Recent Progress in Layered Transition Metal Carbides andor Nitrides (MXenes) and their Composites Synthesis and Applications
Recent Progress in Layered Transition Metal Carbides andor Nitrides (MXenes) and their Composites Synthesis and Applications
Recent Progress in Layered Transition Metal Carbides andor Nitrides (MXenes) and their Composites Synthesis and Applications
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University, 50 Nanyang Avenue, Singapore 639798. 1, the layer will consist of a single block of octahedral, when n
d. Electronic Materials Research Laboratory, School of Electronic and Information
=2 and 3, there will be two and three blocks, respectively. These
Engineering, Xi’an Jiaotong University, Xi’an, P. R. China, Email:
[email protected] new materials have been termed as MXenes in recognition of
Electronic Supplementary Information (ESI) available: [details of any supplementary the loss of A element from the parent M n+1AXn phase and 2D
information available should be included here]. See DOI: 10.1039/x0xx00000x
morphology reminiscent of graphene.
Cumulatively, extensive studies have indicated that there
are certain constraints in the synthesis of the parent Mn+1AXn
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1
phases and selective extraction of A element from parent View Article Online
phase. In the synthesis of parent Mn+1AXn phases with Al, the M (a) (b) 10.1039/C6TA06772G
DOI:
components are observed to be limited to only Ti, V, Cr, Nb, Ta,
Zr and Mo. Selective removal of A element from parent Mn+1AXn
phases at elevated temperature is possible however structural
2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx
Ti2AlC in a 10 % concentration HF at RT for 2h. The divergences was observed to be 8 h. Based on the existence of
View Article Online
in M-A bond energies from Ti2AlC (ca. 0.98 eV) to Nb2AlC (ca. corresponding by-products ((NH4)3AlF6, NH DOI: 10.1039/C6TA06772G
4AlF 4 and AlF3.3H2O
1.21 eV) result in the longer etching duration (ca. 90 h) and in a ratio of 10: 1: 1 for reaction with NH4HF2), probable reaction
higher HF concentration (50 % HF, RT), in order to eliminate Al mechanism between Ti3AlC2 and bifluoride etchant solution has
from Nb2AlC than that from Ti2AlC.14, 15, 23 Precariously, been proposed.27
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 3
mixture with equal mass of Ti4AlN3 powders (> 37 µm) and (a) (b) View Article Online
fluoride salt at 550 °C for 0.5 h in Ar at identical ramping and DOI: 10.1039/C6TA06772G
cooling rate at 10 °C/min.35 In order to proceed at lower
temperature, the ternary eutectic composition in this salt
system, which consisted of 59 wt. % KF, 29 wt. % LiF and 12 wt.
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few layers were possible. Advantageously, the as-synthesized (instead of 6 M) increased the concentration of View delaminated
Article Online
multi-layered Ti3C2Tx and Mo2CTx from the HCl/LiF etchant Ti3C2Tx further, as more protons (H+) wereDOI: 10.1039/C6TA06772G
available to exchange
solution route as initially proposed by Ghidiu et al., can be fully with Li+.
and easily delaminated by mere sonication in water. 30, 32 This Lipatov et al. evaluated the quality of Ti3C2Tx flakes
significantly effective delamination have been attributed to synthesized with different molar ratios of LiF to Ti3AlC2 (5:1 and
conditions of 35 °C for 24 h.30 Zhang et al. observed a larger c resolution transmission electron microscopy (HRTEM).
lattice parameter of ca. 31 Å and a significant increase in the Expectedly, the larger exfoliated Ti3C2Tx flakes are mechanically
delamination ratio of HCl-LiF etched Ti3C2Tx from 6.5 % to 29.2 more robust (coarse shiny flakes after grinding) than smaller
% after 1 h of sonication, which can be achieved by prior ones (fine black powders after grinding). Exfoliated Ti3C2Tx
washing the exfoliated products with ethanol instead of DI flakes, with molar ratio of LiF to Ti3AlC2 to be 5:1, are less
water. It was suggested that ethanol could have acted as a co- ordered and have varied thicknesses (Fig.4 e), in accordance to
intercalant, together with impurity ions, which improved the the XRD pattern with only (001) reflection and some remnant
yield of the delaminated HCl-LiF etched Ti3C2Tx.40 peaks of the parent Mn+1AXn phase (not exfoliated) and atomic
Shahzad et al. presented a modified procedure with an force microscopy (AFM) height profiles. Exfoliated Ti3C2Tx
increased molar ratio of LiF to Ti3AlC2 of 7.5:1 (instead of 5:1), flakes, using 7.5:1 molar ratio of LiF to Ti3AlC2, are more orderly
to have more Li+ ions available for intercalation and thus double stacked, with a uniform height of ca. 2.7 nm (single layer with
the molar ratio of HCl to LiF to facilitate the etching of surface adsorbates) (Fig. 4f) as indicated by the series of (00l)
aluminium. Consequently, while all other aspects of the XRD peaks and AFM height profiles measurement.
procedure (35 °C for 24 h) remained identical to that reported Unfortunately, to date, only Ti3C2Tx and Mo2CTx have been
by Ghidiu et al., Ti3C2Tx could be delaminated without reported to demonstrate concurrent delamination by mere
sonication.41 Noticeably, using a more concentrated HCl of 9 M HCl/LiF etching of parent Mn+1AXn phases. Therefore, much
more works are necessary to validate if this method can be
(a) (b) extended to other MXenes. Attempts for hydrate HF-etched
multi-layered Ti3C2Tx and Mo2CTx to replicate the above results
have previously been futile, necessitating the consideration of
other intercalants.30 Importantly, Ghidiu et al. experimentally
investigated cation substitutions and related their effect on
interlayer spacing of HF-etched multi-layered Ti3C2Tx. It was
noted that only when intercalant source, LiCl, was present as
(c) (d)
part of the etchant solution—rather than as a later addition—
can the Li+ ions and a dynamic layer of H2O lead to greater
structural ordering in the HF-etched multi-layered Ti3C2Tx
(higher crystallinity as evidenced by the sharp (002) XRD peak),
which demonstrated clay-like (hydrated) behaviour. As
evidenced by XRD pattern, a discontinuous structural expansion
(e) (f) in the direction normal to the basal plane of Ti3C2Tx as H2O
molecules intercalate, and variance of intercalated cations (with
different hydration enthalpy) expectedly cause quite different
structural changes in response to relative humidity.43
Although only weak residual forces hold and prevent HF-
etched multi-layered MXenes from readily separation into
Fig. 4 TEM images of Ti3C2Tx flakes produced by using: (a) Route 1 individual layers (hence the accordion-like morphologies), a
(ratio of LiF to Ti3AlC2 is 5:1), and (b) Route 2 (ratio of LiF to Ti3AlC2 is sonication procedure without preceding intercalation of species
7.5:1), respectively. Small panels in (a) and (b) show HRTEM images between the layers can only result in low yield of single/few-
and SAED patterns of monolayer 2D crystals of Ti3C2Tx. AFM images
of the Ti3C2Tx flakes deposited on Si/SiO2: (c) Route 1, and (d) Route layered MXenes. This was illustrated by the pioneering work by
2. (e) AFM height profiles measured along the dashed lines in (c). The Naguib et al., where accordion-like HF-etched Ti3C2Tx was
colors of the height profiles in (e) correspond to the colors of the exfoliated upon sonication in methanol for 300 s, which
dashed lines in (c). (f) AFM height profile measured along the dashed however resulted in low yield of Ti3C2Tx nanosheets and scrolls,
line in (d) [reprinted with permission from ref. 42. Copyright 2016 approximately ten-layer thick and even lower yield of single-
John Wiley & Sons, Inc.].
layer Ti3C2Tx.1
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Mashtalir et al. reported the first high yield delamination of (a) (b) View Article Online
accordion-like Ti3C2Tx into a mixture of narrow sized distributed DOI: 10.1039/C6TA06772G
single and few-layered Ti3C2Tx by intercalation of dimethyl
sulphoxide (DMSO) between the multi-layered Ti3C2Tx at RT for
18 h under constant stirring, followed by sonication in DI water
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addition to extending the approach beyond Ti3Si0.75Al0.25C2 and conclude the fabrication of composite solvent resistant
View Article Online
Ti3Al0.9Si0.1C2. nanofiltration (SRNF) membranes.53 Ti3CDOI: 2Tx 10.1039/C6TA06772G
additives acquire
good compatibility with the PEI polymeric matrix, as driven by
2.3 MXene-based Composites hydrogen-bonding interaction, with noticeable weakened
Ling et al. fabricated the first conductive, flexible, and free- Fourier transform infrared spectroscopy (FTIR) characteristic
fabrication process, the Ti3C2Tx layers were highly oriented and ability of the PAN/PEI-Ti3C2Tx membrane for polyethylene glycol
mostly parallel to the film surface. With 10 wt. % and 60 wt. % (PEG) solute is greatly improved, with molecular weight cut-off
PVA, tensile strength of the Ti3C2Tx/PVA composite, as (MWCO) of approximately 200 Da. Expectedly, the inclusion of
compared with pure Ti3C2Tx, was synergistically improved by hydrophilic Ti3C2Tx fillers slightly decreases the permeate flux
about 34 % and 100 % respectively. However, its electronic for weak- or non-polar solvents, such as ethyl acetate, butanone
conductivity was greatly compromised by a factor of 101 and 108 and n-heptane, whereas the transfer ability for polar
accordingly. A hollow, 6 mm in diameter and 10 mm tall, made isopropanol is enhanced (ca. 30 %). It is proposed that the –OH
with 4-5 μm thick 90 wt. % Ti3C2Tx/PVA film was able to sustain groups on the Ti3C2Tx surface function as adsorption sites and
2.9 MPa as compared with the 1.3 MPa by its pure Ti3C2Tx facilitate the storage of isopropanol molecules through
counterpart.51 Restacking of single- and few-layered Ti3C2Tx hydrogen bonding interaction, which provide additional
flakes remained an unresolved issue. pathway for isopropanol molecules to transport along the
Naguib et al. prepared a Ti3C2Tx/polyacrylamide (PAM) surface and the inter-lapped gap. PAN-PEI SRNF membrane with
nanocomposite by casting a well-mixed solution of Ti3C2Tx/PAM 2 wt. % Ti3C2Tx exhibits concurrent enhancement in membrane
onto a Teflon tray, followed by air-drying at room temperature flux and rejection ability, overcoming the hitherto trade-off as
over several days. A well dispersed Ti3C2Tx/PAM composite was demonstrated by other inorganic or graphene oxide fillers.
formed as the DMSO-intercalated Ti3C2Tx was swelled Similarly, DMSO-intercalated HF-etched Ti3C2Tx fillers were
considerably and spontaneously attracted PAM (Mw 600 000 — added into a hydrophobic polydimethylsiloxane (PDMS) matrix
1 000 000 g mol-1) solution when mixed, so that the hydroscopic to prepare a different hybrid active layer for modifying SRNF
PAM was favourably infiltrated and in-situ polymerized in membrane. (3-Aminopropyl) triethoxysilane (APTES) and
between the Ti3C2Tx layers.52 In a 6 wt. % Ti3C2Tx film, large dibutyltin dilaurate (DBTDL) were used instead of TMC.
quantity of PAM was available to intercalate into Ti 3C2Tx. Thus, Although the Ti3C2Tx additives are less compatible and weakly
few-layered Ti3C2Tx sheets were dispersed and randomly interact with PDMS matrix in the PAN/PDMS-Ti3C2Tx membrane,
oriented. In comparison, in 31 wt. % Ti3C2Tx film, multi-layered as evidenced by SEM, FTIR and XRD, PAN/PEI-Ti3C2Tx membrane
Ti3C2Tx flakes were predominantly observed (TEM). With the exhibits concurrent enhancement in membrane flux for alcohol
incorporation of a mere 6 wt. % Ti3C2Tx, the insulating polymer and rejection ability.
matrix of PAM became semi-conducting, with an electrical Aïssa et al. prepared a highly conductive Ti3C2Tx/graphene
conductivity to be 3.3 × 10-2 S m-1. As the loading level of Ti3C2Tx sandwich-like nanocomposite by alternatively depositing
with further increased to 31 wt. %, the electrical conductivity Ti3C2Tx and graphene layers on a glass substrate, by using an
behaviour of the Ti3C2Tx/PAM nanocomposite became metal- electrohydrodynamic atomization (EHDA) deposition method.54
like, indicating that the electrical percolation threshold of PAM These composite films were then annealed under vacuum at
matrix had been overcame. Such composites may find 200 °C for 2 h. The subsequent absence of F peak in XPS spectra
applications in radio frequency (RF) shielding or static charge suggested that this thermal treatment probably passivated the
dissipation. Although no detailed quantitative characterization –F terminations. Both structural and electronic properties of the
of mechanical properties of the Ti3C2Tx/PAM nanocomposite Ti3C2Tx composite thin films are shown to be positively affected
was conducted, it was generally observed that the addition of by the integration of graphene.
Ti3C2Tx expectedly increased the stiffness of PAM. Zhao et al. proposed a repeated procedure of alternating
Wu et al. incorporated DMSO-intercalated HF-etched vacuum filtration of delaminated HF-etched Ti3C2Tx suspension
Ti3C2Tx fillers into a hydrophilic polyethyleneimine (PEI) matrix and carbon nanotubes (CNTs) dispersion to prepare a flexible,
through solution mixing to prepare a hybrid active layer. free-standing sandwich-like 95 wt. % Ti3C2Tx/CNT composite
Sequential drop-casting of homogeneous Ti3C2Tx/PEI and film (Fig. 6a). For comparison, a randomly mixed 95 wt. %
mixture of trimesoyl chloride (TMC) and n-hexane solution onto Ti3C2Tx/CNT was prepared by direct vacuum filtration of mixed
the surface of commercial polyacrylonitrile (PAN) ultrafiltration 95 wt. % Ti3C2Tx/CNT dispersion. The sandwich-like 95 wt. %
membrane and subsequent heat treatment at 60 °C for 2 h to Ti3C2Tx/CNT composite was observed to have a more ordered
remove residual solvent and complete the cross-linking reaction structure, whereby sandwich-like superposition of Ti3C2Tx and
CNT layers (Fig. 6b) can be clearly identified to be unlike the
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pit produced on the top of the CNF when Co catalyst was for 1h or hydrothermal treatment at 150‒250 °C at 1 Article
View to 5 Online
MPa
removed. for various durations, a hybrid structureDOI: 10.1039/C6TA06772G
with low content of
Similarly inspired by the ion exchange occurring at the unreacted Ti3C2Tx (as evidenced by remnant XRD peaks) and
hydroxyl (–OH) groups on Ti3C2Tx surfaces, Luo et al. synthesized varied shaped and sized anatase TiO2 nanocrystals embedded in
a PVP-Sn4+@Ti3C2Tx nanocomposite (Fig. 7b). By adding HF- amorphous carbon sheets was formed instead. Hydrothermal
(Fig. 7c). 2D conductive Ti3C2Tx matrix serves varyingly as ion al. investigated the Ti3C2Tx oxidation mechanism by using in situ
exchange sites, buffer layer to accommodate the volumetric TEM analysis. 61 They found that TiO2 nanoparticles were
change during electrochemical reaction, partial capacity of the formed from top and bottom of the Ti layers during flash
entire composite and endowment of excellent rate oxidation whereas nanocrystalline TiO2 sheets were formed
performance. Interestingly, a synergistic “pillar effect”, i.e., instead during slow oxidation.
spontaneous expansion of anchored Sn (Fig. 7d) and alloying Coincidentally, Li et al. also identified that Ti3C2Tx could be
with Li+, which concurrently pushed the Ti3C2Tx interlayers partially oxidized by O2 at low temperature of 200 °C for an
further apart to allow more Li+ ions to intercalate, was proposed accumulated period of 40 min to form evenly distributed
to significantly contribute to its overall exceptional anatase TiO2 nanoparticles on Ti3C2Tx sheets, variant to that of
electrochemical capacity of the composite that far exceeds that TiO2-C hybrid structure by Naguib et al.; and at higher
of pure Ti3C2Tx.59 temperature, the synthesized anatase TiO2 nanoparticles would
Naguib et al. actualized and proved the concept of oxidizing then be transformed to rutile TiO2 nanoparticles.62
HF-etched multi-layered Ti3C2Tx in air, CO2, or pressurized DI Zhang et al. synthesized a layered hierarchical structure
water. Hampered by uncontrolled synthesis condition, anatase composite of orthorhombic Nb2O5 nanoparticles, which were
TiO2 nanocrystals, with divergent morphologies and sizes, uniformly decorated on surface of the Nb4C3Tx flakes and
embedded in amorphous carbon sheets (TiO2-C hybrid intertwined with amorphous carbon, by using a facile one-step
structure), were formed when Ti3C2Tx powders were flash oxidation of HF-etched Nb4C3Tx powders in CO2 at 850 °C for 0.5
oxidized in air at 1150 °C for 30 s. However, when subjected to h (Fig. 8a). Similarly, hierarchical composites of Nb2O5@Nb2CTx
either isothermal oxidation in pure CO2 between 150 to 300 °C and TiO2@Ti3C2Tx were derived from Nb2CTx and Ti3C2Tx,
respectively by using the CO2 partial oxidation method.63 Such a
(a) (b) hierarchical design is advantageous for electrochemically active
and high rate-response metal oxide nanocrystals, i.e., Nb2O5 or
TiO2, are at the edges (Fig. 8b) and interlayers and directly
exposed to the electrolyte, so that ion diffusion paths are
effectively shortened. Meanwhile, the internal network of the
highly conductive carbon and unoxidized MXenes promotes the
overall electronic conductivity of the composites. Additionally,
the carbon can probably also function similarly to that of a
(c) (d) binder and strengthen interaction between the metal oxide and
MXene particles.
In a separate study, the same group explored the influences
of oxidation temperature, time and CO2 feed rate on the phase
composition, particle size of Nb2O5, constitutions of the
hierarchical composites and the corresponding electrochemical
performances (Fig. 8c).64 A similar phenomenon for Ti2CTx was
reported, laying the groundwork for modification and/ or
Fig. 7 (a) SEM image of HF-etched multi-layered Ti3C2Tx-CNT elimination of surface groups by using heat treatment or post-
composite. Inset shows that some CNFs grew within the interlayer etch annealing in various gas environments to structurally alter
spaces of Ti3C2Tx flakes [reprinted with permission from ref. 58.
Copyright 2015 The Royal Society of Chemistry]. (b) TEM image of the morphology of Ti2CTx, partially oxidize Ti2CTx to form TiO2
PVP-Sn4+@Ti3C2Tx. Inset shows the lateral size distribution of the under certain conditions and thus favourably impact its
anchored Sn4+ nanocomplex particles. (c) STEM image of PVP- electrochemical performance.65, 66 In the latter, it was noted
Sn4+@Ti3C2Tx. Inset shows the corresponding elemental mapping of that annealing Ti2CTx in various controlled atmospheres, such as
Ti, O, and Sn. (d) Close-up XRD patterns of three different samples Ar, N2 or N2/H2, retained its initial chemical structure but caused
(Ti3C2Tx, alk-Ti3C2Tx, and Sn4+@Ti3C2Tx) [reprinted with permission
from ref. 59. Copyright 2016 American Chemical Society]. slight thinning of the layers (i.e., larger interplanar distance and
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(a) (b) (c) Ag/Ti (Ag0.9Ti0.1) bimetallic nanowires (Fig. View 10c). This
Article Online
nanocomposite, with enhanced conductivity, DOI: 10.1039/C6TA06772G
numerous oxygen
adsorption sites and shortening the diffusion path of adsorbed
oxygen, displayed encouraging electrocatalytic activity for ORR,
whereby its onset potential and half-wave potential are higher
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 11
single/few-layered MXenes are prepared, their incorporation performances amongst some composites will beView
discussed in
Article Online
into polymeric composites with new properties and the following section. DOI: 10.1039/C6TA06772G
applications are to be explored in the near future.
Critical to fabricating a well-mixed MXene/polymer
composite, the selection of polymer must also take into 3. Structures, Properties and Applications
As mentioned above, one early strategy to improve the variety of organic and inorganic molecules or ions (e) and subsequent
electrochemical performance of MXene-based composites is to delamination to single or few layers via sonication have been
open the structure of the multi-layered MXene matrix through demonstrated.25, 26, 31, 35, 43, 45-48 Understanding both the surface
delamination and reassembling them into a porous “paper”-like terminations and the interlayer interactions is the prerequisite to
structure. Incorporation of interlayer spacers, such as CNTs, or purposefully manipulating the properties of MXenes for their various
conductive polymers, such as PPy, have further enhanced the applications. Consequently, modelling and simulation, such as
electrochemical performance of the free-standing “papers” by density functional theory (DFT) and to a lesser extent, molecular
increasing their electrical conductivities (with additional dynamics (MD) simulations, have been extensively applied to
electron conductive pathways) and interlayer spaces that understand the structure, to predict properties and to identify
promote electrolyte ion access and transportation.47, 55-58 Since potential applications of MXenes, guiding much of the experimental
no polymeric binders or conductive additives are included, research in the field of MXenes, although most of earlier modelling
undesirable dead volume and interface are reduced and works are regarding uniform terminating species.34, 82-105
associated overpotentials are eliminated. On the basis of DFT calculations, Srivastava et al. detailed the
Surface terminations of MXenes are chemically modified, so mechanism of exfoliation and simultaneous functionalization of
that it is able to change from one predominant surface group
to another, so as to more effectively attach cations to increase (a)
interlayer spacings, or to facilitate subsequent procedures such
as oxidation or self-assembly, and achieve hitherto properties
and improved performances than their non-composite
counterparts.59, 80, 81 Functionalization of MXene-based
additives or matrices to endow desirable and hitherto
properties, such as enhancement of the matrix-filler interfacial
strengths, remains to be conducted. Passivation or removal of
MXenes’ inherent surface functional groups is also possible
through thermal treatment in Ar, hence presenting a wide
array of probable modifications to be studied for work with or
around microscopically defective and varyingly surface (b) (c)
terminated MXene-based materials. Hydrothermal oxidation,
which offers scalable products and highly reproducible
crystallinity, well morphological and compositional control,
relatively low temperature and short duration, seems to be
most preferred method to develop MXene/oxide composites,
and alternative methods remain yet to be explored.60, 63, 68-74
Similarly, intimate contact between the conducting MXene
matrices and well-dispersed fillers, be it as-synthesized oxides
or CNTs, is crucial to the overall homogeneity and properties of
MXene-based composites. It remains intriguingly challenging Fig. 11 (a) Crystal structure model of MAX phase Ti3AlC2 (left), MAX
to alternatively attain a hierarchical structure with such phase Ti3AlC2 projected along the a axis (middle), and MXene phase
Ti3C2Tx projected along the a axis (right) with −OH-terminated
intimate contact and well-distribution of exposed foreign functional groups. The three Ti sublayers are labelled Ti1, Ti2, and
additive material(s) amongst the MXene matrix network if the Ti3 [reprinted with permission from ref. 108. Copyright 2016
MXene does not participate as both the precursory source of American Chemical Society]. (b) Atomic resolution HAADF-STEM
metal cations and as the supporting matrix structure itself. image of a typical Ti3C2Tx sheet with the positions of surface groups
Details for the performance of various composites in their labelled by the arrows. (c) HAADF-STEM image of a Ti adatom on a
single Ti3C2Tx sheet [reprinted with permission from ref. 107.
respective applications and the comparison in electrochemical Copyright 2015 American Chemical Society].
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Ti3C2Tx by HF etchant.106 The Ti atoms on the edges of parent phase (a) (c) View Article Online
Ti3AlC2 were proposed as the initial sites for dissociated H/F ions to DOI: 10.1039/C6TA06772G
attach onto, subsequently weaken Ti-Al bonds and increase
interlayer gap for more HF molecules to intercalate. Al was then
removed from Ti3AlC2 due to the formation and release of AlF3 and
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abruptly collapses along the out-of-plane direction and is sandwiched between M’’ layers and the C atomsViewoccupy the
Article Online
accompanied by shrinkage of Ti–C bonds and relaxation of stress (Fig. octahedral sites between them) may be achieved DOI: 10.1039/C6TA06772G
through surface
15c-d). Importantly, surface functionalization (=O, –OH or –F) is terminations and choice of outer M’ layers.125
observed to form covalent bonds with Ti (disappearance of lone pair Lee et al. and Ma et al. investigated and reported the possibility
electrons from Ti atoms) and enhance the mechanical flexibility of to hypothetically induce an indirect-to-direct band gap of Sc2CO2
unavailable.32, 118 Computationally, Zha et al. predicted Mo2CTx to theoretically obtained through doping with Cr or Mn.128
have more widespread of potential applications beyond high More recently, Wang et al. proposed experimentally derived
capacity anode material for it was found be nonmagnetic, possessed atomistic models that encompassed total neutron scattering and
a high electrical conductivity (106 Ω–1m–1), favourable thermal multilevel refinement methods, accounting for the coexistence and
conductivity (48.4 Wm–1 K–1), small thermal expansion coefficient random surface groups (Fig. 16a-f) in certain MXenes, so as to
(2.26 × 10–6 K–1) and as well as high mechanical strength.119, 120 improve the accuracy in predicting the properties of MXene from the
Aston et al. calculated the theoretical thermodynamic stability of existing idealized, limited, hypothetical and unrealistic models.129 As
54 MXene compounds to streamline and identify yet-to-be- most theoretical studies to date have been calculated based on
synthesized but stable MXenes. From a thermodynamic perspective, single, isolated sheets, deviating from most experimentally obtained
oxygenated transition metal nitrides such as Ti3N2O2, Ti3N3O2, few-/multi-layered MXene flakes, ensuing models should also
V3N2O2, V4N3O2 and Cr4N3O2 were predicted to be experimentally accommodate interlayer interactions such as van der Waals forces
probable and six fluorinated Sc-based Mxenes (Scn+1XnF2) were and hydrogen bonding for more realistic computations. It is also to
expected to easily exfoliate and produce single layers.121 be noted that although DFT calculations produce stable and
Theoretically, Ti2CO2, Hf2CO2, Zr2CO2, Sc2CO2, Sc2CF2 are consistent geometries, the computed electronic properties (whether
predicted to possess indirect band gap while Sc2C(OH)2 is expected metallic or narrowly-band semiconducting) are much dependent on
to have a small direct band gap.100 Theoretical studies by L. Li, the choice of the exchange-correlation functional.130 As compared to
Khazaei et al., and Si et al. indicated that Mo2Ti2C2O2 to be
topological semiconductor.122-124 Anasori et al., using DFT (a) (b)
calculations in conjunction with experimental data, predicted the
controlled modifications to electronic properties (from metallic to
semiconducting) of a subfamily of ordered layered double transition
metals carbides (M’2M’’C2 and M’2M’’2C3, where M’ layers are
(a) (b)
(c)
(d) (e)
(c) (d)
(f)
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storage media (using Sc2C, Ti2C, V2C and Cr2C), NH3 electrosynthesis be less drastically impacted by oxidation and remained stable in
(using V3C2 and Nb3C2), and additives for tribological studies are air over two months. By annealing the films between 100 °C and
however still in their hypothetical or infancy stage will not be covered 200 °C, sheet resistance was further decreased due to the
in this review.79, 88, 89, 131-136 removal of any remnant adsorbed water, intercalated species
on and within Ti3C2Tx layers, however at temperature beyond
3.1 Transparent conductive films 250 °C, the films began to oxidize and sheet resistance reverted
Berdiyorov et al. theoretically derived the isolated effect of each to its initial values.139
individual surface termination group on dielectric and optical Ali et al. fabricated conductive and transparent thin films of
properties of Ti3C2Tx. Generally, the different surface groups Ti3C2Tx using EDHA, a scalable electrospray technique which
were observed to similarly decrease the static dielectric involved deposition of solution in the absence of a vacuum
function and increase ultraviolet reflectivity of Ti3C2Tx than that under the influence of an electric field at ambient temperature.
of pristine Ti3C2, though, in the visible range, only –F and –OH
demonstrated lower absorption and reflectivity than pristine (a) (b)
Ti3C2.105
Halim et al. first demonstrated the potential application of
MXenes as transparent conductive electrodes, by using a
transparent (85 % transmittance) and highly conductive
intercalated Ti3C2Tx thin film (19 nm) that was prepared by
chemically etching a magnetron-sputtered Ti3AlC2 with NH4HF2
solution at RT.25 However, it is not scalable due to the high cost
and small quantity of magnetron-sputtered films.
Dillon et al. reported a low cost and scalable fabrication (c) (d)
method to prepare continuous, optically transparent (Fig. 17a)
and highly in-plane conductive (bulk conductivity = 6500 S cm-1)
Ti3C2Tx thin films (Fig. 17b) by spin-casting, the basal planes of
individual Ti3C2Tx flakes showed a high degree of alignment,
parallel to the substrate as reflected by the high intensity of 002
XRD peak at 7.1 °. Stability and performance of these Ti3C2Tx thin
films in ambient atmosphere are still a work in progress though,
since their conductance was degraded rather quickly by a factor
of three when exposed to either O2 or moisture albeit retaining Fig. 17 (a) UV-vis-NIR transmittance spectra of spincast Ti3C2Tx film
their good transmittance.137 with varying thickness. (b) Sheet conductance vs. film thickness
(lower x-axis) and ln (transmittance) (upper x-axis) of spincast
More recently, Hantanasirisakul et al. fabricated
Ti3C2Tx films. Red circles represent thickness of Ti3C2Tx film
homogeneous, transparent conductive Ti3C2Tx thin films by deposited on Si-SiO2 substrate as measured by AFM; dashed red line
using spray coating from colloidal HCl/LiF etched Ti3C2Tx on is the linear fit with slope σ = 6600 S cm-1. Black solid squares
various substrates (Fig. 17c). As revealed by the measurement represent thickness of Ti3C2Tx film deposited on glass, quartz and
of ultraviolet-visible (UV-vis) spectrophotometry, a polyetherimide, derived from measured transmittance; black line is
the linear fit to the data points of derived thickness with slope σ =
comparatively thick Ti3C2Tx film of 70 nm still retained 44 %
6500 ± 800 S cm−1 [reprinted with permission from ref. 137.
transmittance in the visible region while a thin Ti3C2Tx film had Copyright 2016 John Wiley & Sons, Inc.]. (c) Sheet resistance vs.
a transmittance of as high as 91%. Intuitively, a trade-off transmittance at 550 nm of Ti3C2Tx sprayed from ethanol and water
between transparency and conductivity exists in terms of the solutions. Inset shows the low sheet resistance region. (d) Change
film thickness. Although the changes in transmittance are yet to in %T of Ti3C2Tx films due to chemical intercalation (positive change
indicates an increase in %T as compared to pristine Ti3C2Tx films
be fully understood and insignificant to be practically applied,
[reprinted with permission from ref. 138. Copyright 2016 John Wiley
reversible changes of %T during electrochemical & Sons, Inc.].
16 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx
A low resistivity of 3.4 × 10−4 Ω cm and ca. 86.7 %T was recorded complex processes, such as selective adsorption, degradation of
View Article Online
for a 135 nm Ti3C2Tx thin film.140 various molecules and catalysing reactions.DOI: 10.1039/C6TA06772G
It was also found
Aïssa et al. reported to exhibit a similarly low resistivity of that the as-synthesized Ti3C2Tx was not stable in water,
ca. 3.4 × 10−4 Ω cm for an electrosprayed thin film of Ti3C2Tx (250 especially in the presence of O2, because they could be partially
nm thick on a glass substrate), even lower than that of an oxidized to form TiO2, thus requiring more work to address this
to form a binary, fully percolated composite.54 This markedly this composite could be suitable for applications in purification
improved electrical conductivity (9.5 × 104 S cm-1) is attributed of contaminated water or air.69
to filling up and smoothening of HF-etched Ti3C2Tx inherent Peng et al. elucidated the preferential reversible adsorption
defects (such as nanopores which acted as resistance for of lead ions (Pb2+) from a solution with effluent contents below
electron flow) by graphene deposition, as observed under SEM 2 µg L-1, as well as high level Ca2+ and Mg2+, by using HF-etched
and AFM. The formation of a cross-linked and electrically multi-layered Ti3C2Tx treated with alkalization intercalation. The
conductive network of graphene within the film that provides sequestration of heavy metal pollutant is enhanced by cation
additional interconnecting path throughout the composite for (Na+) substitution for the –OH groups, thus forming active sites
more electrons flow and probable alignment of graphene flakes favourable for ion-exchange. It is anticipated that the exhausted
through interaction with Ti3C2Tx surface, especially so in low materials could be efficiently regenerated.81 Based on first-
graphene content (< 0.5 wt. %). principles calculations, this group further elucidated the
Lipatov et al. fabricated field-effect transistors (FETs) with adsorption mechanism as heavy-metal ions being trapped
large HCl/LiF etched Ti3C2Tx monolayer flakes (using 7.5:1 molar within hydroxyl potential traps (with sufficient opposite-spin
ratio of LiF to Ti3AlC2) as conductive channels, by first drop- electron pairs) and examined the effect of different hydroxyl
casting diluted colloidal solution of delaminated HCl/LiF etched
Ti3C2Tx onto a Si/SiO2 substrate, followed e-beam lithography (a) (b)
for device patterning and e-beam evaporation for the
deposition of 3 nm Cr and 20 nm Au as metal contacts. The
average resistivity and field-effect electron mobility of 10
similarly fabricated devices under vacuum were respectively
measured to be 2310 ± 570 Ω □−1 and 2.6 ± 0.7 cm2 V-1 s-1. The
resistivity of a Ti3C2Tx single layer (ca. 1 nm) was thus calculated
to be 2.31 ± 0.57 μΩ.m (4600 ± 1100 S cm-1). Sheet resistivity of
bulk HCl/LiF etched Ti3C2Tx film (ca. 9 μm thick) was measured
to be 15.8 ± 1.3 μΩ.m via van der Paw method.42 The small (c) (d)
difference of within one order of magnitude between resistivity
of a single Ti3C2Tx monolayer and that of a Ti3C2Tx film, was
consistent with the reported resistance anisotropy in an earlier
theoretical prediction and in situ experimental work by Hu et al.
and implied decent inter-flake conductance through the surface
functional groups.141 Environmental degradation and decrease
in the conductivity of the devices in humid air were caused by
p-doping due to electron accepting adsorbates such as oxygen Fig. 18 (a) Time dependence of MB (C0 = 0.05 mg mL-1) and AB80 (C0
and water molecules and oxidation at the edges of Ti 3C2Tx = 0.06 mg mL-1) concentrations in aqueous Ti3C2Tx suspensions in the
absence of light [reprinted with permission from ref. 46. Copyright
flakes. 2014 The Royal Society of Chemistry]. (b) Schematic of hydroxyl trap,
top view of Ti3C2(O2H2–2mPbm) structure when Pb coverage is 1/9 ML.
3.2 Environmental remediation S1–S6 represent the different atom sites of the hydroxyl [reprinted
with permission from ref. 142. Copyright 2015 American Chemical
Mashtalir et al. first demonstrated that negatively surface Society]. TEM images of (c) E. coli and (d) B. subtilis treated with 200
charged Ti3C2Tx could be used to remove a cationic dye, μg/mL of Ti3C2Tx for 4 h. The cell wall stripped down after exposure
methylene blue (MB), from solution in dark, due to favourable to Ti3C2Tx nanosheets (red arrows b, d), Ti3C2Tx nanosheets tightly
adsorption (Fig. 18a). Under ultraviolet (UV) irradiation, in the adsorbed around the cells and entered the cells (red arrows a, c). The
presence of the HF-etched multi-layered Ti3C2Tx, both MB and intracellular densities of both cells decreased and Ti3C2Tx attached to
the cellular membrane of both bacteria (red arrows b, d) [reprinted
an anionic dye, acid blue 80 (AB80), were observed to undergo with permission from ref. 147. Copyright 2016 American Chemical
rapid photodegradation, suggesting the presence of possible Society].
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 17
sites (Fig. 18b), different functional groups on the adsorption the interlayer distances instead, and reduced permeation
View Articlerates.
Online
behaviour thus extending intercalated Ti3C2(OH)2’s applicability Intuitively, bulky MB+ dye ions (> 6.4 Å) were
DOI: 10.1039/C6TA06772G
excluded by these
to adsorb other heavy metal.142 Ti3C2Tx membranes because they are too large to pass
Ying et al. observed simultaneous reduction of Cr (VI) to Cr through.145 From DFT calculations, Berdiyorov et al. explained
(III) and adsorption of Cr (III) at pH 5.0, as well as reduction of the origin of ionic selectivity to be from the variation of energy
Ti3C2Tx nanosheets, are promising candidates for efficient (Fig. 18 c-d). Its negatively charged surfaces, high hydrophilicity,
removal of high valence toxic metal compound from industrial hydrogen bonding between oxygenate groups have been
wastewater. suggested to be the contributing factors towards the strong
Similarly, a sandwich-like, magnetic Ti3C2Tx/Fe3O4/Fe2O3 antibacterial behaviour observed. However, the exact
composite was prepared by Zhang et al. for phosphate removal antibacterial mechanism is yet to be fully understood.147
by exploiting its sorption selectivity with both Ti-O and Ti-F Smith et al. first proposed, conceptualized and theoretically
surface terminations, readily forming Ti-O-P complexes across a simulated the use of symmetric Na-ion intercalation electrodes
wide acidic pH range of 2.5 to 6.0.74 Nanosized Fe2O3 separated by Na-blocking membrane to desalinate NaCl from
intercalated between the HF-etched Ti3C2Tx layers, increased water.148 Most recently, Srimuk et al. demonstrated the first use
available surface area for reaction and the surface embedded of HF-etched multi-layered Ti3C2Tx as a novel intercalation
magnetic Fe3O4 would be responsible for the effective electrode for desalination via capacitive deionization (CDI).
separation. It is expected that the separation kinetics could Tapping into its exceptional pseudocapacitance, a CDI cell, with
greatly enhance, when an industrial magnetic field is applied. both electrodes based on drop-casted HF-etched multi-layered
Additionally, the exhausted Ti3C2Tx/Fe3O4/Fe2O3 can be readily Ti3C2Tx onto commercial porous separator, was set up and
regenerated in binary alkaline brine solutions. evaluated to have an average salt adsorption capacity of 13 ± 2
Wang et al. experimented with multi-layered HF-etched mg/g over 30 CDI cycles.149 Beyond carbonaceous materials and
V2CTx as a potential and efficient adsorbent for the capture of ion immobilization via double layer formation, ion intercalation
radionuclide, uranium (U(VI)), with a high normalized U(UI) into the layered Ti3C2Tx structure presents itself as an
adsorption capacity at 256 mg g-1 over pH range of 3.0 to 5.0. alternative towards enhanced electrochemical desalination.
Encouragingly, these multi-layered V2CTx with adsorbed U(VI)
could be regenerated when exposed in highly acidic (pH < 3) 3.3 Electromagnetic interference (EMI) absorption and shielding
solutions. Based on DFT calculations and extended X-ray Qing et al. first explored the use of HF-etched multi-layered Ti3C2Tx
absorption fine structure (EXAFS) results, the preferential as fillers (50 wt. %) to an epoxy composite of 1.4 mm thickness and
adsorption of uranyl ions by –OH bonded to V of the V2CTx layers achieved a low reflection loss (RL) of – 11 dB (excellent microwave
suggested the work of an ion-exchange mechanism.144 absorption performance exceeding 92%) over the frequency range of
Chang et al. vacuum filtrated dilute suspensions of HCl/LiF 12.4 — 18 GHz. It was proposed that the presence of surface
etched Ti3C2Tx (0.01 mg/ mL) to fabricate membranes of functional groups, intrinsic defects and dangling bonds of HF-etched
thicknesses 1.5 ± 0.1 μm with water flux ca. 38 L/ (Bar.h.m2) on Ti3C2Tx and the numerous interfaces between Ti3C2Tx and epoxy
commercial polyvinylidene fluoride (PVDF) supports. It was matrix, resulted in more electron relaxation polarization and
distinctively observed that HCl/LiF etched Ti3C2Tx membranes interfacial polarization under an alternating electrical field and thus
exhibited better selectivity, than graphene oxide membranes, contributed significantly towards dielectric loss.150
towards small (<4.5 Å) metal cations with increasing charges
from +2 to +4, under similar testing conditions, with single- Han et al. investigated the post-etching heat treatment of Ti3C2Tx
charged cations having an order of magnitude faster and its related surface structural change and influence on its
permeation of water as compared to multiple-charged cations. dielectric properties and EM wave absorption performance (Fig.
It was explained that single-charged and small radii (< 6.4 Å) 19a). The removal of Al layers through HF-etching was reaffirmed to
cations (Li+, Na+, K+) capably penetrated between Ti3C2Tx lead to a significant enhancement of complex permittivity because of
interlayers and adsorption of ions on both sides of Ti3C2Tx the surface functional groups and improved electrical conductivity.
formed electric double layer on the surface of each individual Rapid annealing of HF-etched multi-layered Ti3C2Tx at 800 °C for 2 h
flake and subsequently led to repulsion of the sheets which in argon with a heating rate of 10 °C/min resulted in the oxidation of
enabled higher permeation rates. For multiple-charged cations the surface Ti layers to form localized sandwich structure of anatase
(Mg2+, Ca2+, Al3+), beyond an initial increment of the Ti 3C2Tx and rutile TiO2 nanoparticles and amorphous carbon sheets
interlayer distances, as more of such multi-charged ions were supported by the layered Ti3C2Tx flakes. The decrease in hydroxyl
intercalated, the electrostatic attraction between the groups and formation of amorphous carbon improved the electronic
negatively charged Ti3C2Tx and highly charged cations shrank conductivity, and coupled with the formation of capacitor-like
18 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx
(a) (b) many desirable properties for commercialization such View as high EMI
Article SE
Online
at 57 dB, low density of 2.31 g cm-3, low thickness
DOI: 10.1039/C6TA06772G
of 8 µm, oxidation
resistance, high flexibility and ease of processing.41
Evidently, even though this three EMI shielding with MXenes
similarly involved Ti3C2Tx, the variances in synthesis conditions
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 19
interlayer distance.87, 99 Zhao et al. assessed the influences of strain View Article Online
(a) (b) DOI: 10.1039/C6TA06772G
and Li concentration on Li-ion storage capacity of Ti2C and reported
that the low diffusion barriers (favourable for good rate
performance) remained invariant under high strain or Li
concentration and only binding energy of Li (related to stability)
20 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx
resulted in a comparatively reduced conductivity of the hybrid negatively affected by a higher thickness or mass loading.
View ArticleMost
Online
film. It was established that the activated (through pre-cycling work to date has been evaluated as LIBDOI: 10.1039/C6TA06772G
electrode in half-cell
at low rates) spray-coated 50 wt. % Ti3C2Tx/planar NiCo2O4 configuration, with few assembled into full cell to determine
hybrid film (3 μm) displayed the best performance amongst the their energy and power densities which are in fact more critical
threes samples as it retained a reversible capacity of ca. 1010 for practical applications.
whereby Naguib et al. first demonstrated HF-etched multi- pseudocapacitors. The former is based on the reversible
layered Nb2CTx’s prospect as anode of LIBs as it maintained a accumulation of electrolyte ions at the electrode-electrolyte
reversible capacity of 170 mAh g-1 at 1 C, 110 mAh g-1 at 10 C; interfaces without redox reactions, while the latter relies on fast and
both after 150 cycles.15 Mashtalir et al., in the same study that reversible surface redox reactions, however retaining rectangular-
reported i-PrA as intercalant to assist in delaminating HF-etched shaped CV curves. In general, pseudocapacitors possess higher
multi-layered Nb2CTx, prepared a flexible and free-standing 90 volumetric capacitances and lowered cycling stability. MXenes, with
wt. % Nb2CTx/MWCNTs composite, which exhibited an their 2D characteristics, large surface areas and highly defined
unprecedented capacity of 220 mAh g-1 at 10 C after 100 morphology, present themselves as promising electrode materials
cycles.47 Similar to that of the high-density Ti3C2Tx electrode, by for supercapacitors.
cold-pressing HF-etched multi-layered Nb2CTx with CB, Kim et Lukatskaya et al. used electrochemical in-situ X-ray
al. prepared a practical Nb2CTx electrode with even higher areal absorption spectroscopy (XAS) to probe the mechanism of high
capacity of 6.7 mAh cm-2 at C/3.156 Although Nb2CTx anode
performance for LIBs, in terms of reversible capacity and high (a) (b)
rate performance, is promising, the observed sloping/linear
charge-discharge profiles over a large potential range
resembles more of electrochemical behaviour of a capacitor
than a battery. Byeon et al. assembled and tested three
prototypical hybrid cells using Nb2CTx as either a cathode or an
anode and both in a symmetrical setup.158
As an experimental LIB anode material, HF-etched multi-
layered V2CTx displayed a reversible capacity of 210 to 260 mAh (c) (d)
g-1 at 1 C, 125 mAh g-1 at 10 C; both after 150 cycles. However,
its appeal as a prospective anode material was greatly
diminished for its requirement of high lithiation voltage.15 A
synergistic composite of orthorhombic Nb2O5 nanoparticles
with Nb4C3Tx and amorphous carbon as synthesized by Zhang et
al., exhibited a reversible capacity of 195 mAh g-1 at 0.25 C after
400 cycles.63
(e) (f)
Recently, two Mo-based MXenes have also been prepared
and examined as anode material for LIBs. Anasori et al.
identified the resemblance of electrochemical behaviour of
Mo2TiC2Tx to be quite different to that of Ti 3C2Tx and with
reversible capacity of 145 mAh g-1 at 1 C after 160 cycles.17
Synthesized by Halim et al., the first Mo2CTx with an addition of
8 wt. % MWCNTs, reported a reversible capacity of 250 mAh g-1
at 5 A g-1, 76 mAh g-1 at 10 A g-1, both after 1000 cycles.32 Table
S1 in Supplementary Information shows the list of investigated Fig. 21 (a) Ti K-edge XANES spectra of Ti3C2Tx at −0.4 V (blue line)
Ti-, Nb-, V-, and Mo-based MXenes as prospective LIB anode and 0.1 V (green line), together with those of TiO (red line) and TiO2
(black line). (b) Average Ti oxidation state determination in Ti3C2Tx
material.
at various applied potentials (see inset), using the Ti K-edge energy
It is noted that device manufacturing requirements such as shift of the reference TiO and TiO2 compounds [reprinted with
current collectors, conductive agents, polymeric binders etc. permission from ref. 159. Copyright 2015 John Wiley & Sons, Inc.].
inevitably compromise the eventual volumetric capacities, thus (c) Digital photograph showing the transferred L-s-Ti3C2Tx MXene
there have been much effort towards preparing free-standing, MSC on flexible scotch tape, and the corresponding (d) CVs, (e)
charge–discharge curves, and (f) variation in areal capacitances with
binder-free MXene electrodes. The gravimetric capacity
scan rates [reprinted with permission from ref. 169. Copyright 2016
(normalized to the total electrode mass) is also observed to be The Royal Society of Chemistry].
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 21
capacitance of Ti3C2Tx in 1 M H2SO4 aqueous electrolyte (Fig. electrochemically optimized free-standing PPy/ Ti3View C2TxArticle
film Online
with
21a). Changes in Ti oxidation state of Ti3C2Tx are detected during volumetric and gravimetric capacitances DOI: F cm-3 and 485
10.1039/C6TA06772G
of 291
charge/discharge, indicative that the predominant F g-1, respectively at 1 mA cm-2 and excellent cyclic stability with
electrochemical behaviour of Ti3C2Tx is pseudocapacitive (which ca. 100 % capacitance retention after 20 000 cycles.162
produces rectangular-shaped CVs. More importantly, the Lin et al. prevented the restacking of delaminated Ti3C2Tx
shown to spontaneously wet the Ti3C2(OH)2 slit nanopore even partial oxidation of Ti3C2Tx, Zhu et al. synthesized a TiO2/ Ti3C2Tx
in the absence of external potential. Additionally, cyclic composite with a gravimetric capacitance of 143 F g-1 at 5 mV s-
1.71 Rakhi et al. and Tang et al. have coincidentally explored
variation of spatial distribution of ions and orientation of cation
dipoles within the pore during charging/discharging help different forms of MnO2 as interlayer spacers for Ti3C2Tx and
screened external electric potential. Ions are theoretically attained improved electrochemical performances.166, 167 Wang
observed to be significantly accelerated and have more ordered et al. synthesized a 38 wt. % delaminated HF-etched
dipole orientation within Ti3C2(OH)2 electrode with a narrower Ti3C2Tx/nickel-aluminium layered double hydroxide composite
slit (analogous to layer distance).160 by a liquid phase deposition with outstanding specific
Ghidiu et al. pioneered the work to preparation of a clay-like capacitance of 1061 F g-1 at current density of 1 A g-1.168
paste of HCl/LiF etched Ti3C2Tx with intercalated water and ions Progressively, towards the development of flexible energy
from that could be conveniently used to assemble flexible and storage devices, Peng et al. fabricated an all-Ti3C2Tx solid-state
freestanding film. When evaluated in a three-electrode interdigital prototype microsupercapacitor (MSC) by solution
configuration in 1 M H2SO4 electrolyte at scan rate of 2 mV s-1, spray-coating of large size (3–6 μm laterally) HCl/LiF eteched
these as-prepared films displayed high volumetric capacitance Ti3C2Tx as the current collector, followed by spray-coating small
of 900 F cm-3 in the absence of faradaic redox reaction.30 size HCl/LiF etched Ti3C2Tx (ca. 1 μm) with more defects and
Comparatively, Dall’Agnese et al. attempted surface chemistry edges on top as the electroactive layer (Fig. 21c-f). The
modifications to replace –F in HF-etched Ti3C2Tx with hydroxyl interdigital pattern was carved by a photoresist-free direct laser
groups and delaminated multi-layered Ti3C2Tx that were pre- cutting method and then meticulously filled with a PVA/H2SO4
intercalated with DMSO; and the prepared electrode only gel electrolyte. The all-Ti3C2Tx device, with comparatively lower
registered a moderate volumetric capacitance of 520 F cm-3 contact resistance than those with platinum current collectors,
under similar testing conditions.80 Hu et al. via a facile dropping- recorded areal and volumetric capacitances of ca. 27 mF cm−2
mild baking (DMB) method to prepare electrode of Ti3C2Tx films and ca. 357 F cm−3, respectively, at a scan rate of 20 mV s−1 and
on nickel foam with excellent gravimetric capacitance of 499 F demonstrated exceptional cyclic stability with a 100 %
g-1 (albeit low active material loading and tested in a two- capacitance retention after 10 000 cycles at scan rate of 50 mV
electrode configuration), provided some food for thought to s−1.169
alternative fabrication of MXene-based energy storage Kurra et al. adopted a scalable and cost-efficient Meyer rod
devices.161 coating of HF-etched Ti3C2Tx and HCl/LiF etched Ti3C2Tx slurries
In view of the inclination of delaminated Ti3C2Tx stacks on commercially available A4 printing paper. These flexible
restacking and limiting full access of electrolyte ions to their fabricated devices, when supported on a flat plastic or glass
surfaces during electrode preparation, Zhao et al. introduced a substrate, were capably carved by laser patterning. The HCl/LiF
simple procedure of repeated, alternating filtration of Ti 3C2Tx etched Ti3C2Tx microsupercapacitor (ca. 125 µm), with larger
suspension and SWCNTs dispersion and obtained a volumetric interlayer spacing and better conductivity, showed an areal
capacitance of 390 F cm-3 at 2 mV s-1. Although MgSO4, a less capacitance of 25 mF cm-2 and 10.5 mF cm-2, respectively, at
toxic and affordable neutral electrolyte, offers a broader scanning rates of 20 mV s-1 and 1000 mV s-1. Its HF-etched
operating voltage window, its poorer conductivity limits the counterpart (ca. 125 µm) only recorded areal capacitance of 6.2
measured capacitance.55 mF cm-2 and 4.2 mF cm-2.170
In line with the idea to incorporate interlayer spacers, Boota Li et al. assembled a conventional sandwich-type all-solid-
et al. managed in situ polymerization of PPy and alignment of state supercapacitor with a PVA/H3PO4 soaked glass fiber
PPy chains between Ti3C2Tx layers and attained a more membrane inserted between two pieces of 75 wt. % HF-etched
conductive, pseudocapacitive composite with exceptional Ti3C2Tx/electrochemically exfoliated graphene nanocomposite
volumetric capacitance close to 1000 F cm-3 at 5 mV s-1.56 Zhu et film electrode. This device delivered a volumetric capacitance
al. electrophoretically deposited HF-etched Ti3C2Tx onto of 184 F cm-3 at current density of 0.2 A cm-3 and retained 85.2
fluoride-doped tin oxide (FTO) substrate for 30 s, and % of initial volumetric capacitance after 2500 cycles. A flexible
subsequently immersed in an electrochemical polymerizing interdigital microsupercapacitor was fabricated by spray-
electrolyte and polymerized for 600 s to fabricate an coating the same composition of HF-etched
22 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx
Ti3C2Tx/electrochemically exfoliated graphene solution onto a (a) (c) View Article Online
(b)
polyethylene terephthalate (PET) substrate through a mask. DOI: 10.1039/C6TA06772G
This fabricated device measured an areal capacitance of 3.26
mF cm−2 and volumetric capacitance of 33 F cm−3 at 5 mV s-1.171
Although Ti2CTx has a higher calculated gravimetric
capacity of 68.3 mAh g-1 at 200 mA g-1 even after 1000 cycles, polysulfides and surface Ti atoms was attributed to mitigation
demonstrating its long-term cycling stability and experimentally of the loss of active material, and consequential good cycling
observed the formation of double Na-atomic layers amongst performance.178 Recently, Lin et al. incorporated delaminated
the Ti3C2Tx interlayers, thus reaffirming the possibility of multi- HCl/LiF-prepared Ti3C2Tx into a glass fiber membrane for Li-S
layer adsorption (Fig. 22a-f).174 Kajiyama et al. related a small batteries via simple vacuum filtration. Highly active surfaces of
portion of Na+ being trapped within the structure of Ti3C2Tx even Ti3C2Tx chemically bonded with lithium polysulfides (LiPSs) via
after full desodiation to an increase of interlayer distance from strong metal-sulfur interactions, thereby suppressing the
9.7 Å to 12.5 Å; together with the penetrated solvent molecules, dissolution of LiPSs. The performance of commercial bulk S
they beneficially swelled the interlayer spaces of Ti3C2Tx during cathode was greatly improved to a high reversible capacity of
initial cycles of sodiation.175 Xie et al. experimented with a self- 591 mAh g-1 at 1.5 A g-1 after 100 cycles.179 Bao et al. synthesized
assembled porous multi-layered Ti3C2Tx/MWCNTs composite a hierarchical structure of 20 wt. % HF-etched
that measured a high volumetric capacity of 421 mAh cm-3 at 20 Ti3C2Tx/Mesoporous C by a single-step pyrolysis of Ti3C2Tx/MOF-
mA g-1.57 Another MXene, V2CTx, was paired with hard carbon 5 at 900 °C for 3 h in argon and subsequent HF etching to
and assembled into full cell, achieving a capacity of 50 mAh g - remove ZnO. Ti3C2Tx/MOF-5 was obtained from solvothermal
1.176
synthesis of a 40 mL DMF mixture, containing 10 mg of Ti 3C2Tx,
0.6 mmol of zinc nitrate hexahydrate, 0.2 mmol of terephthalic
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 23
acid and 0.085 mL triethylamine, at 105 °C for 24 h. The (a) (b) View Article Online
Ti3C2Tx/Mesoporous C/S composite cathode, from heating DOI: 10.1039/C6TA06772G
Ti3C2Tx/Mesoporous C and elemental sulfur at 155 °C for 10 h
in Ar, attained a high reversible capacity of 704.6 mAh g-1 at
current density of 837.5 mA g-1 (C/2) after 300 cycles. Its good
3.5 Electrocatalysts
Published on 13 December 2016. Downloaded by Freie Universitaet Berlin on 14/12/2016 01:13:30.
24 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx
By screening 48 MXenes using ab initio calculations, Guo et Because a myriad of cations is observed to spontaneously
View Article Online
al. shortlisted two yet-to-be-synthesized but stable MXenes, intercalate MXenes, the implications DOI: are 10.1039/C6TA06772G
far-reaching and
Zr2CO2 and Hf2CO2, with good optical absorption in the influential as seen with delaminating stacked MXenes,
wavelength from 300 to 500 nm and high and directionally preparation of MXene composites and their various potential
anisotropic carrier mobility as candidate single photocatalyst applications.
Ti3C2Tx provided effective electron pathway for the transfer of potential applications, are to be explored.
electron from Ti or C to Ag and numerous favourable oxygen Experimentally, in most polymeric-based composites,
adsorption sites. The Ti-doping of Ag nanowires, increased the beyond the ubiquitous single/few layers of DMSO-intercalated
concentration of defects or vacancies, which provided even HF-etched Ti3C2Tx fillers, incorporation and studies of other
more oxygen adsorption sites. These Ti-doped Ag nanowires experimentally viable, exfoliated single/few-layered MXenes as
could also act as a bifunctional catalyst to catalyse different ORR fillers in polymer composites remain bewildering unexplored.
steps.77 Detailed investigations of mechanism of matrix-filler interfacial
Xie et al. explored the use of HF-etched Ti3C2Tx as more interaction(s), quantification and characterization of enhanced
active and durable support for platinum (Pt) nanoparticles mechanical properties of polymeric composites with inclusions
cathode catalyst for proton exchange membrane fuel cells. The of different MXene-based fillers, variation in processing
20 wt. % Pt/ Ti3C2Tx was prepared by refluxing a homogeneous pathways to manipulate stacking of fillers within polymeric
mixture, containing ethylene glycol, 320 mg of Ti3C2Tx, 240 mg matrices can provide invaluable insights and contribute to the
of trisodium citrate dehydrate and 160 mg of chloroplatinic development of future applications.
acid, at 160 °C for 2 h in N2. The numerous –OH and –F groups As the most well-studied MXene, Ti3C2Tx and its composites
on HF-etched Ti3C2Tx served as anchor points that facilitated have been explored as candidates for the sequestration of
well dispersion and strong binding of Pt nanoparticles. It was heavy metal pollutants and absorption of dyes and
also suggested that the strong Pt-Ti3C2Tx interaction could have radionuclide. Also, they could be used as biocide in water
altered the electronic structure of Pt nanoparticles prevented treatment, which has demonstrated promising results.
the oxidation and subsequent dissolution of Pt catalyst.184 Experimentally, much work remains to be conducted to fully
understand the difference in absorption of various ions, when
deploying in a more complex but realistic environmental setup.
4. Conclusions and Outlook To evaluate the reliability and lifespan of the proposed systems,
In summary, we have provided an overview of the progress in more comprehensive studies are required to clarify the actual
synthesis, characterization and applications of the new family mechanism and reversibility of absorption and release
of 2D early transition metal carbides, carbonitrides and nitrides, ions/molecules/pollutants/radionuclide by Ti3C2Tx and
by using different fluoride compounds as etchants under investigate the degradation in performance after repeated
various conditions. Two of the most mature synthesis routes to usage. One such example reported up to date is the first use of
layered carbides and carbonitrides are HF etching and HCl/LiF HF-etched multi-layered Ti3C2Tx as a novel intercalation
etching, electrode for desalination via capacitive deionization (CDI).
each brings about multi-layered MXenes with different By varying the synthesis conditions, fundamentally different
morphologies and surface chemistries. Although only weak Ti3C2Tx, in terms of the degree of exfoliation and delamination
residual forces hold and prevent HF-etched multi-layered (i.e., number of atomic layers) and the proportion of surface
MXenes from readily separating into individual layers, a mere terminations, and consequently electromagnetic wave
sonication procedure without preceding intercalation of species absorption or shielding performance, have been discussed.
between the layers can only result in low yield of single/few- More interestingly, surface modification to the MXene, use of
layered MXenes. other members in the MXenes family or MXene-based
Most recently, with a modified HCl/LiF etching procedure composites with the inclusion of magnetic nanostructures all
with an increased molar ratio of LiF to Ti3AlC2 of 7.5:1 instead of deserve to be further explored.
5:1, while other aspects of the procedure (in 6 M HCl solution at The use of MXene-based composites, with different filler(s),
35°C for 24 h) remained identical to that reported by Ghidiu et such as metal oxides with higher specific capacity, for energy
al., delaminated Ti3C2Tx flakes have been reportedly obtained storage applications, are inevitable, due to the inherent
without sonication and their yield can be further improved with moderate theoretical capacity of MXenes. Incorporation of
a more concentrated HCl etchant solution. These delaminated interlayer spacers, such as CNTs or PPy, to provide additional
Ti3C2Tx flakes are observed to be 4‒15 μm laterally, have well- electron conductive pathways and maintain interlayer spaces
defined and clean edges and exhibit no visible pin holes. that promote electrolyte ion access and transportation, has
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 25
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