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25th Anniversary Article: MXenes: A New Family

of Two-Dimensional Materials
Michael Naguib, Vadym N. Mochalin, Michel W. Barsoum, and Yury Gogotsi*

All known MAX phases are layered hex-

Recently a new, large family of two-dimensional (2D) early transition metal agonal with P63/mmc symmetry, where
carbides and carbonitrides, called MXenes, was discovered. MXenes are the M layers are nearly closed packed,
produced by selective etching of the A element from the MAX phases, and the X atoms fill the octahedral sites.
The Mn+1Xn layers are, in turn, interleaved
which are metallically conductive, layered solids connected by strong with layers of A atoms.[12] In other words,
metallic, ionic, and covalent bonds, such as Ti2AlC, Ti3AlC2, and Ta4AlC3. the MAX phase structure can be described
MXenes combine the metallic conductivity of transition metal carbides with as 2D layers of early transition metal car-
the hydrophilic nature of their hydroxyl or oxygen terminated surfaces. In bides and/or nitrides “glued” together
essence, they behave as “conductive clays”. This article reviews progress— with an A element (Figure 1). The strong
M–X bond has a mixed covalent/metallic/
both experimental and theoretical—on their synthesis, structure, properties,
ionic character, whereas the M–A bond is
intercalation, delamination, and potential applications. MXenes are expected metallic.[13] So, in contrast to other layered
to be good candidates for a host of applications. They have already shown materials, such as graphite and TMDs,[2]
promising performance in electrochemical energy storage systems. A detailed where weak van der Waals interactions
outlook for future research on MXenes is also presented. hold the structure together, the bonds
between the layers in the MAX phases are
too strong to be broken by shear or any
similar mechanical means. However, as
1. Introduction discussed here, by taking advantage of the differences in char-
acter and relative strengths of the M–A compared with the M–X
Two-dimensional (2D) solids—defined as crystals with very
bonds, the A layers can be selectively etched by chemical means
high aspect ratios and thicknesses corresponding to a few
without disrupting the M–X bonds.
atomic layers—have garnered tremendous interest recently. By
Because the M–A bonds are weaker than the M–X bonds,
far the most studied is graphene, which is comprised of atomi-
heating of MAX phases under vacuum,[14] in molten salts,[15,16]
cally thin layers of sp2-bonded carbon atoms connected by aro-
or in certain molten metals[17] at high temperatures results in
matic in-plane bonds. Since graphene’s outstanding electronic
the selective loss of the A element. However, because of the
properties were discovered by Novoselov, Geim et al.,[1] other
elevated temperature needed, de-twinning of the Mn+1Xn layers
2D materials, such as hexagonal boron nitrides,[2] transition
takes place which results in formation of a 3D Mn+1Xn rock salt
metal dichalcogenides (TMDs),[3] metal oxides, and hydroxides,
structure.[16,18] On the other hand, the use of strong etchants,
have attracted much renewed attention.[4]
such as Cl2 gas, at temperatures above 200 °C results in the
Recently, the constellation of 2D materials has been aug-
etching of both the A and M atoms, to yield carbide derived car-
mented by a new, and potentially quite large, group of early
bons (CDC).[19,20] Similarly, reaction of Ti2AlC with anhydrous
transition metal carbides and/or carbonitrides labeled MXenes.
hydrofluoric acid (HF) at 55 °C resulted in the formation of a
These are produced by the etching out of the A layers from
new, ternary metal fluoride phase, Ti2AlF9.[21] It follows that,
MAX phases.[5–7] The latter are so-called because of their compo-
in order to selectively etch the A element, while preserving the
sition: namely, Mn+1AXn, where M is an early transition metal,
2D nature of the Mn+1Xn layers, a delicate balance between tem-
A is mainly a group IIIA or IVA (i.e., groups 13 or 14) element,
perature and the activity of the etchant needs to be maintained.
X is C and/or N, and n = 1, 2, or 3. Currently more than 60 dif-
In 2011 we reported, in Advanced Materials, on the selective
ferent pure MAX phases are known.[8] However, given that the
etching of Al from Ti3AlC2 using aqueous HF at room temper-
MAX phases can also be synthesized with different combina-
ature (RT).[5] In this process, the Al atoms are replaced by O,
tions, or solid solutions, of M atoms, such as (Ti0.5,Nb0.5)2AlC,[9]
OH and/or F atoms. The removal of the Al layers dramatically
A atoms, such as Ti3(Al0.5,Si0.5)C2,[10] and in the X sites such as
weakens the interactions between the Mn+1Xn layers that, in
Ti2Al(C0.5,N0.5),[11] their potential number is quite large indeed.
turn, allows them to be readily separated. We labeled these new
M. Naguib, V. N. Mochalin, M. W. Barsoum, Y. Gogotsi materials MXenes, to emphasize the loss of the A element from
Department of Materials Science and Engineering, the MAX parent phase and to highlight their 2D nature, which
and A.J. Drexel Nanotechnology Institute is similar to graphene.
Drexel University Today, the MXene family includes Ti3C2, Ti2C, Nb2C, V2C,
Philadelphia, PA 19104, USA
(Ti0.5,Nb0.5)2C, (V0.5,Cr0.5)3C2, Ti3CN, and Ta4C3.[6,7] Because
E-mail: [email protected]
the n values for the existing Mn+1AXn phases can vary from 1
DOI: 10.1002/adma.201304138 to 3, the corresponding single MXene sheets consist of 3, 5

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or 7 atomic layers for M2X, M3X2 and M4X3, respectively, (see
Figure 1). In all cases, the individual MXene layer thicknesses Michael Naguib is a Ph.D. can-
are less than 1 nm, while their lateral dimensions can reach didate and research assistant
tens of microns. in the Department of Materials
With the increased attention to 2D materials beyond gra- Science and Engineering at
phene, and with MXenes representing a new large family Drexel University. He received
extending the world of 2D materials,[22–24] it is timely to have a his M.S. and B.S. degrees in
progress report on the state of MXene research, covering exper- Metallurgical Engineering from
the Faculty of Engineering
imental and theoretical studies related to their synthesis, struc-
in Cairo University, Egypt.
ture, properties, and potential applications. This article sum-
His research focuses on the
marizes the current progress in MXene research and outlines
synthesis and characteriza-
the outstanding challenges, both experimental and theoretical.
tion of novel and advanced
We also provide an outlook of future directions for research of functional nanomaterials for
these new and exciting 2D materials. energy storage. He has published 18 papers in international
journals, in addition to presenting oral presentations and
posters in many international conferences, and filed a patent
2. Synthesis based on his Ph.D. research. He has received many interna-
tional awards, including the Graduate Excellence in Materials
As noted above, MXene synthesis is achieved by selective Science (GEMS) Award, and Ross Coffin Purdy Award.
etching of the A element layers from the MAX phases at room
temperature. In this process (Figure 2), the MAX phase powder
Vadym Mochalin received
is stirred in aqueous HF, of a specific concentration, for a
his Ph.D. degree in physical
given time followed by centrifugation and/or filtration of the
chemistry from L. M. Litvinenko
mixture to separate the solid from the supernatant with sub- Institute of Physical Organic
sequent washing of the solid with deionized water (DI) until and Coal Chemistry, National
the pH of the suspension reaches values of between 4 and 6. Academy of Sciences of Ukraine.
As a result of this treatment, solid dense MAX particles (not He is now a research asso-
shown) are converted to a loosely packed accordion-like struc- ciate professor in Department
ture (Figure 3a) resembling exfoliated graphite.[25] Following of Materials Science and
the convention used in the graphene/nanotube literature, we Engineering at Drexel University.
refer to these loosely packed, stacked particles as multilayer, or His research interests include
ML–MXenes. When the number of stacked layers is less than synthesis, characterization, chem-
5, they will be referred to as few-layer MXenes (FL–MXene). ical modification, computational
Given that various surface terminations—the exact chemistries modeling, and development of applications of MXene, graphene,
of which are still being explored—are possible (see below), a nanodiamond, nanoonions, and other nanomaterials for energy
general labeling scheme is needed. Here we denote these sur- storage, composites, biology, and medicine. He has authored 50
faces with the general formula: Mn+1XnTx, where T stands for research papers in peer reviewed journals, has been invited to
surface-terminating functional groups (OH, F, O, H, etc.). write several book chapters and review articles, and obtained 8
If a MAX phase is fully transformed to MXene, all but the international patents. He currently serves on the editorial board of
(000l) peaks in the X-ray diffraction (XRD) patterns will weaken or Scientific Reports.
vanish, especially in the case of the thinner M2X structures. Fur-
thermore, the (000l) peaks should not only broaden, but down- Yury Gogotsi is Distinguished
shift to lower angles, an indication of a larger c lattice parameter. University Professor and Trustee
If registry along the [0001] direction is lost (see below) then no Chair of Materials Science and
XRD peaks are expected. Typical results for Nb2AlC are shown Engineering at Drexel University.
in Figure 3b, where indeed only (000l) peaks are present after He also serves as Director of
etching. It is important to note that the diffractograms shown the A.J. Drexel Nanotechnology
in Figure 3b are obtained on samples that were cold pressed to Institute. His Ph.D. is in physical
450 MPa, a procedure that greatly enhances the intensity of the chemistry from Kiev Polytechnic
and D.Sc. in Materials
(000l) peaks. Also noteworthy is that in case of incomplete con-
Engineering from Ukrainian
version, MAX phase peaks coexist with the MXene (000l) peaks.
Academy of Sciences. He works
Along the same lines, and primarily because XRD peak
on nanostructured carbons and
intensities tend to fade with increasing degree of exfoliation
other nanomaterials for energy
(decreasing number of layers in the MXene lamellas), XRD related and other applications. He has co-authored more than
alone cannot be used to quantify the fraction of unreacted 350 journal papers and obtained more than 40 patents. He
MAX phase in a sample. Instead, energy-dispersive spectros- has received numerous national and international awards for
copy (EDS) is used to quantify the A:M atomic ratio. In a fully his research and was elected a Fellow of AAAS, MRS, ECS and
converted sample, this ratio would be negligible. However, this ACerS and a member of the World Academy of Ceramics.
method tends to overestimate the MAX phase concentration

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that the atomic weight of Al is close to the combined weight of

atoms in (OH)2. If the two are interchanged and if the resulting
MXenes do not dissolve in the etchant, little weight loss is
expected, as observed. The assumption of replacing each Al
atom by two surface groups is reasonable, as one Al layer glues
two Mn+1Xn layers in the MAX phases (each Al layer is shared
by two Mn+1Xn layers) so after etching the Al, surface groups
terminate the surface of each MXene layer.
The etching times and HF concentrations needed to fully
convert a given MAX powder depend primarily on its particle
size, time, temperature, and HF concentration.[6,27] Tuning
the etching conditions is important for achieving high yields
and the complete conversion of MAX into MXene. Prolonged
etching can result in the formation of defects, such as the holes
observed in Figure 3c in Ta4C3Tx.[6] Reducing the V2AlC particle
size by attrition milling reduces the etching time for complete
conversion from 90 h to 8 h.[7]
Although all of the MAX phases listed in Table 1 contain
Al as an A element, the etching conditions varied widely, a
fact that in part reflects the different M–Al bond energies in
the different MAX phases. For example, the Ti–Al and Nb–Al
Figure 1. Structure of MAX phases and the corresponding MXenes. bond energies in Ti2AlC and Nb2AlC have been estimated to
be 0.98 eV and 1.21 eV, respectively.[29] This difference, in turn,
can explain the experimental finding that the etching of Al
because, in addition to its presence in the MAX phase, the A from Nb2AlC requires longer times and higher HF concentra-
element could also be present in the MXene samples in the tions than from Ti2AlC (see Table 1).
form of A-element-containing salts, if the etching products are Another important variable is the value of n for a given
not completely removed during washing. For example, the pres- Mn+1AlCn phase. In general the higher the n, the more stable
ence of aluminum fluoride after HF treatment of Ti3AlC2 was the MXene. For example, immersing Ti2AlC powders in 50%
confirmed using X-ray photoelectron spectroscopy (XPS).[5,26] HF—the same conditions that yields Ti3C2—resulted in their
Table 1 summarizes the HF etching conditions needed complete dissolution. It is only by reducing the HF concentra-
to synthesize various MXenes, along with their c-lattice para- tion from 50% to 10% that Ti2C was obtained from Ti2AlC.[6]
meters and the c lattice parameters of their corresponding To date, all attempts to produce nitride-based MXenes, such
MAX phases. The MXene yield—defined here as the weight of as Ti2N or Ti4N3, have failed. By contrast, it is possible to selec-
powders after HF treatment divided by the weight of powders tively etch the Al from Ti3AlCN to produce Ti3CN (see Table 1).
before HF treatment ×100—varied between 60–100%. Note Note that the calculated cohesive energies of Tin+1Nn are less
than those of Tin+1Cn, whereas the formation
energies of Tin+1Nn from Tin+1AlNn are higher
than those of Tin+1Cn from Tin+1AlCn.[30] The
lower cohesion energy implies lower stability
of the structure, whereas the higher forma-
tion energy of the MXenes from their corre-
sponding Al containing MAX phases implies
that the Al atoms are bonded more strongly
in Tin+1AlNn compared to Tin+1AlCn and thus
require more energy for their extraction.
These two factors may explain why nitride
MXenes have to date not been produced.
Another distinct possibility is that the Tin+1Nn
layers dissolve in the HF solution due to
their lower stability.
The replacement of the strong Al–M
bonds by weaker hydrogen or van der Waals
bonds allows for the facile delamination of
MXene. This is best seen in Figure 3c–g, in
which various delaminated MXene layers
are imaged in a transmission electron
Figure 2. Schematic describing the synthesis process of MXenes from MAX phases. Reproduced microscope (TEM) and under an optical
with permission.[6] Copyright 2012, American Chemical Society. microscope (OM) (Figure 3h). To obtain the

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2D conversion of the material. Furthermore,
no evidence for carbide amorphization was
observed in the TEM. It is important to note
here that the Ti3C2 sheets are significantly
more stable than graphene sheets under a
200 kV electron beam in the TEM.[31,32]
Figure 3e shows a cross-sectional TEM
micrograph of two MXene layers, whereas
Figure 3f shows their corresponding atom-
istic model.[5] During ultrasonication, some
of the delaminated layers form scrolls with
inner radii of <20 nm (Figure 4a–c).[5] Similar
scrolls were also reported for graphene after
ultrasonication.[33,34] In addition to scrolls,
MXene nanotubes were also predicted to be
stable and to become more stable as their
radii increase owing to reduced strain.[35]
In contrast to Tin+1Cn(OH)2 MXene sheets,
which can be semiconducting (see below),
the seamless MXene nanotubes, formed
from either Tin+1Cn or Tin+1Cn(OH)2 are
predicted to have metallic character. The
synthesis of seamless MXene nanotubes
remains to be demonstrated.
Very recently, Zhang et al.[36] reported on
the exfoliation of Ti3Si0.75Al0.25C2 by the aid
of ultrasonication in various solvents. They
suggest that when the A layer is composed
of different atoms instead of single elements,
breaking the bonds between the carbide layers
becomes easier. The resulting ultrathin sheets
had thicknesses of ≈4 nm and lateral dimen-
sion of 100–200 nm. The resulting sheets had
the same composition as the parent MAX
phase, and the yields were quite low. It was
found that the above approach worked only
Figure 3. a) Scanning electron microscopy (SEM) image for Ti3AlC2 after HF treatment. Repro- for doped MAX phase; pure Ti3SiC2 could not
duced with permission.[6] Copyright 2012, American Chemical Society. b) X-ray diffraction (XRD) be exfoliated by this technique.
patterns for Nb2AlC before and after HF treatment. Reproduced with permission.[7] Copyright
2013, American Chemical Society. c) Transmission electron microscopy (TEM) image of Ta4AlC3
after prolonged HF treatment. Reproduced with permission.[6] Copyright 2012, American
Chemical Society. d) Low-magnification TEM image of Ti3AlC2 after HF treatment. Reproduced 3. Structure
with permission.[5] e) High-resolution transmission electron microscopy (HRTEM) cross-sec-
tional image of Ti3AlC2 after HF treatment. Reproduced with permission.[5] f) Atomistic model From the outset, modeling has played a crucial
of OH-terminated Ti3C2. Reproduced with permission.[5] g) HRTEM of (Ti0.5Nb0.5)2AlC after part in understanding the structure and prop-
HF treatment and the inset (top left) showing the corresponding SAED pattern. Reproduced erties of MXenes. In fact, the first structure
with permission.[6] Copyright 2012, American Chemical Society. h) Optical transmittance micro- of ML–MXenes—namely, stacked OH-termi-
graph of Ti3CNTx. Reproduced with permission.[6] Copyright 2012, American Chemical Society.
nated Ti3C2 layers—was proposed on the basis
of a density functional theory (DFT) simula-
delaminated MXenes, the HF treated powders are ultrasoni- tion.[5] The calculated c parameter from the XRD pattern of the
cated in isopropyl alcohol or methanol. We note in passing that geometry-optimized structure of the fully hydroxylated MXene
this technique results in small yields of delaminated flakes.[5–7] was a close match with the experimental XRD results, despite the
An intercalation approach that dramatically increases the yield fact that a mixture of hydroxyl and fluorine terminations could
is discussed below.[26] The delaminated layers were found to be not be ruled out.[5] The real situation may be even more complex
transparent not only to the electron beam in TEM (Figure 3c, with incomplete or mixed F, OH, and O terminations present
d) but also to visible light (Figure 3h).[6] Selected area electron (the presence of both OH and O was confirmed experimentally
diffraction (SAED) of delaminated MXene (inset in Figure 3g) using XPS).[5,26] Further complicating the situation is the high
imaged along [0001] clearly show that the atomic arrangement probability that water molecules can be present in the interlayer
in the basal planes is identical to that in the parent MAX phase. space,[7] especially in the case of V2C and Nb2C, in which the c
These results provide further compelling evidence for the 3D to values after etching are quite large indeed (see Table 1).

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Table 1. Process conditions and c-lattice parameters for MXene synthesis from MAX phases. ascribed to steric repulsion between T groups
Also listed are the c values of the parent MAX phase. and the underlying C atoms.[37] Another pos-
sible configuration, where the T termina-
MAX MAX MXene RT etching conditions c lattice parameter, Å Ref. tions are connected to, and positioned just
Structure
HF Conc.% Time, h MAX MXene above the Ti(1) atoms of Ti3C2, was shown
211 Ti2AlC Ti2CTx 10 10 13.6 15.04 [6] to be unstable and often transformed into
V2AlC V2CTx 50 8 a)
13.13 23.96 [7]
configurations I–III during geometry opti-
mization and will therefore, not be discussed
90 19.73
further.[37] It is necessary to emphasize again
Nb2AlC Nb2CTx 50 90 13.88 22.34 [7] that MXenes produced to date may have
(Ti0.5,Nb0.5)2AlC (Ti0.5,Nb0.5)2CTx 50 28 13.79 14.88 [6] mixed functional groups (such as OH, O
312 Ti3AlC2 Ti3C2Tx 50 2 18.42 20.51 [5,6] and F) on their surfaces that may affect their
40 20 18.62 20.89 [28]
configurations. However, no MXenes models
with mixed surface functional groups have
(V0.5,Cr0.5)3AlC2 (V0.5,Cr0.5)3C2Tx 50 69 17.73 24.26 [6]
been published to date.
Ti3AlCN Ti3CNTx 30 18 18.41 22.28 [6] These configurations, and the order
413 Ta4AlC3 Ta4C3Tx 50 72 24.08 30.34 [6] of their stability, for a broader range of T
Nb4AlC3b) Nb4C3Tx 50 90 24.19 30.47 [7] groups, including H, O, OH, and F, have
a)The 8 h treatment of V AlC was carried out on attrition-milled powders; b)Nb AlC was present as a sec-
been confirmed in other DFT studies for
2 4 3
ondary phase in a Nb2AlC sample. [ 7 ] many MXenes with different n values and
elemental compositions,[38,39] including solid
solutions (carbonitrides).[40] The relative total
Soon after their discovery, DFT studies [ 35,37]
found two ener- energy differences between configuration I, and either II or III,
getically favorable orientations for T in Ti3C2T2, resulting in were found to not be very sensitive to the layer thicknesses,
two distinct configurations: I and II (Figure 5). In configura- with the largest differences observed in case of Mn+1XnO2 com-
tion I, the T groups are located above the hollow sites between pared with Mn+1XnH2, Mn+1XnF2, and Mn+1Xn(OH)2 for X = C
three neighboring C atoms or, said differently, the T groups or N. Moreover, the energy differences for I–III Mn+1NnT2 are
point directly toward the Ti(2) atoms on both sides of the Ti3C2 smaller than for I–III Mn+1CnT2.[39]
layers. In configuration II, the T groups are positioned above The important question of the thermodynamic stability of
the C atoms on both sides of the Ti3C2 layers. A mixed struc- fully terminated compared to partially terminated structures
ture, where one side of the sheet is in configuration I, and the (that is, Mn+1XnTx, 0 < x < 2) or mixed structures with dif-
opposing side is in configuration II, was also considered and ferent Ts remains open. Thus far, the only study addressing this
referred to as configuration III. Different authors have used question[38] shows that in a wide range of oxygen gas chemical
different notations to distinguish between these configura- potentials between –4 and 0 eV, the fully oxygen terminated
tions. For example, a configuration labeled I in one study was Ti2CO2 structure is thermodynamically the most favorable
labeled “model II” or “conformation A” in another, and so on. configuration compared with other configurations with lower
Throughout this progress report, we rename the configurations oxygen contents. Phonon dispersion curves calculated in the
explored in the different studies to be consistent with those same paper for Ti2CO2 have no imaginary frequencies, again
shown in Figure 5. signifying that this structure is stable.
The structural stabilities of different Ti3C2F2 and Ti3C2(OH)2 Gan et al.[41] found, using both DFT and ab initio molec-
configurations—estimated by comparing their relative DFT ular dynamics (MD) calculations with the climbing image
total energies—were found to decrease in the order I > III > nudged elastic band method to calculate the energy barriers,
II. This suggests that both F and OH groups tend to adopt con- that O2 adsorbs on Ti2C surface forming super- and per-oxo
figuration I. The lowest structural stability of configuration II is species, which then dissociate without any barrier, producing

Figure 4. a) Ti3C2Tx nanoscroll of about 20 nm in outer diameter. b) Cross-sectional TEM image of a scroll with an inner radius of less than 20 nm.
Reproduced with permission.[5] c) Atomistic model of OH-terminated Ti3C2 nanotube. Reproduced with permission.[35] Copyright 2012, Elsevier.

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Figure 5. Configurations of functionalized MXenes with different arrangements of the surface atoms: side views of a) bare Ti3C2, b) I-Ti3C2(OH)2,
c) II-Ti2C(OH)2, and d) III-Ti3C2(OH)2; e,f) top views of I-Ti3C2(OH)2 and II-Ti3C2(OH)2. As configuration III is a mixture of I and II, its top view is not
shown. Reproduced with permission.[35] Copyright 2012, Elsevier.

Ti2COx. Once saturation is achieved by forming Ti2CO2, addi- intercalated with hydrazine (N2H4), a comparison of the
tional O2 is repelled by the surface even at temperatures as experimental and MD derived XRD patterns for different num-
high as 550 °C. This suggests that Ti2CO2 is stable and does bers of N2H4 molecules in the interlayer space of Ti3C2(OH)2
not form TiO2 in oxidizing environment, in contrast to many showed that the intercalated N2H4 molecules were most prob-
transition metal carbide nanoparticles, such as tungsten car- ably arranged in an orientation that is parallel relative to the
bide. The predicted Ti2CO2 stability in these conditions may MXene basal planes and formed a complete monolayer (see
be important for catalytic applications. It is worth noting Figure 6).
that this study was based on perfect Ti2C surfaces (with Here again the theoretical calculations have to be taken with
no defects such as Ti vacancies) which could change the a grain of salt. For example, owing to the unusual combination
conclusions. of elements in N2H4-intercalated Ti3C2(OH)2, including Ti, C,
In addition to OH, O, and F surface terminations, Enyashin O, N, and H, a universal force field, which is broad in terms
et al.[42] found—using density-functional tight-binding (DFTB), of included elements but not very precise, had to be used in
DFT, and MD calculations—that methoxy-terminated MXenes the MD simulations.[26] Configuration III taken from Naguib
may be stable. These findings suggest MXenes can be prom- et al.[5] was used for stacked Ti3C2(OH)2 in these simulations,
ising catalysts in, e.g., esterification processes. which as we now know, is not the most stable in the case of
Most, if not all, DFT calculations to date have been car- Ti3C2(OH)2 monolayers. As noted above, however, nothing is
ried out on single, isolated MXene sheets. Experimentally, the known about the relative stabilities of configurations I to III in
latter are the exception rather than the rule. For the most part, multilayer or stacked MXenes.
the MXene flakes, similar to other 2D materials, are stacked In most cases, the intercalation results in an increase in
as shown in Figure 3a. Indubitably, the stacking, and just as the c lattice parameters values. For example, the intercalation
importantly what is in between the layers, will have a signifi- induced changes in the c values (Δc) of Ti3C2Tx vary from 0.7 Å
cant effect on the energetics of the system. for sodium sulfate to 15.4 Å for dimethylsulfoxide (DMSO).[26,45]
The large Δc after DMSO intercalation is due to the sponta-
neous co-intercalation of ambient moisture. Storing DMSO-
4. Intercalation and Large-Scale Delamination of intercalated Ti3C2Tx samples in air for 3 weeks, resulted in a
doubling of the c lattice parameter over its value for Ti3C2Tx.
MXenes
This extraordinary increase of the interlayer spacing further
Intercalation is a well known phenomenon for many layered weakens the bonds between the MXene layers to the extent
materials for which the bonds between the layers are not very that weak sonication of DMSO intercalated Ti3C2Tx powders in
strong, such as graphite[43] and clays.[44] The same is true of deionized (DI) water for 6 h resulted in further delamination
MXenes: the weak bonds between the Mn+1Xn layers allow for of most of the layers, as schematically shown in Figure 7.[26]
the intercalation of different species (organic, inorganic, and It is important to differentiate between as-produced multilayer
ionic) between the Ti3C2 layers.[26,45] In case of Ti3C2(OH)2 Ti3C2Tx and delaminated single- or few-layer Ti3C2Tx. As MXenes

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Figure 6. Molecular dynamics simulations of OH-terminated Ti3C2 intercalated with hydrazine. a) Change in MXene c value as a function of the
number of N2H4 intercalated molecules. As the latter is increased, first a monolayer of N2H4 molecules is formed, corresponding to an N/C ratio 0.4
(c ≈ 25–26 Å). Further increase in the number of N2H4-intercalated molecules results in the onset of the formation of a second layer, which is not com-
plete up to the maximum N/C ratio used in the simulations (N/C ≈ 0.875). b) Molecular dynamics snapshot of hydrazine intercalated MXene for N/C
ratio 0.375 (six N2H4 per a 4×2×1 MXene supercell) showing a nearly complete N2H4 monolayer. c) Comparison of simulated (black) and experimental
(blue) XRD patterns of N2H4 intercalated OH-terminated Ti3C2 with detailed (002) peak area presented in the inset. Reproduced with permission.[26]
Copyright 2013, Macmillan Publishers Ltd.

are hydrophilic, once delaminated, they form stable, surfactant- 5. Properties

free colloidal solutions in water (Figure 7 bottom left). To date,
the only MXene that has been successfully delaminated in large The electronic properties of MXenes are of special interest as
quantities is Ti3C2Tx. they can, in principle, be tuned by changing the MXene ele-
The possibility of intercalating MXenes with various organic mental composition and/or their surface terminations. The
molecules goes beyond delaminating MXenes on a large scale. MXenes’ band structure and electron density of states (DOSs)
This phenomenon will indubitably play a critical role for a have been extensively studied by DFT. Bare MXene monolayers
range of MXene applications, from polymer reinforcements to are predicted to be metallic, with a high electron density near
energy storage systems (see below). Furthermore, it was found the Fermi level.[5,30,37–39] Interestingly, the electron DOS near
that the resistivities of cold pressed MXene discs increase by the Fermi level (N(Ef)) for bare individual MXene layers is
1–2 orders of magnitude after intercalation with organic com- higher than in their parent MAX phases. To understand these
pounds.[26] Selectivity to intercalants, and changes in resistivity changes one needs to examine the partial electron density of
after intercalation, suggest that MXenes may also work as sen- states (Figure 8).[30,39,40,46]
sors for various chemicals. In the MAX phases, N(Ef) is dominated by M 3d orbitals.
Referring to Ti2AlC (Figure 8a), it is clear that the valence
states below Ef group into two sub-bands: sub-band A, which is
near Ef and is made up of hybridized Ti 3d-Al 3p orbitals; and
sub-band B, which is between –10 and –3 eV below Ef and is
due to hybridized Ti 3d-C 2p and Ti 3d-Al 3s orbitals. In other
words, sub-bands A and B give rise to the Ti-Al and Ti-C bonds,
respectively. Removal of the A layers results in a redistribu-
tion of the Ti 3d states, or “dangling bonds”, from the missing
Ti–Al bonds into delocalized Ti–Ti metallic-like bonding states
that appear around Ef in Ti2C (Figure 8b). Thus, in MXenes,
N(Ef) is 2.5–4.5 times higher than in the corresponding MAX
phases for Tin+1Cn and Tin+1Nn according to Shein et al.[30]; or
1.9–3.2 times higher for Tin+1Cn and 2.8–4.8 times higher for
Tin+1Nn according to Xie et al.[39], where the range of studied n
was broader.
The high N(Ef) values in Tin+1Xn, contributed by the Ti 3d
states can lead to a magnetic instability, if the Stoner criterion
I·N(Ef) > 1 (where I is Stoner exchange parameter, equal to
0.9 eV for 3d elements)[47] is satisfied, resulting in magnetic
MXenes.[30,37–39,48] Magnetic MXenes can be both ferromagnetic
(such as Cr2C, Cr2N,[38] or Ta3C2)[48] or antiferromagnetic (such
as Ti3C2 or Ti3N2).[30] The acquired total magnetic moments per
Figure 7. Schematic of the intercalation and delamination process
of Ti3C2Tx, the aqueous suspension of Ti3C2Tx flakes with laser beam
unit cell are in the range 2–3 μB for Tin+1Cn or fluctuate around
showing the Tyndall scattering effect, and the SEM image shows delami- 1.2 μB for Tin+1Nn as n increases from 1 to 9.[39]
nated flakes filtered from the aqueous suspension. Reproduced with per- Although magnetism is an important property, for the most
mission.[26] Copyright 2013, Macmillan Publishers Ltd. part it is only predicted for MXene with bare surfaces. When

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(III-Ti3C2F2), 0.05 eV (I-Ti3C2(OH)2) and 0.07 eV (III-
Ti3C2(OH)2). Interestingly, the same materials in configura-
tion II are predicted to be metals.[37] Although most MXenes
are metallic or have small bandgaps, DFT results predict
that: Sc2CF2 should possess an indirect bandgap of 1.03 eV;
Sc2C(OH)2 should have a direct bandgap of 0.45 eV; Sc2CO2
should have an indirect bandgap of 1.8 eV; Ti2CO2 should have
an indirect band gap of 0.24 eV; Zr2CO2 should have an indi-
rect bandgap of 0.88 eV; and Hf2CO2 should have an indirect
bandgap of 1.0 eV.[38] Thus, many MXenes, especially O-termi-
nated ones, are predicted to be semiconducting.[38]
To understand these changes, it is necessary again to examine
the partial electron density of states (Figure 8).[30,39,40,46] In
addition to sub-bands A and B, mentioned above, in surface
terminated MXenes a new sub-band C, corresponding to Ti–T
bonds, is formed below sub-band B, causing a shift of the gap
between sub-bands A and B to lower energies and a depletion
in the N(Ef). It is the latter effect that reduces the propensity
for magnetism in Mn+1XnT2.[39] This is the basic mechanism
through which chemical termination changes the electronic
and magnetic properties of MXenes, although additional dif-
ferences exist between different MXenes. For example, in
Mn+1NnT2, the T contributes to both, the newly formed C sub-
band and the existing B sub-band, in contrast to Mn+1CnT2,
where T contributes only to sub-band C.[39] Note that in the
carbonitrides, such as Ti3CNTx,[40] the increased electron count
due to the presence of the N atoms, may outweight the with-
drawal of electrons by surface groups, thus preserving their
metallic character.
Concluding the discussion of computational results, it
Figure 8. Total and partial DOS of Ti2AlC, Ti2C, Ti2CO2 and Ti2C(OH)2, should be noted that while producing stable and consistent
illustrating changes in the density of states upon removal of Al from the geometries, DFT is known to have issues with predicting band-
parent MAX phase to produce MXene, and further changes upon termina- gaps. Thus, a thoughtful choice of the exchange-correlation
tion of the MXene surface by different T. Reproduced with permission.[39] functional must be made in order to correctly predict the dif-
Copyright 2013, American Physical Society. ferences between metals and narrow band semiconductors. A
proper inclusion of interlayer van der Waals interactions is also
important, as they may not only influence the geometric struc-
surface terminations (T, even when T = H) are present, the tures, but may also change the band structures (as has been
magnetism disappears due to the formation of p–d bonds demonstrated for other materials, for example, see Govaerts
between the M atoms and T groups, leading to a partial depop- et al.[49]). In this context, a comparison of the band gaps of
ulation of the near Fermi states, which reduces N(Ef) (Ti2CO2, Ti3C2(OH)2 and Ti3C2F2 calculated using the GGA-PBE (Gen-
Ti2CF2, Ti2CH2, and Ti2C(OH)2 in Figure 8c, d and e, respec- eralized Gradient Approximation–Perdew-Burke-Ernzerhof)[37]
tively). Prominent exceptions are Cr2C and Cr2N, which are pre- and HSE06 (Heyd-Scuseria-Ernzerhof) functionals is instruc-
dicted to retain significant magnetic moments in their termi- tive.[39] According to GGA-PBE, Ti3C2(OH)2 and Ti3C2F2—in
nated state (T = O, OH, or F) up to nearly room temperature.[38] their most stable configurations I—are narrow band semi-
Unfortunately, to date there have been no reports of experimen- conductors with band gaps <0.1 eV.[37] However, the same
tally produced Cr2XTx MXenes to test this important prediction. MXenes, in the same configurations, are predicted to be
Surface terminations can influence other MXenes’ electronic metallic when HSE06 functional is used instead.[39] Another
properties, such as their bandgaps. In the first MXene paper,[5] example is Ti3C2O2, in configuration I, for which PBE func-
it was theoretically shown that although Ti3C2 is a metallic tional predicts a band gap of 0.24 eV, whereas HSE06 gives a
conductor, small bandgaps of 0.05 eV and 0.1 eV open up for value of 0.88 eV.[39] The HSE06 is a hybrid functional, which
Ti3C2(OH)2 and Ti3C2F2, respectively. At the time, we suggested combines one-quarter of the exact Hartree–Fock exchange
that it would be possible to tune the electronic structure of energy with three-quarters of an approximate exchange-corre-
MXenes by varying T. It was further confirmed that the elec- lation energy. This combination in general produces more reli-
tronic structure of MXenes is sensitive not only to the type of able bandgaps than PBE.[39] Therefore, this functional should
surface terminations, but also to their orientation relative to be preferred over PBE in calculations of electronic properties.
the MXene sheets. In particular, Ti3C2F2 and Ti3C2(OH)2 in In another study,[50] Wu–Cohen (WC) functional within GGA
configurations I and III (see above) were shown to be semicon- formalism was chosen, because it was deemed superior to
ductors with narrow band gaps of 0.04 eV (I-Ti3C2F2), 0.03 eV PBE, in describing the electronic structure.

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The importance of modeling in discovering novel and unex- Table 2. First principles calculated in-plane elastic constant (c11) for
pected properties of MXenes is, and will remain, indispensible. different MXenes with the corresponding a lattice parameter and DOS
at Ef.[50] The c11 values for the corresponding MAX phases are listed in
Modeling can also be used for screening different MXenes, brackets in column 3.
some of which have not been synthesized yet and determining
which ones have attractive properties, thus guiding experi-
Layer a, Å c11, GPa MXene (MAX) DOS at Ef eV−1 atom−1
mental efforts.
M2C
Some of the predictions have already been confirmed experi-
mentally. The conductivities of MXene free-standing thin discs Ti2C 3.007 636 (312) 2.63
(thickness around 300 μm)—prepared by cold pressing addi- V2C 2.869 718 (338) 1.45
tive-free MXene powders at RT under a load corresponding Cr2C 2.787 690 (340) 2.55
to a stress of ≈1 GPa—were comparable to those of multilayer
Zr2C 3.238 594 (261) 1.77
graphene.[51] For example, the resistivities of those discs were:
Hf2C 3.239 658 (291) 2.25
22 Ω 䊐–1 for Ti3C2Tx to 339 Ω 䊐–1 for Ti2CTx depending on
their surface chemistry and n (M2X, M3X2, and M4X3). Contact Ta2C 3.138 788 (334) 0.89
angle measurements of DI water on these cold-pressed MXene M3C2
discs revealed hydrophilic behavior, with contact angles in Ti3C2 3.071 523 (368) 2.19
the 27 to 41 degrees range.[6] These values are comparable to
Ta3C2 3.196 575 (368) 1.44
oxygen terminated carbon surfaces.[52]
M4C3
MXenes’ 2D morphologies, combined with their metallic
electrical conductivities may be beneficial for integration with Ti4C3 3.066 512 (403) 1.83
other layered semiconducting materials, such as MoS2. In these Ta4C3 3.172 633 (437) 0.56
hybrid systems, MXenes may be used as conductive 2D pads.
They could also be used to modify the electronic properties of
other 2D materials in contact with MXene in vertical hybrid
heterostructures. To date, no experimental studies have been graphene, as many MXenes consists of at least 3 atomic layers.
carried out in this promising direction, although recent com- Moreover, t and the consequent elastic rigidity anisotropies can
putational results[53] predict that metallic behavior emerges in also be readily tuned by varying n in Mn+1Xn.[50]
MoS2 when Ti2C is deposited on it as a consequence of strong
chemical bonds formed at the MoS2/Ti2C interfaces. By con-
trast, the bonding on MoS2/Ti2CF2 and MoS2/Ti2C(OH)2 inter-
6. Applications
faces is non-covalent (physisorption), preserving the semicon-
ducting nature of MoS2. The bond alignment induces weak and The rich chemistries and unique morphologies of MXenes, in
strong n-type doping of the MoS2 in MoS2/Ti2CF2 and MoS2/ addition to their good electronic conductivities, render them
Ti2C(OH)2 with corresponding n-type Schottky barrier heights strong candidates for many applications that range from sen-
of 0.85 and 0.26 eV, respectively.[53] sors and electronic device materials to catalysts in the chemical
In another study,[38] high Seebeck coefficients were predicted industry, conductive reinforcement additives to polymers, elec-
for MXenes by DFT. The Seebeck coefficients ≈1000 μV K–1 pre- trochemical energy storage materials, among many others. For
dicted for semiconducting Ti2CO2 and Sc2C(OH)2 at ≈100 K the most part many of those applications are still hypothetical.
are comparable to the reported giant Seebeck coefficients of The few experimental results that exist to date have explored
SrTiO3 (850 μV K–1 at ≈90 K). This prediction opens a totally the use of MXenes in energy storage applications such as
new area of potential applications for these surface terminated lithium ion batteries, LIBs, electrochemical capacitors (superca-
MXenes. pacitors), and fuel cells.[26,45,54–56]
The mechanical properties of MXenes are also of great Early DFT calculations on Li intercalation into multilayer
interest as the M–C and/or M–N bonds are some of the Ti3C2 predicted the formation of Ti3C2Li2 in Li rich environ-
strongest known. At this juncture the only information available ments, with a slightly positive enthalpy explained by the larger
on how MXenes would respond to stress, are the elastic con- size of Li versus Al atoms.[5] The theoretical Li capacity in that
stants when they are stretched along the basal planes, i.e., c11. case was found to be 320 mAh g–1. Soon afterwards, DFT was
An early DFT study of Ti3C2(OH)2 predicted a c11 ≈300 GPa.[5] again used to study the adsorption and diffusion of Li on mono-
A follow up study[50] predicted that the c11 values of different, layers of Ti3C2, Ti3C2F2 and Ti3C2(OH)2.[37] The most favorable
bare, or unfunctionalized, Mn+1Cn layers would be higher than Li adsorption sites for all three materials, in their most stable
in their parent MAX phases (Table 2). This could be due to configuration I, were the positions above the C atoms of the
the strengthening of the M–X bonds when the A atoms are carbide sheets. The adsorbed Li atoms become partially or fully
removed and the electron density is more concentrated within ionized due to charge transfer between Li and Ti3C2, I-Ti3C2F2
the Mn+1Cn layer. However, the enhanced mechanical properties or I-Ti3C2(OH)2. This charge transfer suggests that the adsorbed
could also be due to the difficulty in accurately estimating the Li strongly interacts with MXenes via coulombic interactions.
exact thickness of a MXene layer. The calculated Li adsorption energies on Ti3C2, I-Ti3C2F2, and
And although the c11 values for MXenes are lower than those I-Ti3C2(OH)2 monolayers were found to be 0.50, −0.95, −0.20 eV
of graphene, the bending rigidity, which scales as ∼t3, where t per Li atom, respectively. The Li diffusion rates follow the order
is the layer thickness, should be significantly higher than for Ti3C2 > I-Ti3C2F2 > I-Ti3C2(OH)2, thus, bare Ti3C2 monolayers

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should possess the highest Li transport rates. The higher Li dif-
fusion barriers on the I-Ti3C2F2 and I-Ti3C2(OH)2 surfaces were
ascribed to steric hindrances induced by the surface F and OH
groups.
The open circuit voltages were predicted to be 0.62, 0.56, and
0.14 V for Ti3C2Li2, I-Ti3C2F2Li and I-Ti3C2(OH)2Li0.5, respec-
tively. The corresponding theoretical specific capacities were
found to be 320, 130, and 67 mAh g–1, respectively.[37] All in
all, the authors[37] conclude that bare 2D Ti3C2 monolayers
would be better anode materials for LIBs than TiO2 due to their
enhanced electronic conductivity (metallic character), smaller
open circuit voltage, and improved Li storage capacity. Also,
the predicted diffusion barrier (0.07 eV) for an isolated Li atom
on a Ti3C2 surface was much lower than that in anatase TiO2
(0.35−0.65 eV) or graphite (≈0.3 eV), meaning that Ti3C2 should
sustain higher charge/discharge rates than these materials, ren-
dering it promising for high power batteries. However, as noted
above, all MXenes produced to date are terminated with surface
groups, which may affect their performance as LIBs anodes. It
follows that modeling will probably continue to have a pivotal
role in identifying optimal MXene compositions and surface Figure 9. Comparison of the performance of multilayer Ti3C2Tx powder
terminations for ion intercalation, as well as in uncovering new film electrode (exfoliated MXene) and Ti3C2Tx paper electrode prepared
important details of the mechanisms of these processes. from delaminated few-layer MXene as anode materials in Li-ion batteries.
Inset shows cross-sectional SEM image of an additive-free MXene paper
Several MXenes (Ti2CTx,[54] Ti3C2Tx,[26] V2CTx, and Nb2CTx[7])
on a porous anodic alumina membrane. Reproduced with permission.[26]
were experimentally investigated as electrode materials in LIBs. Copyright 2013, Macmillan Publishers Ltd.
Among these compounds, in non-delaminated forms, V2CTx
showed the highest capacity (280 mAhg−1 at a cycling rate of
1 C and 125 mAhg−1 at 10 C). Although Nb atoms are heavier (110 mAhg−1 at 36 C after 700 cycles).[26] Although the MXenes’
than Ti, the gravimetric capacity of Nb2CTx is higher than that gravimetric capacities are not as high as Si,[57] they have the
for Ti2CTx at the same cycling rates (180 mAhg−1 for Nb2CTx great advantage of combining high cycling rates with good
versus 110 mAhg−1 for Ti2CTx at 1C). An in situ XRD study on capacities. The cycling rates reported are as good as, and prob-
Ti2CTx showed that the mechanism governing lithiation and ably better than, lithium titanium oxide (LTO) based anodes.[58]
delithiation was Li intercalation and de-intercalation between These comments notwithstanding, first cycle irreversibility is
the layers, respectively.[55] For a given chemistry, M2X electrodes a challenging problem in all tested MXenes so far. The exact
will have higher gravimetric capacities than their M3X2 and reasons for the irreversibilities are not clear but could be due to
M4X3 counterparts. For example, the gravimetric capacity of solid-electrolyte interphase (SEI) formation or irreversible reac-
Ti2CTx was ≈1.5 times higher than that of Ti3C2Tx[26,54] for the tions between Li and the MXene surface groups. This problem,
simple reason that the former has the least number of atomic in principle, can be solved by prelithiation of the MXene elec-
layers per MXene sheet. trodes, similar to what was reported for other nanostructured
More recently, we showed that each MXene has its own systems.[59]
active voltage window. For example, more than two-thirds of the All the work to date on MXene electrodes in LIBs was car-
reversible lithiation capacity of Nb2CTx is below 1 V; for V2CTx ried out on as-synthesized materials, with no tailoring of their
more than two-thirds of the reversible delithiation capacity is surface chemistries. Thus, many opportunities for enhancing
above 1.5 V.[7] Considering the rich chemistry of MXenes and the performance and reducing first cycle irreversibility remain
solid solution compositions, it may in principle be possible to unexplored. For example, and as noted above, bare MXene
fine-tune and design the MXenes for specific battery applica- surfaces are predicted to perform better than terminated ones
tions. Thus, some MXenes could function as anodes and some in LIBs.[37] Delaminating other MXenes may increase their Li
could be used as cathodes for lithium ion and other batteries. uptake, similar to what was reported for Ti3C2.[26] Thin and
As noted above, Ti3C2Tx can be readily delaminated, lightweight M2X MXenes are of special interest for this pur-
resulting in a colloidal solution of single- and few-layer Ti3C2Tx pose. Similar to other 2D materials, further optimization and
flakes, by sonicating a suspension of DMSO-intercalated Ti3C2 enhancement can be achieved by engineering electrode archi-
in DI water. Filtration of this solution yields additive-free, flex- tectures using different additives.[60–62]
ible paper that detaches readily from the anodic aluminum The capability of MXenes to handle high cycling rates
oxide filter membranes. This paper was in turn used to fabri- renders them good candidates for use in asymmetric, non-
cate electrodes that were tested as LIB electrodes.[26] As shown aqueous energy storage devices (hybrid cells), that combine
in Figure 9, such an electrode yielded a reversible capacity of the high energy densities characteristic of LIBs and the high
410 mAhg−1 at 1 C (≈4 times higher than the capacity of the power densities of electrical double layer capacitors (EDLCs).
cast Ti3C2Tx film that has binder and carbon additives), and pos- Typically, in Li-ion capacitors activated carbon (AC) and a Li
sessed excellent ability to handle extremely high cycling rates host material are used as the positive and negative electrodes,

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respectively.[63–65] When Ti2CTx was used as the negative elec- one—solid to a 2D solid. This new family of 2D materials has
trode, an energy density of 30 Wh kg−1 at 930 W kg−1 for 1000 been labeled “MXenes” to denote the loss of the A element
cycles was obtained.[55] from the MAX phases and to emphasize their 2D structure. To
Spontaneous chemical intercalation of different cations date, the following MXenes have been produced: Ti3C2, Ti2C,
between Ti3C2Tx layers from aqueous salt solutions resulted in Nb2C, V2C, (Ti0.5Nb0.5)2C, (V0.5Cr0.5)3C2, Ti3CN, Ta4C3, and
outstanding supercapacitors.[45] Reversible capacities—stable Nb4C3. Many more have been predicted theoretically.
for more than 10 000 cycles—of more than 330 F cm–3 were XPS and EDS results indicate that MXenes are terminated
achieved when Ti3C2Tx paper was tested in a KOH electrolyte, with a mixture of O, OH, and/or F groups. The as-synthesized
using a current of 1 A g–1.[45] This capacitance is higher than MXenes are simultaneously electronically conducting and
the volumetric capacitance of the best all-carbon EDLCs.[66] hydrophilic, an uncommon combination. Sonication can be
Ti3C2 paper electrodes showed better performance in super- used to separate the 2D Mn+1Xn layers from each other and pro-
capacitors than their multilayer counterparts made from duce single-layer and few-layered flakes. Sonication also results
MXene powders in a conventional way (i.e., rolling films of in nanoscrolls with inner radii less than 20 nm.
active material with binder and conductive additive).[45] The dif- The yields are high and the process is simple and readily
ference, however, was not as dramatic as observed when they scalable. This comment notwithstanding, other synthesis tech-
were used as electrodes in LIBs. The better performance can in niques need to be explored. For example, it would be beneficial
part be attributed to the better overall electronic conductivity of to identify etchants that are safer than HF. The use of non-
the Ti3C2-paper electrodes, because they are additive-free, while aqueous etchants could in principle avoid O or OH termination
the powder electrodes contained a nonconductive polymer of the MXene sheets. Furthermore, the etching of A elements
binder. Spontaneous intercalation of cations between MXenes’ other than Al needs to be explored to cover all possible transi-
layers makes each layer accessible for ion adsorption. Electro- tion metals carbides that form the MAX phases. For example,
chemical intercalation of Na+ and multivalent ions, such as Al-containing Mo, Zr, and Hf-based MAX phases currently do
Mg2+ and Al3+, suggests MXenes can be promising host mate- not exist. If other A elements can be etched out, it would be
rials in multivalent ion batteries beyond Li. possible to synthesize MXenes based on these metals.[12]
Very recently, Xie et al.[56] used Ti3C2Tx as a supporting mate- As described above, some of the etching by-products can
rial for platinum nano particles (Pt NPs) for fuel cell applica- coexist with the MXene after etching the A element. The effect
tions. They found that the Pt/Ti3C2Tx combination was more of these etching reaction by-products and surface contamina-
durable and more electrochemically stable than the Pt/C cat- tions on the performance and properties of various MXene
alysts that are conventionally used. For example, after 10 000 layers need to be well investigated, understood and ultimately
cycles, the Pt/Ti3C2Tx catalyst lost 15.7% of its initial Pt electro- controlled.
chemical surface area; the Pt/C electrode lost 40.8%. The space between the MXene sheets is extremely versa-
To conclude this section, we note that although no MXene tile and amenable to a host of compounds and cations. For
dispersion in polymers has been reported so far, Zhang et al.[36] example, Ti3C2Tx can be intercalated with various organic mol-
used ultrathin nanolaminates of Ti3Si0.75Al0.25C2, as a conduc- ecules as well as inorganic salts dissolved in water. In principle,
tive additive to poly(methyl methacrylate) (PMMA). The com- ionic liquids and other intercalants can also be utilized. Sonica-
posites possessed excellent mechanical and thermal properties tion of DMSO intercalated Ti3C2Tx in DI water resulted in the
that were comparable to PMMA/graphene composites.[67] As large-scale delamination into single- and few Ti3C2Tx layers. Fil-
the in-plane elastic properties of MXenes (Table 2) were found tration of the latter resulted in thin, free-standing MXene paper
to be even higher than their parent MAX phases,[50] MXenes that was flexible, hydrophilic, and conductive.
can potentially be used as additives to polymers to fabricate MXenes’ 2D morphology and their good electronic conduc-
composites with outstanding mechanical properties and good tivities render them promising electrode materials for LIBs,
electrical conductivities. As noted above, an important advan- hybrid cells, and supercapacitors. They offer excellent capability
tage of MXenes over the MAX phases is that the former have to handle high cycling rates in LIBs, and outstanding volu-
surface functional groups that should enhance the matrix-filler metric capacitance in supercapacitors.
interface strengths and even allow for covalent bonding of the The majority of current publications on MXenes are theo-
polymer to the MXenes layers, similar, for example, to nanodia- retical studies, mostly using DFT, as well as classical and ab
mond–polymer composites.[68] These considerations certainly initio molecular dynamics. However, many challenges remain
suggest that the use of MXenes in polymer matrices should pay for modeling as well, and the research in this area will likely
large dividends. continue at an increasing pace. First of all, we still need to fully
understand the surface chemistry of the MXenes. Which func-
tional groups are present on their surfaces after synthesis, and
how the latter change over time when MXenes are stored or
7. Summary and Outlook
treated needs to be studied and understood. Upon drying of
In summary, a new family of 2D materials comprised of early MXenes, a fraction of OH groups may be converted into O ter-
transition metal carbides and carbonitrides has been produced minations by H2O elimination. Most current models assume
by selectively etching the Al layers (A layers in MAX) with HF complete termination by F, OH, or O groups. However, the
at room temperature. The replacement of the strong primary coverage may well be incomplete or nonuniform or both, i.e.,
Al–M bonds in the Mn+1AXn phases with O, OH and F surface different functional groups may coexist with bare areas on
terminations allows for the conversion of a 3D—albeit a layered the surface of a single MXene particle. In addition, water may

1002 wileyonlinelibrary.com © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2014, 26, 992–1005
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PROGRESS REPORT
be present on the surface and between the layers, forming magnetic, optical, thermal, and mechanical properties.
hydrogen bonds and affecting MXene interlayer interactions. • Exploring MXenes in various applications, such as composite
How these factors affect the predicted structural, electronic, reinforcement, catalysis, transparent electronic conductors,
magnetic, and other properties of MXenes remains an open sensors, etc.
question. • Expanding the family through synthesis of new MXenes.
Although DFT showed that fully terminated Mn+1XnT2 mono-
layers may exist in three different configurations with one of Success in addressing these points should lead to numerous
them being energetically favored, it is still not clear which (if applications. These comments notwithstanding, the discovery
any) of these configurations would be favored in stacked multi- of MXenes is an exciting development that greatly expands the
layer MXenes. The properties of multilayer MXenes comprised family of 2D materials.
of Mn+1XnTx monolayers stacked in different geometric configu-
rations have never been probed by DFT. Despite its clear impor-
tance, this problem is likely to pose a significant challenge for
Acknowledgements
DFT, which is inherently poor in describing weak interactions,
such as the van der Waals and hydrogen bonds that are believed This article is part of an ongoing series celebrating the 25th anniversary
to hold the MXene monolayers in stacks. Recent developments of Advanced Materials. The authors thank Dr. Kevin Cook for his valuable
comments on the manuscript. This work was supported by the Assistant
in DFT for weakly interacting systems may prove useful in this
Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle
situation. Many other properties of monolayer, few layers and Technologies of the US Department of Energy under Contract No.
multilayered MXenes need to be modeled. For example vibra- DE-AC02–05CH11231, subcontract No. 6951370, under the Batteries
tional spectra, especially Raman, which can be easily compared for Advanced Transportation Technologies (BATT) Program. Modeling
with experiments, need to be calculated. Interpreting Raman work was supported by the Fluid Interface Reactions, Structures and
spectra of MXenes is one of the challenges faced by experimen- Transport (FIRST) Center, an Energy Frontier Research Center funded by
talists, and an area where modeling can provide considerable the US Department of Energy, Office of Science, Office of Basic Energy
Sciences.
insights.
Besides monolayers and stacks, other MXene structures, Received: August 16, 2013
such as MXene nanotubes and nanoscrolls[5,35] need to be fur- Revised: September 18, 2013
ther studied. We currently know very little about their geom- Published online: December 19, 2013
etry, electronic structure, and properties. Finally, the develop-
ment of a reliable classical force field for MXenes is urgently
needed. Many practical phenomena such as intercalation, ion
exchange, interactions and dynamics of polymers in MXene [1] K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang,
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S. V. Morozov, A. K. Geim, Proc. Natl. Acad. Sci. USA 2005, 102, 10451.
for MXenes (similar to ClayFF or ReaxFF) will open new pos-
[3] J. N. Coleman, M. Lotya, A. O’Neill, S. D. Bergin, P. J. King, U. Khan,
sibilities for studying these prohibitively large/complex for K. Young, A. Gaucher, S. De, R. J. Smith, I. V. Shvets, S. K. Arora,
DFT systems/phenomena important for development of future G. Stanton, H.-Y. Kim, K. Lee, G. T. Kim, G. S. Duesberg, T. Hallam,
applications. J. J. Boland, J. J. Wang, J. F. Donegan, J. C. Grunlan, G. Moriarty,
Despite the fact that MAX thin films have been well A. Shmeliov, R. J. Nicholls, J. M. Perkins, E. M. Grieveson,
studied,[69] as of yet no work has been published on the exfolia- K. Theuwissen, D. W. McComb, P. D. Nellist, V. Nicolosi, Science
tion of such thin films. Furthermore, some MAX phases, such 2011, 331, 568.
as Ti4GeC3, have only been synthesized in thin film form.[70] [4] R. Ma, T. Sasaki, Adv. Mater. 2010, 22, 5082.
Producing MXenes from thin films is key for the fabrication [5] M. Naguib, M. Kurtoglu, V. Presser, J. Lu, J. Niu, M. Heon,
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[6] M. Naguib, O. Mashtalir, J. Carle, V. Presser, J. Lu, L. Hultman,
Experimentalists working with this emerging family of 2D
Y. Gogotsi, M. W. Barsoum, ACS Nano 2012, 6, 1322.
materials should focus on addressing the following: [7] M. Naguib, J. Halim, J. Lu, L. Hultman, Y. Gogotsi, M. W. Barsoum,
J. Am. Chem. Soc. 2013,135, 15966.
• Controlling and modifying MXenes’ surfaces. [8] M. W. Barsoum, MAX Phases: Properties of Machinable Ternary Car-
• Establishing the exact structure of Mn+1XnTx as a function of bides and Nitrides, John Wiley & Sons, Weinheim, Germany 2013.
T and x. [9] I. Salama, T. El-Raghy, M. W. Barsoum, J. Alloys Compd. 2002, 347,
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MXenes intercalated with various compounds/ions. [10] H. B. Zhang, Y. C. Zhou, Y. W. Bao, M. S. Li, J. Y. Wang, J. Eur.
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[12] M. W. Barsoum, Prog. Solid State Chem. 2000, 28, 201.
• Large-scale delamination of MXenes other than Ti3C2Tx.
[13] Z. Sun, D. Music, R. Ahuja, S. Li, J. M. Schneider, Phys. Rev. B 2004,
• Finding alternative, robust, and safe routes of MAX phase 70, 092102.
exfoliation and MXene delamination. [14] M. W. Barsoum, J. Golczewski, H. J. Seifert, F. Aldinger, J. Alloys
• Synthesizing MXenes without surface functional groups. Compd. 2002, 340, 173.
• Direct gas phase synthesis of single-layer MXene films. [15] M. Naguib, V. Presser, D. Tallman, J. Lu, L. Hultman, Y. Gogotsi,
• Characterizing single-layer MXenes, including electronic, M. W. Barsoum, J. Am. Ceram. Soc. 2011, 94, 4556.

Adv. Mater. 2014, 26, 992–1005 © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com 1003
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