in energy and environmental fields. The past decade has tion metal dichalcogenides (TMDC),[7–9]
witnessed significant developments in 2D material research, yet a number of MXene (i.e., transition metal carbides, car-
critical challenges remain for real-world applications. Nanoscale assembly, bonitrides, and nitrides),[10,11] silicene,[12]
germanene,[13,14] and phosphorene.[15–17]
precise control over the orientational and positional ordering, and complex
The emergence of various 2D materials
interfaces among 2D layers are essential for the continued progress of 2D promises a significant step forward in the
materials, especially for energy storage and conversion and environmental development of sustainable energy tech-
remediation. Herein, recent progress, the status, future prospects, and nologies and environmental remediation.
challenges associated with nanoscopic assembly of 2D materials are high- In particular, their cutting edge features,
including: 1) tunable in-plane electro-
lighted, specifically targeting energy and environmental applications. Geo-
conductivity with charge density waves
metric dimensional diversity of 2D material assembly is focused on, based (CDW),[18] 2) asymmetric out-of-plane
on novel assembly mechanisms, including 1D fibers from the colloidal liquid flexi­bility,[19] and 3) reduction/oxidation
crystalline phase, 2D films by interfacial tension (Marangoni effect), and 3D ability with selective gap manipulation,[20]
nanoarchitecture assembly by electrochemical processes. Relevant critical as well as unprecedentedly large surface
advantages of 2D material assembly are highlighted for application fields, area with chemical reactivity, hold enor-
mous implications for energy storage/con-
including secondary batteries, supercapacitors, catalysts, gas sensors, desali-
version and environmental applications.
nation, and water decontamination. Despite the substantial research effort
accumulated thus far, direct exploitation
of 2D materials for energy and environ-
1. Introduction mental applications has most often been unsatisfactory, due
to the serious tendency for material restacking and irrevers-
2D materials, single and few atomic layers of elements in a ible aggregation. In this regard, the recent challenge for 2D
plane geometry, have long been discussed theoretically due to materials, especially for sustainable energy and clean tech-
their fascinating asymmetric features of matter.[1–4] Unraveling nologies, is to design the feature rich functional microarchi-
and manipulating these complex states in materials chem- tectures whilst maintaining the benefits of 2D materials.[21]
istry has subsequently drawn attention to the development of Recently, frontier research aims to utilize nanoscale assembly
2D materials with various elements or compounds; this was as one essential route toward tailoring of the microstructure,
originally initiated by the discovery of single-layer graphene in exploiting the strong structure-dependent material properties
down to the atomic level.[22–24] Noteworthy that, unlike typical
molecular self-assemble biomolecules or well-designed poly-
Dr. G. H. Jeong, Dr. S. P. Sasikala, Dr. T. Yun, Dr. G. Y. Lee,
Prof. S. O. Kim meric molecules, 2D materials lack any specific intermolecular
National Creative Research Initiative Center interaction for spontaneous assembly, such as hydrogen
for Multi-Dimensional Directed Nanoscale Assembly bonding sites or amphiphilic structures for hydrophobic inter-
Department of Materials Science and Engineering action. Moreover, typical 2D materials show extremely large dis-
KAIST
291 Daehak-ro, Yuseong-gu, Daejeon 34141, Republic of Korea tribution of in-plane shapes and dimensions, as well as various
E-mail: [email protected] layer-stacking numbers, which is also distinctive from the well-
Prof. W. J. Lee defined molecular structures of conventional self-assembling
Department of Fiber System Engineering biomolecules or synthetic polymers. Accordingly, a strong
Dankook University external stimulus is required to trigger effective assembly. In an
Yongin-si, Gyeonggi-do 16890, Republic of Korea
ideal case, for example, 2D materials in their pristine form can
E-mail: [email protected]
be assembled on a liquid surface by heterogeneous interfacial
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.201907006. tension (Marangoni effect).[25] However, chemical modification
of 2D materials is commonly required to mediate the driving
DOI: 10.1002/adma.201907006 force for assembly, as in the example of 1D fiber spinning from

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graphene oxide liquid crystal (GOLC).[26] Herein, judicious con-

sideration of chemical modification is critical for the realization Gyoung Hwa Jeong received
of optimal physicochemical characteristics for target energy or her Ph.D. degree in chem-
environmental issue. istry from Pusan National
Here, we review the recent progress, status, and future University (Korea) in 2005.
prospects and challenges facing the nanoscopic assembly of She joined Prof. Sang Ouk
2D materials for energy and environmental applications. We Kim’s group as a research
devote attention to the crucial roles that tailored microstructure assistant professor in 2018
can surpass its challenge to reveal its ultimate potential for the and her current research
urgent technological area for human sustainability. interest is nanoscale
assembly of various materials
including 2D materials.
2. Physical Properties and Attractive Features
of 2D Materials for Energy and Environmental
Application Won Jun Lee is the assistant
professor in the Department
The intriguing physical properties of 2D materials have trig- of Fiber System Engineering
gered tremendous research interest for the development of at Dankook University,
various energy and environmental applications. Owing to their Yongin, Korea. His research
atomically thin and confined geometry, 2D materials exhibit interest centers on the
properties dramatically different from those of their bulk fabrication of intelligent
counterparts. Apart from the most widely investigated mate- architectures with emergent
rial, graphene (monolayer of sp2 carbon), there are a host of nanoscopic functionalities.
2D materials that have garnered interest, including transition
metal dichalcogenide (MX2), MXene (Mn+1AXn), silicene, phos-
phorene (i.e., black phosphorous), and germanene. Table 1
summarizes the typical electronic properties (bandgap (eV)[27–32]
and work function (eV)),[33–38] structural property (bond
length (Å)),[39–44] transport properties (electrical conductivity Sang Ouk Kim is a pro-
(S cm−1)[45–50] and thermal conductivity (W m−1 K−1)[51–55]), fessor in the Department
mechanical in-plane stiffness (Young’s modulus (GPa)[56–61]), of Materials Science and
and surface energy (mJ m−2)[62–66] of these representative 2D Engineering at KAIST, and
materials. the director of the National
Ability to manipulate electrons in 2D geometry with dif- Creative Research Initiative
ferent periodic super-lattices can manifest itself in different (CRI) Center for Multi-
band structures. Analogous to the elemental chemical poten- Dimensional Directed
tials of bulky counterparts (3D), the bandgap of 2D structures Nanoscale Assembly and
has been shown to vary with constituent materials. The precise Graphene Liquid Crystalline
control of edge geometry and crystal shape of 2D materials can Fiber Center, Daejeon, South
significantly influence the chemical potential and thereby effec- Korea. His research group is
tively tune the bandgap.[67,68] For semiconducting 2D materials, actively researching the nanoscale assembly and chemical
such as MX2, silicene, and phosphorene, electronic properties modification of various nanomaterials, including 2D
can be further altered beyond the constraints of bulky mate- materials.
rials by imposing nanoscale confinements.[15,68,69] Indeed, other
fundamental electronic parameters, such as carrier density and
dimensionality of Fermi surface, can also be affected; such owing to their linear energy dispersion within two dimen-
properties are closely related to the work function, in terms of sions, which suppresses carrier scattering during charge
equivalent electrical potential. transport.[71] While there is a generally positive correlation
Interestingly, modification of the lattice constants can between electrical conductivity and thermal conductivity, it is
also be realized by chemical modification, such as substitu- noteworthy that one of TMDC (SnS2) confirms a negative cor-
tional doping, which introduces new density of states near relation (i.e., increase of electrical conductivity with decrease
the Fermi level.[70] Along with heteroatom doping, the bond of thermal conductivity) with structural coupling.[72] In
length and lattice constant of 2D structures can be strained. mechanical features, 2D materials render a unique combina-
It is well-recognized that atomically thin 2D materials have tion of high in-plane stiffness and strength with low flexural
relatively higher electrical and thermal conductivities than rigidity. The variation of in-plane stiffness can be ascribed to
those of their bulk counterparts, which may contribute to per- the bond strength (i.e., bond length), whereas out-of-plane
formance improvement in many different types of devices. flexibility is offered by the genuine 2D geometry with atomic
In principle, 2D materials possess excellent screening effect thin thickness.

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Table 1. Physical properties of various 2D materials.

Graphene TMDC (MX2) MXene (Mn+1AXn) Silicene BP Germanene

Bandgap [eV] 0 (BL) [27]
≈1.8 (ML, MoS2) Metallic (Ti3C2TX) ≈1.27 (ML)[29] ≈1.88 (ML)[31] 0 (ML)[32]
≈1.57 (ML, MoSe2) ≈0.24 (Ti2CO2)[28] ≈0.55 (BL)[30] ≈0.05 (BL)[32]
≈1.45 (ML, WS2) ≈1.80 (Sc2CO2)[28]
≈1.67 (ML, WSe2) ≈0.88 (Zr2CO2)[28]
≈1.0 (Hf2CO2)[28]
Work functiona) [Φ, eV] ≈4.5 ≈5.1 (ML, BL, ≈4.37 (Ti3C2TX)[35] ≈4.76[37] ≈5.16 (ML)[38] 4.66[37]
MoS2)[33,34] ≈3.35 (Sc10C9)[36] ≈4.56 (FL)[38]
≈4.3 (ML, WS2)[34]
≈4.6 (ML, WSe2)[34]
Bond length [Å] 1.42 (C–C) ≈3.15–4.03[39] ≈2.10 (Ti–C)[40] ≈2.25 (Si–Si)[42] ≈2.22 (P–P)[43] 2.49–2.56 (Ge–Ge)[44]
≈1.99 (Ti–O)[41]
≈2.15 (Ti–F)[41]
Electroconductivity [S cm−1] ≈106[45] ≈5.0 (MoS2)[46] ≈104[47] 6.5 kΩb)[48] ≈300 (with ≈105[50]
graphene)[49]
Thermal conductivity [W m−1 K−1] 5300[51] ≈19.5 (MoS2)[46] ≈55.2 (Ti3C2TX)[52] ≈16[53,54] 2000–5000[55] ≈15.95[54]
Young’s modulus [GPa] ≈1000[56] ≈270 (MoS2)[57] ≈330 ± 30 (Ti3C2TX)[58] ≈82.2[59] 106.4[60] ≈44 GPa nm[61]
Surface energy [mJ m−2] 46.7[62] 50–120 (MoS2 )[63] >40 1.36–1.82 (Si–Si)[65] 35–40[66] 1.0–1.71 (Ge–Ge)[65]
62.1 (GO)[62] (Ti3C2TX)[64]

a)ML, BL, and FL represent mono, bi-, and few layers, respectively; b)Sheet resistance measured with 4 point probes.

Systematic understanding of interfaces among 2D assem- 3. Nanoscale Assembly of 2D Materials

bled structures requires detailed analysis of chemical compo-
sition, atomic level interaction, defects, impurities, and so on, Straightforward translation of the interesting properties of 2D
which integrate to offer different chemical affinities for sur- materials for a variety of target applications has diverged sig-
face energy.[73] In general, the surface energy for single-ele- nificantly from the early day prospects, partly due to the uncon-
mental 2D systems (i.e., graphene, silicone, germanene, and trolled polydispersity of their lateral shapes, sizes, and layer
black phosphorus, BP) is always positive and relatively high, stacking numbers. Indeed, the underlying low symmetry and
with nonpolar neutral bonding within the hexagonal honey- CDW of layer materials commonly lead to peculiar arrangements
comb lattice.[17,74–77] It is noteworthy that the roughness of the that may be difficult to generalize.[110] One well-known example
surface with intrinsic topography can significantly influence is the strong clumping tendency of 2D materials (i.e., agglomer-
the surface energy. For multicomponent systems (i.e., TMDCs ates) that, arising from the high surface energy with asymmetric
and MXene), chemical effects such as polar bonding and dis- out-of-plane flexibility, commonly accompanies undesired deteri-
persive energy should be considered.[10,78–80] Interestingly, oration of material properties along with random structural dis-
both systems have intrinsically highly dispersive surfaces tortion as well as heterogeneous interlayer interference.[23,111,112]
that account for the long range van der Waals (VdWs) forces One promising direction toward efficient nondamaging control
between layers. The observed surface energies of 2D materials of 2D materials is the judicious exploitation of the nanoscale
are summarized in Table 1.[62–66] Apart from their intrinsic assembly principle, which can be used to manipulate geo­
function in the construction of VdWs layered structures, 2D metry, charge, and polarizability, as well as weak interactions
materials can interact on both faces via noncovalent interac- among planar geometries.[113–118] As shown by Figure 1, we have
tion, and therefore identification of their surface energy is a recently introduced three novel mechanisms for the nanoscale
key parameter for the design of hierarchical structures, cata- assembly of 2D materials, including liquid crystal assembly, sur-
lytic reactions, ion adsorption, and chemical sensors.[76,81–83] face tension assembly, and electrochemical assembly. Accord-
Indeed, heteroatom doping can endow 2D materials with ingly, compelling opportunities exist for the design of various
tunable surface energies, which extends their potential for a dimensional macroscopic architectures, including 1) 1D fibers,
spectrum of energy conversion and storage.[84–93] As a matter 2) 2D films (or sheets), and 3) 3D structures.
of fact, the chemically inert surface of graphene can be altered
by molecular or atomic doping, which are now commonly uti-
lized for secondary batteries and supercapacitors.[84–86,94–96] 3.1. Fibers (1D)
Together with unique flat geometry with microdefects such
as edges and pores, tunable surface energy gives rise to the State-of-the-art, smart textiles (i.e., intelligent systems with
practical energy and environmental applications.[83,97–109] electronic components in textile forms) pays a particular
Table 2 briefly summarizes the attractive structural- and attention to the structured filaments consisting of 2D mate-
chemical features of 2D materials and their relevant versatile rials. Introducing 2D materials into filaments or yarns could
applications. knit the new functionalities of 2D materials into fabric and

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 Table 2. Attractive features of 2D materials for energy and environmental applications.

Secondary batteries[87] Energy applications Electrocatalysts[89] Environmental applications

Supercapacitors[88] Water purification[83]
Filtration[100] Desalination Photocatalytic
decontamination
Graphenea) [Anode] [EDLC electrode] [HER catalysts] [Porous substrate] [Reverse osmosis [Dye degradation]

Adv. Mater. 2020, 1907006

Active Li intercalation (Li2C6744 mAh g−1) Intrinsically high EDLC capacitance N-doping, (quaternary/pyridinic Pore functionalization membrane][97] Heterojunction with TiO2,
with high surface area (2630 m2 g−1) (21 µF cm−2)[96] N)[85,86] via edge exposure Sieving of ions with ZnO[83]
[Cathode] Single layer capacitance [OER catalysts] (GO, rGO)[97] spacer geometry [Heavy metal ion
www.advancedsciencenews.com

Conductive additives with facile charge (≈550 F g−1)[96] P,N-codoping[85,86] [Organics absorbents] (0.1–1 nm) reduction]
transport (106 S cm−1) [Pseudocapacitor electrode] [ORR catalysts] Tunable oleophobicity [Forward osmosis Magnetic separation with
Encapsulants for sulfur spheres N-doping, pyridinic N B,N-doping[85,86] [Heavy metal ion removal] membrane][107] hybrid structure[83]
4+
(rGO for Li–S battery) (CHNH + 2e− + H2O ↔ (Graphene) 4e− pathway Cs+ remediation Sieving of ions with Cr to Cr3+ (rGO–ZnO)
[Electrolyte] CHNHOH: redox reaction)[84] (rGO)-2e− pathway[84] (Cs+ + COO−/CO−Na)[105] size exclusion via tun- [Bacterial disinfection]
Conductive additives with high Li+ rGO (>COH ↔ CO +H+ + e−, [Catalytic support] able pore size (K+ > Abundant oxygen enriched
diffusivity (10−7 to 10−6 cm2 s−1) irreversible)[84] Metal–N–C modificationb)[89] Na+ > Mg2+ > Ca2+) edges ∙OH−, ∙O2−, H2O2
[Conductive binder] (reactive O species)[97]
Conductive additives with high
electrical conductivity
(0.337 S cm−1)
TMDCc) (MX2) [Cathode] [Pseudocapacitor electrode] [HER catalysts] [Heavy metal ion removal] [Reverse osmosis] [Heavy metal ion
Active Li intercalation[79] Multivalent transition High proton mobility Theoretical adsorption Elastic sup- reduction]
MoS2 (670 mAh g−1, Li-ion battery)[79] (Mo2+ to Mo6+, W2+ to W6+)[8] (148 cm2 V−1 s−1, MoS2) through capacity of MoS2 port with high Capture of nuclear waste
Weak van der Waals force[81] metallic edge[78] (for Hg2+ = 2506 and for Young’s modulus with sulfur enriched
van der Waals Ag+ = 1348 mg g−1)[249] (200–300 GPa)[98] edges[98]
heterostructures[81] [Bacterial disinfection]

1907006 (4 of 23)
Facile redox reaction
with tunable bandgap
(1.2–1.6 eV)[78]
MXene [Anode] [Pseudocapacitor electrode] [HER catalysts] [Heavy metal ion removal] [Dye degradation]
(Mn+1AXn)d) High theoretical capacity for Li+ High electrical Free energy for hydrogen Facile absorption of Superior cationic dye
(320 mAh g−1, Ti3C2Tx) and Na+ conductivity(≈104 S cm−1) adsorption[91] cations via electrostatic capture with negative
(268 mAh g−1, Ti3C2Tx).[90] Intrinsic capacitance (≈900 F cm−1, attraction[103] surface charge[104]
T = F, OH Ti3C2Tx)[11] T = F, OH
[Cathode]
Conductive additives with facile metallic
conductivity
[Separator]
Low metal diffusion energy barrier[80]
BP [Anode] [EDLC electrode] [OER catalysts] [Dye degradation]
High theoretical capacity for Li+ van der Waals interaction between Long charge-carrier diffusion Facile redox reactions
(2786 mAh g−1) and Na+ (2596 mAh g−1) layers[77] paths[92] with tunable bandgap
with directional diffusion[76,77] [HER catalysts] (0.3–2 eV)[108] and
Facile charge transport with electron mobility
edge enriched structure[93] (1000 cm2 V−1 s−1)[109]

a)
Graphene derivatives including graphene oxide (GO) and reduced graphene oxides (rGO); b)Metal–N–C: metal = Co, Fe, Ni, Mn, and so on; c)TMDC: transition metal dichalcogenides, MX2: M = Mo, W, V, and so on,

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X = S, Se, Te; d)MXene, Mn+1AXn: M = Ti, V, Cr, Nb, and so on, A = Al, Sn, Si, and so on, X = C and/or N.
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Figure 1. Scheme of nanoscale assembly of 2D materials and applications. We propose to classify nanoscale assembly methods in three ways: surface
tension driven assembly, liquid crystal assembly, and electrochemical assembly. Top left photograph: Reproduced with permission.[121] Copyright 2011,
Wiley-VCH. Top left SEM image: Reproduced with permission.[183] Copyright 2017, American Chemical Society. Top right photo and SEM images:
Reproduced with permission.[142] Copyright 2014, American Chemical Society. Bottom-left photo: Reproduced with permission.[155] Copyright 2017,
Wiley-VCH. Bottom-right SEM image: Reproduced with permission.[158] Copyright 2010, Wiley-VCH.

textiles, which empowers the implication of 2D materials. uniaxial alignment of planar 2D materials in their liquid
Indeed, many different 2D materials haven been exploited for crystalline phase can be a valuable regulator particularly for high-
the wet-spinning of functional fiber systems, taking advantage performance fiber, which is analogous to the case of high per-
of the ready alignment of their highly anisotropic 2D geometry formance liquid crystalline polymer (LCP) fiber system, such as
in fiber axis directions under strong shear flow, which can sub- aramid fiber. This promising research direction is pioneered by
sequently mediate strong interplanar interaction among the Kim et al. based on their world-first discovery of colloidal nematic
neighboring aligned 2D materials to sustain the macroscopic type LC phase formation of graphene oxide (GO) (Figure 2a).[121]
fiber geometry.[119] While the prerequisite for wet-spinning pro- Typical colloidal nematic LC phase shows orientational ordering of
cess is not rigorous especially in spinning dope preparation anisotropic molecules or particles without any specific positional
(concentration, purity, etc.), structural manipulation could be order above a critical concentration in a stable solvent disper-
constrained by inherently low viscosity and random alignment sion. Highly purified aqueous dispersion of oxygenated form of
particularly at low concentration dispersions, which can also graphene, GO, was discovered to form stable nematic LC phase,
enrich structural defects like geometric voids. Key parameters which can be exploited for many different routes to graphene-
for a successful structure manipulation of 2D material based based novel material fabrication (more details can be found in the
fiber structure include: 1) stable solvent dispersion of 2D mate- previously published review articles for GOLC).[26,119,122]
rials up to a sufficiently high concentration, 2) ready alignment Among many different material fabrication strategies relying
of 2D structures along fiber axis, and 3) uniform interlayer dis- on GOLC, wet-spinning of 1D fiber assembly is one of the most
tance among 2D constituents in a spinning dope (i.e., thermo- promising active research fields. Noteworthy that 1D analog of
dynamically stable colloid is highly desired).[119] graphene, carbon nanotube (CNT), has been exploited for the
Importantly, the discovery of the liquid crystalline (LC) phase of wet-spinning of carbon fiber by means of its LC phase forma-
2D graphene was timely for the scientific challenge for 2D based tion typically in strong acids. Unfortunately, the inherent high
nanoscale assembly while offering unprecedented opportunity cost of high quality CNTs as well as the toxic strong acid based
for highly ordered structure control.[120] Indeed, well-defined solvent system has been the principle issue.[26,123–125]

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Figure 2. Liquid crystal and 1D fiber with 2D materials. a) GO liquid crystal with typical disclination structures and GO liquid-crystal polymer composite
fiber with optical birefringence. Reproduced with permission.[121] Copyright 2011, Wiley-VCH. b) SEM image of graphene fiber with tilted, transverse,
and longitudinal section views and small-angle X-ray scattering patterns of the graphene fiber. Reproduced with permission.[128] Copyright 2015,
American Association for the Advancement of Science. c) SEM images of: i,iii) pure graphene fiber and ii,iv) dopamine hybridized fiber. Reproduced
with permission.[129] Copyright 2018, Wiley-VCH. d-i) Schematic figure, ii,iii) optical image of graphene belt, and iv) SEM image of graphene belt.
d) Reproduced with permission.[130] Copyright 2019, IOP Publishing.

The idea of LC based wet-spinning of graphene based fiber packed fiber geometry with intercalation of small-sized GOs
was initiated even from the first report of GOLC behavior by into voids among large GO alignment; this gave rise to excel-
means of aqueous soluble polymer additive for a facile viscosity lent mechanical performance and record-high thermal conduc-
control. Gao and co-workers immediately followed this initial tivity (Figure 2b).[127,128] In addition, a noticeable advancement
idea by reporting the first additive-free fiber wet-spinning from beyond typical macroscopic wet spinning was enabled by defect
GOLC phase. Without any additive, as-spun GO fibers directly engineering with a mussel-adhesive, polydopamine (PDA)
spun from sufficiently concentrated GOLC dispersion in pure (Figure 2c).[129] Surface energy adjustment with PDA, which
water can be briefly thermally reduced to restore the electrical successfully enhanced the interlayer adhesion among aligned
conductivity by moderate thermal treatment. The resultant low GO platelets, precluded the formation of folds and wrinkles in
cost mechanically flexible graphene fibers could be woven into the fiber geometry. Such a densely packed structure led to the
conventional textiles.[126] increase of both mechanical stiffness and electrical conductivity.
Recently, Lian and co-workers demonstrated high align- Another innovative method for 1D fiber assembly from 2D
ment graphene LC fiber with low defects by optimizing densely materials is shear-induced structural manipulation, as reported

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by Xin et al. (Figure 2d).[130] In this approach, strong size and within a range of a few nanometers.[145] This approach could
shape confinement effects were investigated and found to pro- be compatible with the roll-to-roll process, with its superior 2D
foundly impact the sheet alignment of 2D materials by allowing flake alignment. In general, high quality films composed of
a manipulation of liquid flow, typically two competitive flows of 2D materials should exhibit lamellar structure, resulting from
1) elongational flow and 2) step expansion flow. Indeed, various uniform alignment of 2D geometry.[146] The resultant film may
2D material-based fibers, including TMDC, MXene, and phos- demonstrate a freestanding character, along with mechanical
phorene, have been widely investigated, and novel structures flexibility (Figure 3c);[147] its distinct lamellar geometry could
have been proposed such as: 1) core–shell, 2) Janus, and 3) sea- offer distinct characteristics, such as 1) uniform gallery spacing
island morphologies.[121,131–134] Notably, structural manipula- between adjacent 2D sheets and 2) a high degree of lateral align-
tion through interlayer interaction is essential to stabilize the ment of 2D materials. As such, such films have been exploited
constituents, and also advantageous for novel structures with for various applications, including mechanical actuators,[148]
mechanical reliability. electromagnetic shielding,[149] filtration membranes,[150] super-
capacitors,[151] and so on.

3.2. Films (2D)

3.3. 3D Structure
Genuine potential to translate the inherent planar geometry
of 2D materials into macroscopic structures has motivated the The extremely high surface area and small particle dimen-
production of films or sheet structures that exhibit: 1) mechan- sions of 2D materials inevitably bring about a serious general
ical flexibility with ultrathin thickness, 2) high optical transpar- issue of restacking tendency in both dried and solvent disper-
ency, 3) CDW, 4) dipole-type polaritonic excitation and so on. A sion states, which is also associated to the intrinsic thermo-
large diversity of conventional and more advanced methodolo- dynamic nature of unstable interfaces. Restacking hinders
gies have been introduced to produce 2D material based film the effective exposure of the active surface of 2D materials,
structures, including: 1) spin-, spray-, dip- coating,[135] 2) drop which can be a critical drawback particularly for energy and
casting,[136] 3) self-assembly of monolayers,[137] 4) Langmuir– environmental applications, such as charge storage electrodes,
Blodgett techniques,[138] 5) photolithography,[139] 6) layer-by-layer catalysis, and pollutant capture. One ultimate approach to
(LBL),[140] and 7) vapor deposition.[141] These methods are rela- address this inherent restacking issue and to maintain the gen-
tively well-understood and have been thoroughly documented uine large surface area of 2D materials is to build robust 3D
in previously published review articles.[135–141] nanoscale architectures. Several unique advantages attainable
Nanoscale assembly, as introduced briefly above, frequently from 3D structure formation can be summarized as follows:
utilizes intermolecular interaction mediated by charges and 1) maximum exposure of surface area, 2) mechanical flexibility,
dipoles to engineer the positional and orientation arrange- 3) well-defined nanoporous structure formation, and 4) mechan-
ment of target molecules or particles at desired levels. By ically reliable reversible structure formation. Noteworthy that
contrast, a recent innovation for ultrathin film assembly from the previous predominant approach for 3D nanostructure
2D materials exploits interfacial self-assembly based on fluid formation was nanotemplate-based synthesis, which exploits
mass transfer via liquid convection and interfacial tension amphiphilic surfactant or polymer based self-assembled tem-
gradients at a liquid interface (i.e., Marangoni effect).[25] Inter- plates. Unfortunately, this approach generally yields 3D struc-
estingly, the surface Marangoni effect realizes a surprising tures with low crystallinity and dense structural defects. After
defect-healing film formation behavior, in which, once surface the selective removal of templates, atomically interfaced struc-
film assembly reveals a noticeable void or defect in the assem- ture formation between target functional material and template
bled morphology, constituent particles spontaneously disas- upon a templated synthesis protocol frequently yields defective
semble and reassemble to generate a denser and less defective structures.[152–154]
film morphology. This result also manifests that transforma- Recently, Kim and co-workers utilized the difference in
tion of planar 2D materials into mechanically tunable ultrathin chemical reduction potential between GO and various alkali
planar structures is possible simply based on physical binding metals to reduce structural defects in the 3D assembly pro-
(Figure 3a).[142] Indeed, this method can be used not only to cess. Interestingly, spontaneous redox reaction could readily
readily tune the film thickness with nanoscale precision but build a flexible 3D hydrogel network of graphene, in which
also to fabricate large area thin films (radius ≈8 cm) within a GO platelets were layer-by-layer reduced in an electrochemical
few minutes of processing time. Additionally, as this assembly way on a zinc (Zn) surface (Figure 4a), while Zn is oxidized
behavior is driven purely by external stimuli, it can be univer- in an aqueous dispersion of GO.[155,156] The high reduction
sally applied to many different 2D materials and their heteroas- potential of GO compared to Zn+ is obviously the driving
sembly, including TMDCs and phosphorene, and can also be force for the exchange of surface composition on the Zn
used even for other low-dimensional nanomaterials, including template, which process is similar to the electroless deposi-
0D nanoparticles, fullerenes, and 1D CNTs.[143,144] tion principle. Noticeably, the simultaneous reduction of GO
More recently, Sivula and co-workers reported a self- upon interfacial reduction on Zn templates creates, without
assembly method for 2D WSe2 thin film at a liquid–liquid any further post-reduction process, an electrically conductive
interface (Figure 3b).[145] In this approach, 2D flakes were con- rGO 3D architecture. The relatively slow kinetics of gelation,
fined at the interface between two different immiscible liquids particularly from GOLC dispersion, build up a quasi-parallel
and it was possible to finely control the thickness of thin film, graphene-assembled structure with maximal exposure of

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Figure 3. Thin film geometry with 2D materials. a-i) Schematic figure, ii,iv) optical images, and iii) SEM image of interfacial self-assembly of graphene
flake. Reproduced with permission.[142] Copyright 2014, American Chemical Society. b-i) Schematic figure, ii) optical image, and iii) SEM image of liquid–
liquid interface thin film assembly for WSe2. Reproduced under the terms of the CC-BY Creative Commons 4.0 International License.[145] Copyright 2015,
Macmillan Publishers Limited. c) Vacuum assisted 2D MXene paper with optical image, SEM image, and contact angle analysis. Reproduced with
permission.[147] Copyright 2014, National Academy of Sciences.

constituting graphene platelets.[157] This interesting method on the surface of the organic dispersions (Figure 4b).[158] Con-
also provides a valuable insight that both the thermodynamics sequently, open porous structure with different levels of thick-
and kinetics should be considered for successful design of a ness and pore size is created after all the volatile solvents are
highly ordered architecture. It should be noted that struc- vaporized. Interestingly, 2D materials can be straightforwardly
tural transformation upon nanoscale assembly is desired transformed into 3D structures by simple crumpling or folding.
to be either reversible or to allow assembled components In particular, crumpling of 2D materials can be well-tailored by
to adjust their optimal positions in the relaxation timescale using a controlled wrinkling strategy on the supporting flex-
to attain less-defective, more highly ordered nanoscale assem- ible substrates.[159] Taking advantage of this facile approach,
bled structures.[157] the effective surface area of graphene-based structures can be
Another approach for 3D assembly presents spontaneous remarkably enhanced.
dynamic assembly of aqueous droplets at an organic interface. In contrast to the noticeably accumulated research efforts
This is the called “breath figure” principle, which has been into 3D structures assembled from graphene, other 2D mate-
widely utilized for macroporous polymer film formation from rials, including TMDCs, MXene, and phosphorous, have
volatile organic solution. A thin organic solution of 2D mate- been much less investigated in this regard. The stiffer out-of
rials is prepared, over which a humid air stream is continu- plane mechanical properties of those materials, arising from
ously blown. Aqueous droplets are spontaneously condensed the multiple atomic layer structures (triple layer structure for
from the humid air stream and subsequently laterally ordered TMDCs and MXene) or nonplanar atomic bonded structure

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Figure 4. 3D structure based on 2D materials. a-i) Scheme and ii) SEM image of interfacial gelation of rGO. Reproduced with permission.[155] Copyright 2014,
Wiley-VCH and Elsevier. b-i) Schematic figure and ii) SEM image of breath figure assembly for GO. Reproduced with permission.[158] Copyright 2010, Wiley-
VCH. c) Shrinkage driven 3D crumpled structure with schematic figure and SEM image. Reproduced with permission.[159] Copyright 2016, Wiley-VCH.
d) Template assisted assembly of hollow 3D MXene structure with schematic figure and SEM image. Reproduced with permission.[162] Copyright 2017,
Wiley-VCH.

(phosphorene) cause inherently less flexibility in adapting to functionalization, 3) reversible ion and mass transport, and
a nonplanar geometry. Accordingly, 3D structure formation 4) reliable mechanical robustness, all of which are particu-
using those materials has principally relied on typical 3D tem- larly crucial for energy storage and conversion systems. Mean-
plate based synthesis.[160,161] It is noteworthy that Gogotsi and while, systematic understanding of state-of-the art structural
co-workers recently developed an effective route to 3D struc- engineering methodology is beneficial for optimal design of
tured MXene by exploiting the templated assembly upon sac- appropriate structures, which can be practically used for energy
rificial polymer beads (Figure 4d).[162] In addition, LC phase applications.[87,164,165] Effective control of the spacing among
formation of MXene has been exploited for highly aligned 3D layers in 2D materials has been proposed for the intercalation
electrode structures for supercapacitor application; in these of particles or molecules. The ability of a 2D host to capture
structures, highly aligned 3D geometry allows facile mass charged particles or molecules in a controlled reversible way is
transport through the electrode volume.[163] critical for effective energy storage mechanisms for secondary
batteries and supercapacitors. The possible amount of energy
storage by 2D materials (i.e., maximum energy density) can
4. Energy Applications be predominantly determined by: 1) chemical composition,
2) effective surface area, 3) surface wetting behavior, and
As mentioned above, controlled nanoscale assembly of 2D 4) charge transport properties of an electrode structure. By
materials into desired architectures has opened up valu- contrast, for energy conversion systems, when combined with
able routes to: 1) high specific surface area, 2) surface various energy sources, the surface chemistry/geometry and

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charge/mass transport properties of a catalytic structure will is to design 3D structures with flexible networks consisting
dominate the major performance, including onset voltage and of 2D materials. Such structures not only provide active sites
current density.[88,166–168] for Li+ or Na+ ions but also accommodate the considerable
volume change upon reversible charging/discharging cycles,
thus preventing capacity fading. Indeed, owing to the robust
4.1. Secondary Batteries and open porous framework of these materials, short diffu-
sion pathways are potentially available for Li+ or Na+ ions,
Owing to their crucial role as energy source for electronic which could thereby regulate the voltage window and cou-
devices or vehicles, majority research works for secondary lombic efficiency.
batteries have focused on boosting the energy density and In this popular research area, Lee et al. reported a pioneering
charging/discharging kinetics thus far, noticeably motivated work in which 2D graphene, taking advantage of its genuine asym-
by the recent emergence of novel 2D materials with high sur- metric mechanical flexibility, was introduced as an encapsulant
face area and facile charge transport. These virtues can be for active electrode materials (Si nanoparticles) (Figure 5a).[172]
seen to largely rely on optimal design of the electrode struc- In a similar way, Zhang et al. investigated the potential of an
ture.[169] Despite several recent achievements, there are still architecture of interweaved graphene as anode material.[173]
critical challenges for the immediate utilization of 2D mate- As can be seen in Figure 5b, such a nanoarchitecture could
rials without structural manipulation as follows: 1) capacity effectively constrain the aggregation of active materials and
fading with structure collapse, 2) narrow electrochemical buffer the mechanical strain that arises from large volume
stability window (related to redox potential), and 3) low ini- changes. Noteworthy that nanoparticles encapsulated by 2D
tial coulombic efficiency (related to Faraday effect).[170,171] One materials can play an additional role in structural integrity. The
effective strategy to address the aforementioned challenges ability to encapsulate 0D materials was also exploited for the

Figure 5. Secondary batteries using 2D materials. a) Graphitic self-encapsulation: i) Scheme of graphitic self encapsulation. Mixing pH was controlled
for electrostatic attraction between SiO2 surface and N-doped sites at graphitic carbons, ii) HR-SEM, and iii) HR-TEM images of Si particles with
encapsulated N-doped CNT and graphene. Reproduced with permission.[172] Copyright 2014, The Royal Society of Chemistry. b) Based on a bottom-up
self-assembly strategy, MgH2 nanoparticles (NPs) uniformly anchored on graphene (GR) are fabricated as anode materials for Li-ion batteries (LIBs).
Schematic illustration of the fabrication of MgH2/GR (GMH) composite. GMH composite with 50 wt% MgH2 delivers high reversible capacity of
946 mAh g−1 at 100 mA g−1 after 100 cycles. Reproduced with permission.[173] Copyright 2018, American Chemical Society. c) Synthesis of crumpled
N-Ti3C2Tx/S composites. Cycling performances of samples at 2C for 1000 cycles (1C = 1673 mA g−1) Reproduced with permission.[177] Copyright 2018,
Wiley-VCH.

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development of novel cathode structures. Zhu et al. developed practical performance of SCs can be compromised due to the
3D macroporous composites with Li2FeSiO4 and 2D materials low packing density of 2D materials, which can lead to poor
using silica spheres as templates.[174] 2D materials preferen- volumetric capacity and fragile networks. Accordingly, optimal
tially form interconnected conductive 3D network and con- design of SCs based on 2D materials inevitably requires a judi-
tribute to increases of cyclic stability and high initial coulombic cious counterbalance between the porosity and volume density
efficiency. of the electrode structure.
While graphene has mostly been utilized for improvements For the case of fiber-type SCs, core–shell structures, in which
of Li+ ion batteries, some TMDCs, such as TiS2 and NbS2, have two different components at core and shell may serve in dif-
demonstrated stable cycle windows with improved rate capa- ferent critical roles, will be highly advantageous. As shown in
bilities for Na+ ions.[175,176] In addition, more recent investiga- Figure 6a,[183] conductive polymer core and 2D material shells
tions have suggested the great potential of MXene, a family of in fiber geometry synergistically offer interfacial charge storage
transition metal carbides, nitrides, and carbonitrides, for Li–S as well as intercalated pseudocapacitance, along with reliable
batteries. The key benefits of such developments is dipole-type mechanical robustness. A similar synergy effect was achieved
polaritonic excitation for effective trapping of polysulfide with in a hydrogel structure by introducing certain metal cations
rich surface chemistry. Negatively charged Ti3C2Tx nanosheets into 2D material dispersants (Figure 6b).[155] Multivalent metal
appear to be superior for the formulation of specific microstruc- cations exchanged into 2D materials may induce effective phys-
tures with positively charged melamine (Figure 5c); these struc- ical crosslinking by coordination bonding, which can subse-
tures also maintain an open porous structure after pyrolysis.[177] quently induces stable hydrogel formation with a high EDLC
Apart from these structural advances, nitrogen incorporation performance and yield additional pseudocapacitance with
into MXene framework has allowed the facile adsorption of existing cations.
polysulfides at the MXene surface, which is highly desirable for Unlike pristine graphene, in which the EDLC mechanism is
Li–S battery applications. For secondary batteries, 1D nanoscale dominant because of its genuine chemical inertness, the elec-
assembly is challenging, and only a few studies have been trochemical energy storage of TMDC, MXene, and black phos-
conducted, principally due to the intrinsic difficulty of surface phorous may rely on a pseudocapacitance mechanism based on
contact in 1D geometry.[178] Nonetheless, a number of recent a redox reaction at the electrode surfaces. 3D structured V2CTx
advances have indicated that novel configurations such as wire- (i.e., a type of MXene), fabricated by cation exchange method,
type and fabric-type batteries are within close reach, together has attained remarkable performance of SCs with excellent
with emerging strategies for structural manipulation of 2D rate capability and high gravimetric capacity (Figure 6c).[184] In
materials.[179] the different families of MXene, cation exchange substantially
improves the electrical conductivity as well as the structural
integration. Interestingly, the predominant arrangement of
4.2. Supercapacitors (SCs) 2D materials can be further modified by introducing other low
dimensional materials. Poor electron conduction and prevalent
SCs are the typical energy systems bearing intrinsically high- restacking tendency of block phosphorous suppress its practical
power performance compared to that of secondary batteries. use in SCs, which they have higher interlayer spacing (5.3 Å)
This characteristic stems from their relatively simple charge than that of graphene (3.6 Å). With the aid of simple CNT inter-
storage mechanism of charge holding under an electrical field. calation, structured BP/CNT has revealed its great potential
Recently, nanoscale assembly of 2D materials supports a valu- for high energy density performance (96.5 mWh cm−3) among
able innovation in this device mechanism: the preferential for- previously reported 2D material based structures (MoS2-based,
mation of a 3D network structure can provide favorable charge 1.6 mWh cm−3; graphene-based, 6.3 mWh cm−3; MnO2-
storage via a faradaic (i.e., pseudocapacitors) or nonfaradaic based, 11.1 mWh cm−3, and MXene-based, 32.6 mWh cm−3)
process (i.e., electrochemical double layer supercapacitors). (Figure 6d).[185]
Further information on how electrons and ions can be effec-
tively stored at the surface of 2D materials is detailed in pre-
vious works in the literature.[180,181] The development of high 4.3. Electrocatalysts
power SCs crucially requires interpenetrating transport path-
ways for electrons and ions, which ensure efficient interfacial Catalytic energy conversion is an essential element for next gen-
ion storage or intercalated pseudocapacitance. Without reliable eration renewable energy storage and conversion systems, such
shape engineering, 2D layers generally tend to restack when as fuel cells, water electrolysis, and metal–air batteries.[186–190]
fabricated into an electrode structure due to strong π–π interac- Historically, noble metal or transition metal oxides have been
tions, thereby hindering accessible surface area and transport of extensively explored for electrocatalysis systems, such as
charged species.[182] Nanoscale assembled 2D materials exhib- 1) hydrogen evolution reaction (HER), 2) oxygen evolution reac-
iting desired features, such as 1) out-of-plane flexibility and tion (OER), and 3) oxygen reduction reaction (ORR), with their
2) dipole-type polaritonic behavior, are promising candidates two major distinctive features of low overpotential and high cur-
for the fabrication of idealized SC electrode structures, par- rent density.[191,192] Nevertheless, commercial success has yet to
ticularly with well-tailored hierarchical porosity. Several initial come not only due to the rapid degradation of their surface cat-
research efforts focusing on the design of hierarchical porous alytic activities as well as high cost in the market.[193] Most 2D
structures have already benefited from the high gravimetric materials shed light on their practical use as economical alter-
capacities of these SC electrode structures. Unfortunately, natives along with the dramatic reduction of thermodynamic

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Figure 6. Supercapacitors with 2D materials. a) Process of graphene@polymer core–shell fibers (G@PFs). Also, photograph showing serially con-
nected three G@PEDOT fiber supercapacitors that light up a green LED. Reproduced with permission.[183] Copyright 2017, American Chemical Society.
b) Gelation of graphene: i) Optical image of local gelation at prepatterned Zn substrate. ii) SEM image of graphene gel tube grown Z wire. iii) Optical
image of monolithic graphene gel fiber net. iv,v) Optical images of 3D graphene gel. vi) SEM image of vertical gel tube. vii) CV curves of graphene gel
and capacity retention during 4000 cycles. Reproduced with permission.[155] Copyright 2014, Wiley-VCH. c) Schematic figure. Cation-driven assembly
process to fabricate highly stable pseudocapacitive electrodes with superior electrochemical properties from otherwise unstable 2D V2CTx Mxene flakes.
Reproduced with permission.[184] Copyright 2019, Wiley-VCH. d) Scheme of BP/CNT macrofibers structured by microfluidic-spinning-technique (MST)
fabrication. Reproduced under the terms of the CC-BY Creative Commons 4.0 International License.[185] Copyright 2018, The Authors, published by
Springer Nature.

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Figure 7. HER with 2D materials. a) Defect-rich MoS2 ultrathin nanosheets, i) structural models of defect-free and defect-rich structures and
ii) polarization curves of various samples as indicated. Reproduced with permission.[196] Copyright 2013, Wiley-VCH. b) MoS2 with strained S-vacancies,
i) schematic of the top and side views of MoS2 with strained S-vacancies on the basal plane and ii) LSV curves of monolayer MoS2 with elastic tensile
strain and S-vacancies. Reproduced with permission.[197] Copyright 2015, Springer Nature. c) 2D molybdenum carbide (MXene), i) schematic of the
Mo2CTx, ii) HER activity and stability of MXenes. Reproduced with permission.[198] Copyright 2016, Wiley-VCH. d) Layered black phosphorus, i) surface
of black phosphorus crystal imaged by SEM and ii) HER on basal- and edge-plane black phosphorus electrodes. Reproduced with permission.[199]
Copyright 2016, Wiley-VCH. e) Amorphous MoSx deposited graphene liquid crystalline fiber, i) SEM image of RGO fiber, ii) SEM image of MoSx film
deposited on RGO fiber, iii) LSV of MoSx/RGO. Reproduced with permission.[200] Copyright 2017, Wiley-VCH. f) Cobalt based nanoparticle embedded
rGO aerogel, SEM (inset images), low-magnification TEM images of: i) CoS2/rGO aerogel, ii) CoP/rGO aerogel, and iii) CoS|P/rGO aerogel, and
iv) LSV curves and Tafel slopes. Reproduced with permission.[201] Copyright 2019, Wiley-VCH.

barriers and accelerated kinetics for electrochemical energy edges, are poised to impact on the emerging field of HER
conversion processes.[80,89,194] The remarkable advances of catalysis (Figure 7a).[196] It is Noteworthy that, unlike pristine
electrocatalysis, particularly in the past decade, have provided graphene, chemically functionalized graphene has reported
guidelines to the building of highly efficient electrocatalysts. several advantages for electrochemical activities.[89] An innova-
These catalyst allow us to engage in: 1) edge engineering to tive approach has utilized defect engineering to create point
create more active sites, 2) optimal bandgap for facile charge defects (monovacancies) in MoS2 nanosheets. Introduction
transfer, and 3) multiscale hierarchical structure formation for of sulfur vacancies is able to tune the bandgap and induce
facile mass transfer.[195] mechanical strain in the atomic crystalline structure for pref-
While pristine graphene reveal little electrochemical erential adsorption of hydrogen (Figure 7b).[197] The rather
activity, TMDCs, owing to their polymorphism with abundant complicated structural coordination of MXene and black

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Figure 8. OER and HER using 2D materials. a) N-doped graphene nanoribbons with interconnected 3D architecture (N-GRW): i) schematic of N-GRW,
and ii) LSV curves for OER. Reproduced with permission.[205] Copyright 2016, American Association for the Advancement of Science. b) HRTEM images
and polarization curves of hybrid film (TCCN) coupling g-C3N4 and MXene. Reproduced with permission.[208] Copyright 2016, Wiley-VCH. c) SEM
images, and LSV curves of N-doped COP graphitic carbon (C-COP). Reproduced with permission.[209] Copyright 2014, Wiley-VCH. d) LGO flakes by
liquid crystallinity: i) phase separation (left) and size selection of a GO aqueous dispersion (right), and ii) Koutecky–Levich plots of ORR. Reproduced
with permission.[210] Copyright 2014, American Chemical Society.

phosphorous has emerged as a plausible candidate for HER 4.4. Sensors

(Figure 7c,d).[198,199]
Multiscale hierarchical structure strongly highlights its The fundamental mechanism of gas sensors is rooted in the
importance in electron transfer. Hybridization of two distinct transformation of chemical potential into electrical current
2D materials via nanoscale assembly elicits such multilevel density, which can be effectively controlled by the chemical
pathways for electrocatalysis. Importantly, Lee et al. reported adsorption of gaseous species on the surfaces of 2D materials.
an MoSx/reduced GO (rGO) hybrid structure that shows a Nowadays, it has become apparent that 2D materials can adsorb
dramatic increase in electron transfer and low overpoten- numerous gases, such as NO2, CO2, CO, and NH2, on their
tial (Figure 7e).[200] Similarly, Koo et al. confirmed that their active sties. However, structural collapse or restacking of 2D
assembled hybrid structure manifests its advantages with materials makes it hard to retain the genuine chemical adsorp-
0D nanoparticles (Figure 7f).[201] Interestingly, stable inter- tion characteristics with delayed mass and charge transfer. The
facial assembly with multiscale pore distribution could con- nanoscale assembly of 2D materials could be programmed to
tribute to different electron transfer rates and high surface form multilevel diffusion pathways for gases and secure effi-
area.[155] cient charge transfer. Specifically, hierarchical structures have
Compared with HER in water electrocatalysis, OER has made it possible to ensure: 1) high surface-to-volume ratio,
been known as the rate-determining step due to its inherently 2) maximal exposure of active edges, and 3) superior charge
high endothermic reaction barrier and multiple electron reac- transfer.[211]
tions.[202–204] While many innovative studies have been reported The surface-to volume ratio of 2D materials is strongly
on OER activity, graphene derivatives have received special dependent on the stacking layer number. He et al. reported that
attention because of their high OER and ORR efficiency with the thickness of spin-cast MoS2 thin film has a profound effect
surface functionalization (Figure 8a).[205] In particular, gra- on the performance of NO2 gas sensors (Figure 9a).[212] With the
phene with many functional groups at its edge is known to gradual decrease of the MoS2 thickness, edge active sites can be
have several catalytic active sites.[206,207] Indeed, the graphene more favorably exposed, leading to an increase of the surface-
framework hybridized with other 2D materials could serve as to-volume ratio. In the nanoscale dimensions of the assembled
a synergistic catalyst (Figure 8b).[208] Furthermore, metal-free structure, the fundamental geometry used to manipulate the
electrocatalysts for ORR offer a general strategy toward the surface tension and diffusion pathway provides a set of ground
development of renewable energy technologies. Sophisticated rules for gas absorption. Yun et al. explored the dramatic per-
assemblies of N-doped graphitic carbon materials are known to formance enhancement of gas sensors (i.e., increase of current
show high ORR activity (Figure 8c).[209] Even though it has been density) in a configuration with monolayer dominant MoS2
reported that many graphene derivatives have ORR activity, it is over a large scale (Figure 9b).[143] In contrast to typical laterally
noteworthy that size-selected GO with liquid crystallinity affects assembled 2D structures, Cho et al. built a vertically aligned
hetero-atom dopant structures and electrochemical properties structure of MoS2 for NO2 sensors (Figure 9c).[213] This ver-
(Figure 8d).[210] tical structure is also found to be highly advantageous because

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Figure 9. Sensors using 2D materials. a) Thickness dependent NO2 gas sensor for MoS2, i) schematic illustration of fabrication process of MoS2 TFT.
Array on PET substrate and photograph of TFT sensor array; ii) detection of 1.2 ppm NO2 using MoS2 TFT sensors on PET with different thicknesses
of MoS2 thin film. Reproduced with permission.[212] Copyright 2012, Wiley-VCH. b) Interfacial self-assembled MoS2 gas sensor: i) AFM image of self-
assembled MoS2 thin film, and ii) NO2 response comparison with various film thickness at each concentration. Reproduced with permission.[243]
Copyright 2018, American Chemical Society. c) Vertically aligned MoS2 gas sensor: i) TEM characterizations of grown MoS2 films, and ii) 100 ppm
NO2 gas demonstrates that edge sites of MoS2 show superior gas adsorption properties compared to basal plane. Reproduced with permission.[213]
Copyright 2015, American Chemical Society. d) Edge exposed MoS2 nanomesh gas sensor: i) STEM image of MoS2 nanomesh, and ii) gas sensing
behaviors of MoS2 nanomesh dynamic response transients of nanomesh and film toward NO2 in the concentration range of 1–5 ppm at room tem-
perature. Reproduced with permission.[214] Copyright 2018, Wiley-VCH.

of its abundant active edges, which give rise to high d-orbital specific functions with demanded material properties. Looking
electron density. Several follow-up observations suggest that a at state-of-the-art environmental applications driven by well-
superfine microstructure such as a nanomesh can improve the organized 2D materials inclines us to focus on their positive
performance of gas sensors even further, while exhibiting ultra- impacts on green technologies.
fast response time and significantly increased signal-to-noise
ratio (Figure 9d).[214] Recently, nanoscale assembly with MXene
and black phosphorous has been proposed as a new opportu- 5.1. Safety and Toxicology of 2D Materials
nity for innovation in gas sensing. Originating from their dif-
ferent characteristic atomic configurations, the performance of The available experimental data on 2D material toxicity are not
these materials for gas adsorption has been studied intensively. conclusive due to the diversity of 2D material edge structures
One of the longstanding challenges of gas sensors is their effec- and surface chemistry. Among the wide spectrum of 2D mate-
tive integration into flexible and wearable geometry. Nanoscale rials, graphene, GO, and TMDC have demonstrated biocompat-
assembly into macroscopic structural forms of fibers and films ibility, which is highly desirable for many potential applications
could reinforce the future for wearable gas sensors. such as bioimaging, biosensing, drug delivery, and tissue engi-
neering.[215] To this end, in vitro and in vivo toxicity levels of
graphene and GO with different concentrations (10 µg L−1 to
5. Environmental Applications 300 mg L−1) and lateral sizes (0.1–2 µm) have been system-
atically investigated.[216–219] A general conclusion from these
Advances in sensing of hazardous gases of 2D materials illus- studies is that the cytotoxicity of graphene derivatives is far less
trate key features of nanoscale assembly of 2D materials, espe- than those of other carbon nanomaterials such as CNT and
cially their ability for selective adsorption. More generally, 2D fullerene. Notably, graphene toxicity can be further reduced
nanomaterials have been extensively explored for various envi- by decreasing the lateral size and the oxygen functionality.[220]
ronmental applications, such as membranes, adsorbents, and Apparently, smaller GO sheets impose lesser physical damage
photocatalysts, particularly for water remediation. While there to cells, while decreased oxygen functionality retards the inges-
is still considerable debate regarding the intrinsic toxicity of tion of GO sheets in to the cells.[221] TMDCs, such as MoS2 and
2D materials, nanoscale assembly of 2D materials into free WSe2, were reported to have even less cytotoxicity compared to
standing structures, such as fibers, films, and 3D forms will GO.[222] Pang et al. concluded that a maximum concentration of
not only ensure their feasible and safe implication in water but 100 µg mL−1 may keep the balance of cytotoxicity and antibac-
also will avoid the misleading connotations to the word “nano.” terial ability of graphene and GO.[216] Nevertheless, contradic-
Taking advantage of nanoscale assembly, the structure and tory reports on graphene cytotoxicity warrants the importance
properties of the 2D materials can be precisely tailored to their of forming a standard regulatory framework for 2D material

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toxicity assessment. This framework should take into account of 0.36 nm in water. Several technical approaches such as par-
many parameters, such as lateral size, layer number, degree of tial reduction of GO, covalent crosslinking, photoreduced GO/
functionality, surface charge, and purity and concentration of titania hybrid membranes, physical confinement by epoxy
various 2D materials. coating of GO, and graphene–GO hybrid membranes have been
investigated to prevent the swelling of GO membrane in water.
Consequently, a significantly decreased interlayer spacing of
5.2. Water Purification Membranes 0.64 nm and ≈97% salt rejection were achieved (Figure 10b).
The ion diffusion through electrically conductive graphene and
Synergic opportunities have been realized through the usage MXene based membranes can also be precisely controlled by
of 2D materials as membrane materials for water purification. modulating the interfacial electrical double layer (EDL) with the
Compared to several micrometer thick conventional polymer assistance of small external voltage (Figure 10c,d).[229,231,232]
membranes, one-atom thick 2D material membranes offer TMDCs, such as MoS2 and WS2, have been reported to have
100 times greater water diffusion rate and the ability to separate higher water permeabilities than those of GO based mem-
small molecules.[223] Ideal 2D membranes can be fabricated branes, but with lower salt rejection performance.[228,233] Theo-
using low energy ion irradiation onto monolayers to impart retical studies have suggested that pores in MoS2 sheets with
nanopores 0.1–0.2 nm in diameter in the crystal lattice.[224] exposed Mo atoms yield ≈70% greater water permeation than
These nanopores will allow water molecules to flow through the that of graphene pores.[234] Most importantly, 5 µm thickness
membrane, while rejecting contaminant ions. Unfortunately, it MoS2 membranes structured with organic dyes are reported to
is challenging to create such membranes with a high density reject ≈99% of salt ions, while permitting a water flux higher
of uniform pores. Obviously, pore size uniformity is one of the than that of the GO membrane.[235]
most critical parameters for membrane performance, as any
presence of undesired larger pores can significantly deteriorate
the ultimate membrane separation performance. 5.4. Photocatalytic Water Decontamination
An alternative strategy is to stack 2D materials to form
laminar membranes with interconnected nanochannels Heterogeneous photocatalysis is an attractive tool using solar
(Figure 10a).[150] Many 2D materials such as graphene, GO, energy for cost-effective degradation of pollutants in water. In
hexagonal boron nitride (hBN), MoS2, WS2, and MXene based fact, oxidative species such as •O2−, •OH, and H2O2 photo gen-
laminar membranes are reported to show remarkably improved erated by a semiconductor catalyst can completely mineralize
selective water permeation while rejecting dye molecules and organic contaminants, reduce toxic heavy metal ions, and dis-
metal nanoparticles from water.[225–230] The selectivity of a mem- infect water.[236–238] Integration of photocatalytic nanomaterials
brane with a lamellar structure depends on many factors, such as (i.e., TiO2, ZnO, SnO2,WO3, ZnS, Ag3PO4, and BiVO4) in 2D
1) hydrodynamic, electrostatic and steric interactions of the materials can provide a unique opportunity for assembling
ions in water with the nanopores/nanochannels, 2) distance catalysts into various dimensional forms, such as fibers and
between the 2D material layers, and 3) defects in the 2D mate- films.[239,240] Such assembly not only improves the application
rials.[102,223] Further chemical modification of 2D materials, feasibility of nanomaterials in water streams, but also enhances
including chemical functionalization of pores and sheets, the decontamination efficiency. In principle, the high surface
should be beneficial to improve the membrane selectivity for area of 2D materials triggers an effective accumulation of con-
precise sieving of monovalent ions. taminants on active sites. Indeed, the high electron mobility of
2D materials, such as graphene, suppresses the rapid recombi-
nation of electron–hole pairs, while leading to extended catalyst
5.3. Desalination lifetime. (Figure 11a).[102,241] Importantly, the unique ultrathin
morphology of 2D materials (2–6 nm for a few layers) reduces
Optimal desalination membranes should be mechanically the charge migration distance and thus enhances the decon-
stable, so as to afford high water permeability while consist- tamination performance.[242]
ently rejecting hydrated salt ions and impurities. A strong Compared to pristine graphene with its semimetallic char-
resistance to biofouling is also critical.[231] Compared to car- acteristics, intrinsically semiconducting TMDCs, such as MoS2
boxyl and amino functionalized pores, hydroxyl functionalized and WS2, enable the photocatalytic reaction either on its own
pores in graphene membrane are reported to impart strong free or in conjunction with other 2D materials.[243,244] Notably,
energy barriers against salt permeability. Owing to their abun- the degradation effect of the TMDC catalyst increases with
dant hydroxyl functional groups and hydrophilic nature, GO decreases in sheet size; this is accompanied by enhancement
membranes attracted considerable attention in the early stages of the bandgap due to the stronger quantum confinement
of membrane research as promising candidates for desalina- effect. 2D material based photocatalysts for organic dyes,
tion. Nonetheless, the large swelling nature of GO in water is such as methylene blue, rhodamine B, and methylene green,
a serious intrinsic bottleneck to sustaining its ion selectivity. and for pesticides, methanol, and endocrine disruptors, have
The interlayer spacing of GO increases when it is swollen to been demonstrated with >98% removal efficiency in a short
d ≈ 1.35 nm. It then undesirably allows smaller salt ions to contact time of 1 h.[102] Moreover, assembled 2D materials
flow through the membrane, leading to a very low salt rejection can be used for the selective reduction of carcinogenic Cr(VI)
ratio of 20–40%. In principle, efficient desalination depends on and nitro aromatic compounds, and for the effective inactiva-
effective sieving of hydrated Na+, which has a hydrated radius tion of pathogens, such as viruses, nematodes, and bacteria

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Figure 10. Membranes based on 2D materials. a) 2D materials membrane: i) schematic diagram of graphene membrane, and ii) lamellar GO mem-
brane. Reproduced with permission.[102] Copyright 2015, RSC Publishing. b) GO membranes: i) schematic diagram of physically confined GO mem-
branes with epoxy coating (PGO) for directional permeation of water and ions along graphene planes, ii) optical micrograph of cross-sectional area
of GO laminates (black) embedded in epoxy (bright) and SEM image of GO laminate (right). Scale bar, 1 µm. iii) ion permeation rates through PGO
membranes with different interlayer distances. iv) Difference in ion permeation rates through GO and GO–graphene hybrid membranes (GO–Gr).
The inset includes a schematic of GO–Gr (top) and photographs of GO (left) and GO–Gr membranes (right). Scale bars, 1 cm. Reproduced with
permission.[150] Copyright 2017, Springer Nature. c) Schematic illustration of ion gating in a graphene membrane. Reproduced with permission.[231]
Copyright 2018, Springer Nature. d) Ion diffusion through charged graphene-based nanoporous membranes. Inset shows schematic of electrochemical
cell in which Ag/AgCl reference electrode (RE), graphene membrane working electrode (WE), and platinum mesh counter electrode (CE) are used to
detect ion diffusion. Reproduced with permission.[232] Copyright 2018, Springer Nature.

in contaminated waters.[245] An exceptionally high inactivation a superior chemical reactivity with edge-enriched structure.
(99.99%) of bacteria within 20–40 min of visible light exposure Similarly, incorporating noble metals between vertically grown
has been reported by means of vertically grown MoS2 films MoS2 films is found to increase the antimicrobial efficiency
(Figure 11b).[246] Vertical alignment of MoS2 layers enabled (Figure 11c).[247]

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Figure 11. Environmental applications based on 2D materials. a) Schematic illustrations of photocatalysis mechanism for graphene–TiO2 composite
fiber under visible light irradiation. Reproduced under the terms of the CC-BY Creative Commons 4.0 International License.[241] Copyright 2016, The
Authors, published by Springer Nature. b) Antimicrobial activity of vertically grown MoS2, i) schematic illustrations of vertically grown MoS2, ii) TEM
image (top view) of as-grown MoS2 displaying vertically standing layers, and iii) antimicrobial activity of vertical MoS2 film compared with those of
bulk MoS2 and nanostructured MoS2. Reproduced with permission.[246] Copyright 2016, Springer Nature. c) HRTEM image and microbial degradation
efficiency of Pt nanoparticles on vertically aligned 2D MoS2 film. Reproduced with permission.[247] Copyright 2017, Springer Nature. d) 3D intercon-
nected macroporous framework: i) schematic illustrations of 3D graphene-based materials for removal of dyes, metal ions, oils, and organic solvents
from water. As can be seen, ions and dye molecules are adsorbed on the surface of 2D building blocks, while oils and organic solvents are absorbed
in the pores of the 3D structure; ii) comparison of removal capacity, which shows that 3D graphene structures have higher affinity for hydrocarbons
than for metals and dyes. Reproduced with permission.[248] Copyright 2019, Springer Nature.

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5.5. Adsorption of Environmental Contaminants conversion systems that have minimally negative effects on the
neighboring environment. Unfortunately, environmental pollu-
Given the high surface area originating from their sheet mor- tion has already reached serious critical levels over worldwide.
phology, 2D materials are widely applied as adsorbent materials More active environmental technology aiming at the efficient
for water decontamination. To achieve an effective adsorption, cleaning and remediation rather than at lowering contamina-
the adsorbent surface should have an affinity for the contami- tion, is becoming more and more significant. In this regard,
nants, typically utilizing weak interactions such as π–π inter- nanoscale assembled structures of 2D materials with diverse
action, hydrogen bonding, and the van der Waals force of multilevel functionalities confer broad advantages for green
attraction. In this respect, GO with its abundant oxygen func- and sustainable technologies, including secondary batteries,
tional groups can strongly interact with metal ions. Similarly, supercapacitors, catalysts, gas sensors, desalination, and water
MoS2 with exposed sulfur atoms (a soft Lewis base) has a high decontamination. It is noteworthy that beyond the applica-
affinity for heavy metal ions (a soft-acid). Thus, high adsorption tion scope featured here, nanoscale assembly of 2D materials
performance in wastewater containing heavy metal ions has is anticipated to be valuable for other critical issues, such as
been reported for GO and MoS2 membranes. MoS2 was reported gas separation, air purification filters and collection/disposal
to show a high adsorption capacity for Hg2+ (≈1527 mg g−1); of nuclear waste. While technological advances relevant to 2D
its adsorption capacity decreases in the order of Hg2+ > Pb2+ > materials have in recent years yielded many breakthroughs, the
Cd2+ > Zn2+, which is consistent with its trend of softness.[245] challenge in this prominent field should now move forward to
The maximum adsorption capacity values of graphene and MoS2 the rational design of a sustainable future.
for organic contaminants such as dyes (methylene blue, mala-
chite green, rhodamine B, fuchsin acid, and Congo red) and
antibiotics are in the range of 150–200 mg g−1.[245] Creating 3D Acknowledgements
interconnected macroporous framework with 2D materials was
reported to show a high adsorption capacity due to the increased This work was financially supported by the National Creative Research
Initiative (CRI) Center for Multi-Dimensional Directed Nanoscale
surface area (Figure 11d). Based on hydrophobic interaction, Assembly (2015R1A3A2033061) and Nanomaterial Technology
remarkable adsorption capacity has been reported for oils and Development Program Planning (NRF-2016M3A7B4905613) through the
organic solvents, exceeding 100 times the material weight.[248] National Research Foundation of Korea (NRF) funded by the Ministry of
Science, ICT and Future.

6. Summary and Outlook

Conflict of Interest
This prospect article has featured that nanoscale assembly of
2D materials endows various higher order architectures often The authors declare no conflict of interest.
with amazingly tailored shapes and microstructures, which can
satisfy multiple competing demands in advanced materials.
There is an old piece of Korean wisdom saying that even if you Keywords
have many previous stones, real treasure will come when they 2D materials, energy applications, environmental applications,
are strung together. Along with the recent discovery of many nanoscale assembly
different interesting 2D structures, this old wisdom straight-
forwardly manifests the significance of nanoscale assembly to Received: October 25, 2019
strengthen the potential of valuable nanoscale stones for real- Revised: December 17, 2019
world applications. Published online:
An important realization from recent research efforts for
nanoscale assembly is that a large number of complex structures
can be generated from inherent 2D geometry; these structures
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