Recent Progress in Layered Transition Metal Carbides andor Nitrides (MXenes) and their Composites Synthesis and Applications

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K. Zhou, P. S. Lee, W. Que, Z. J. Xu and L. B. Kong, J. Mater. Chem. A, 2016, DOI: 10.1039/C6TA06772G.

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DOI: 10.1039/C6TA06772G
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Journal of Materials Chemistry A Accepted Manuscript


REVIEW

Recent Progress in Layered Transition Metal Carbides and/or


Nitrides (MXenes) and their Composites: Synthesis and
Received 00th January 20xx,
Applications
Published on 13 December 2016. Downloaded by Freie Universitaet Berlin on 14/12/2016 01:13:30.

Accepted 00th January 20xx


Vincent Ming Hong Ng a, Hui Huang b, Kun Zhou c, Pooi See Lee a, Wenxiu Que d, *, Jason Zhichuan
DOI: 10.1039/x0xx00000x Xu a, * and Ling Bing Kong a, *
www.rsc.org/ Since its inception in 2011, from the inaugural synthesis of multi-layered Ti3C2Tx by etching Ti3AlC2 with hydrofluoric acid
(HF), novel routes with myriad of reducing agents, etchants and intercalants have been explored and added many new
members to the two-dimenisonal (2D) material constellation. Despite being endowed with the rare combination of good
electronic conductivity and hydrophilicity, their inherent low capacities, for instance, temper their prospect in application
for electrodes in energy storage systems. MXene-based composites, however, with probable synergistic effect in
agglomeration prevention, facilitating electronic conductivity, improving electrochemical stability, enhancing
pseudocapacitance and minimizing the shortcomings of individual components, exceed the previously mentioned
capacitance ceiling. In this review, we summarise the development and progress in synthesis of various multi-layered
carbides, carbonitrides and nitrides, intercalants, as well as the subesequent processing in order to delaminate them into
single- and/or few-layered and modifications to MXene-based composites, focusing on their performances and applications
as transparent conductive films, environmental remediation, electromagnetic interference (EMI) absorption and shielding,
electrocatalysts, Li-ion batteries (LIBs), supercapacitors and other electrochemical storage systems.

constellation by quite a large number, when the A layers are


1. Introduction selectively extracted, leaving the Mn+1Xn layers intact. 3-5
These layered hexagonal Mn+1AXn phases are composed of
In 2011, a new two-dimensional (2D) early transition metal two formula units per unit cell, where M layers are nearly closed
carbide, Ti3C2, was first synthesized by selectively etching the Al packed with X atoms filling between the octahedral sites and
atoms in layered hexagonal (space group P63/mmc) ternary the Mn+1Xn layers are interleaved with layers of A atoms.6 These
carbide, Ti3AlC2, with the use of aqueous hydrofluoric acid (HF) laminated structures have anisotropic properties for the M-X
at room temperature (RT).1 Ti3AlC2 is one of the 70-plus bond has an assortment of ionic/covalent/metallic
different known ternary carbides and nitrides with general characteristics while the M-A bond is purely metallic in nature.
chemical composition Mn+1AXn, where M is an early transition The strong bonds between the layers in Mn+1AXn phases, unlike
metal, A is primarily a group 13 or 14 (i.e. group IIIA or IVA) the weak van der Waals interactions present in other layered
element, X is C and/or N, and n = 1, 2, or 3.2 Additionally, materials such as graphite and transition metal dichalcogenides
Mn+1AXn can also be synthesized with solid solutions of M, A and (TMDs), are unsurmountable by mere mechanical exfoliation
X atoms, such as (Mo2Ti)AlC2, Ti3(Al0.5Si0.5)C2 and Ti2Al(C0.5N0.5), into 2D layers.7 However, by exploiting the varied
respectively, prospectively augmenting the 2D material characteristics and relative strengths between M-X and M-A
bonds, the relatively weak bound and reactive A layers can be
selectively etched with suitable chemical(s) leaving behind the
chemically more stable closed packed Mn+1XnTx layers. Tx refers
a. School of Materials Science and Engineering, Nanyang Technological University, to surface-terminating functional groups such as oxygen (=O),
50 Nanyang Avenue, Singapore 639798. Email: [email protected],
[email protected] hydroxyl (–OH) or fluorine (–F) that are attached to the surface
b. Singapore Institute of Manufacturing Technologies (SIMTech), 71 Nanyang Drive, M atoms after the etching procedure. The thickness of the
Singapore 638075. Mn+1XnTx is dependent on the value of n. For example, when n =
c. School of Mechanical & Aerospace Engineering, Nanyang Technological

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

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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

Journal of Materials Chemistry A Accepted Manuscript


transformation and subsequent partial loss of layering are
inevitable.8 High temperature chlorination causes the removal
of both M and A components and yields porous carbide derived
carbons (CDC) instead.9 (c) (d)
Although two existing reviews have been dedicated
extensively to synthesis and potential applications of MXenes,
and a few others on its energy storage applications, none covers
Published on 13 December 2016. Downloaded by Freie Universitaet Berlin on 14/12/2016 01:13:30.

its progress as composite materials.10-13 In this review, the


advancement of MXene and its composites, encompassing both
theoretical and experimental studies of relevance to their
synthesis, properties and potential applications in the field of
transparent conductors, environmental remediation and
energy storage, will be detailed and discussed.
(e) (f) (g)

2. Synthesis and characterizations

Since the pioneering synthesis of multi-layered Ti3C2Tx through


HF etching at RT, much work has been channelled towards
discovering novel routes to preparing existing and new MXenes.
To date, even with the myriad of synthesis conditions and
reagents identified, fluoride-based compounds remain an Fig. 1 (a) Schematic for the structure of −OH-terminated Ti3C2 after
incumbent component to effective preparation of these 2D selective etching of Ti3AlC2; yellow, black, red and white circles
transition metal carbides. Intuitively, the synthesis route represent Ti, C, O and H atoms, respectively. (b) STEM image of the
adopted will be influential over their surface chemistries and first two Ti3C2Tx layers after applying Wiener filter; scale bar is
consequential behaviour. Characterizations of these materials equivalent to 1 nm, atoms are shown with the same colors as (a)
have shed light on some of their properties and prompted [reprinted with permission from ref. 25. Copyright 2014 American
further investigations, studies, and processing to optimally Chemical Society]. (c) Schematic for the structures of parent
exploit the advantages of MXenes, especially so in the case of Mo2TiAlC2 phase and exfoliated HF-etched Mo2TiC2Tx phase,
respectively; red, green, blue and black circles represent Mo, Ti, Al
composites.
and C atoms, respectively. (d) XRD patterns of Mo2TiAlC2 (red), HF-
etched Mo2TiC2Tx (green) and delaminated HF-etched Mo2TiC2Tx
2.1 Multi-layered stacked MXenes (blue). In the delaminated sample, only c-direction peaks, (00l)
The inaugural synthesis of multi-layered Ti3C2Tx was reported peaks, are visible, corresponding to a c lattice parameter of 30.44 Å;
the (110) peak is no longer observed, indicating loss of order in non-
by Naguib et al. Ti3AlC2 powders, prepared by using a typical
basal directions. (e and f) HRSTEM of Mo2TiAlC2 and Mo2TiC2Tx,
route of heating a pre-ball milled mixture of Ti2AlC and TiC (with respectively. Atoms are shown with the same colors as (c). Atomic
a molar ratio of 1:1) at 1350 °C for 2 h in argon (Ar), was ordering is verified by EDX mapping. No Al was observed in EDX of
immersed and kept under stirring in a 50 % concentrated HF Mo2TiC2Tx. (g) Low magnification TEM image of layered structure
solution at RT for 2 h, followed by filtration to separate residue throughout the sample of exfoliated HF-etched Mo2TiC2Tx
[reprinted with permission from ref. 17. Copyright 2015 American
from the supernatant and repeated washing of the residue with
Chemical Society].
deionized (DI) water.1 This simple selective etching of the
parent Mn+1AXn phases with Al was then successfully extended Mn+1AXn phases with Al, as the Mo2CTx layers were formed by
and yielded multi-layered Ti2CTx, Ta4C3Tx, (V0.5Cr0.5)3C2Tx, HF-etching of Ga in Mo2Ga2C.19 Interestingly, Zhou et al.
(Ti0.5Nb0.5)2CTx, Ti3CNxTx, Nb2CTx, V2CTx, Nb4C3Tx, Mo2TiC2Tx (Fig. recently managed to synthesize the first layered Zr3C2Tx by
1c-g), Mo2Ti2C3Tx, Cr2TiC2Tx and (Nb0.8Ti0.2)4C3Tx.14-18 This extending this HF-etching protocol to Zr3Al3C5, an alternative
preferential etching of the M-A bond in Mn+1AXn phases with Al layered ternary and quaternary transition metal carbide beyond
may be summarized as: the Mn+1AXn phases.20
Mn+1AlXn + 3HF → Mn+1Xn + AlF3 +1.5H2 (1) Notably, essential etching conditions such as HF
Mn+1Xn + 2H2O → Mn+1Xn(OH)2 + H2 (2) concentration, duration of immersion and temperature
Mn+1Xn + 2HF → Mn+1XnF2 + H2 (3) necessary to completely convert various parent Mn+1AXn phases
Eqs (2) and (3) indicate the surface terminations by a into multi-layered Mn+1XnTx expectantly vary widely.15, 21, 22 For
combination of –OH and –F as aqueous etching of Al do not instance the very conditions that yield Ti3C2Tx from Ti3AlC2 (50
result in bare M layers.1 Meshkian et al. demonstrated that this % HF, 2 h, RT) completely dissolve Ti2AlC. The less stable (lower
selective etching by HF can be applicable beyond parent n value in Mn+1AlXn) Ti2CTx is instead obtained by immersing

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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

Journal of Materials Chemistry A Accepted Manuscript


complete dissolution or recrystallization of Mn+1XnTx layers may Wang et al. reported a novel hydrothermal synthesis of
occur under excessive heating.14, 24 As smaller particle sizes of multi-layered Ti3C2Tx by using only Ti3AlC2 and NH4F, where the
the parent Mn+1AXn can effectively reduce the required etching influence of reactants’ ratio, reaction duration and temperature
duration and/or HF concentration, the as-synthesized Mn+1AXn on the yield of Ti3C2Tx were detailed. The optimal conditions to
powders are usually subjected to attrition or ball milling and/or produce multi-layered Ti3C2Tx via this hydrothermal synthesis
sieved prior to chemical exfoliation. route was established to maintain the reaction mixture, with 5.0
Halim et al. introduced a less hazardous and milder etchant, g of NH4F and 0.5 g of Ti3AlC2 in 60 mL of DI water, isothermally
Published on 13 December 2016. Downloaded by Freie Universitaet Berlin on 14/12/2016 01:13:30.

i.e., 1 M ammonium bifluoride (NH4HF2) solution at RT albeit at 150 °C for 24 h.28


longer immersion duration, which could concomitantly Xie et al. attempted a fluoride-free reaction via immersing
intercalate ammonium species such as –NH3 and –NH4+ and Ti3AlC2 in a solution of 1 M sodium hydroxide (NaOH) at 80 °C
effectively etch the Al layers in epitaxial Ti3AlC2 films (Fig. 1a- for 100 h, followed by a hydrothermal treatment in 1 M H2SO4
b).25 Such observation of spontaneous intercalation of cations at 80 °C for 2 h. However, it was only partially successful with
(Li+, Na+, Mg2+, K+, NH4+ and Al3+) in between Ti3C2Tx layers was merely the surface Al, but not bulk, leached from parent Ti3AlC2
also reported by Mashtalir et al., with implications that were phase.29
far-reaching and influential in the later development of Ghidiu et al. then introduced another high-yield but safer
delaminating stacked MXenes (to be discussed under Section alternative synthesis route to multi-layered Ti3C2Tx by
2.2. Single/ Few-layered MXenes), preparation of various immersing Ti3AlC2 powders in a milder etchant solution of 6 M
MXene composites (to be discussed under Section 2.3. MXene- hydrochloric acid (HCl) with certain amount of lithium fluoride
based Composites) and potential applications (to be discussed (LiF) under constant stirring at 35 °C for 24 h (Fig. 2a-f).30
under Chapter 3. Properties and Applications) .26 Feng et al. Interestingly, a clay-like paste of Ti3C2Tx with intercalated water
detailed the influence of temperature and etching duration for and ions was collected at the after repeated washing with DI
the synthesis of Ti3C2Tx in 1 M of various bifluoride solution (e.g., water, which could be conveniently shaped to desired forms or
NaHF2, KHF2, or NH4HF2). The minimum etching duration for the rolled to produce flexible, free-standing films (Fig. 2c Inset) in
onset of exfoliating Ti3AlC2 in 1 M of bifluoride solution at 60 °C lieu of the tedious sequence of procedures for HF-etched
samples as reported elsewhere.31 To varying degree of success,
(a)
other fluoride salts, such as sodium fluoride (NaF), potassium
fluoride (KF), caesium fluoride (CsF), tetrabutylammonium
fluoride, calcium fluoride (CaF2), could be added in place of LiF
into either HCl or sulphuric acid (H2SO4) to prepare the etchant
solution. It is highly conceivable that a delicate balance of
etching conditions for different combinations with as
(b) (c)
mentioned acid and salt, can potentially bring about a myriad of
applicable multi-layered early transition metal carbide
compositions and properties, due to modified surface
chemistries and diverse pre-intercalated ions. This one-step
method has been successfully applied to produce multi-layered
Nb2CTx, Ti2CTx, Cr2TiC2Tx, Mo2TiC2Tx, Mo2Ti2C3Tx, Mo2CTx and
(Nb0.8Zr0.2)4C3Tx as well.17, 18, 30, 32
(d) (e) Although selective etching with aqueous acid solutions at RT
has capably used to produce various carbide and carbonitride
MXenes, nitride MXenes such as Ti4N3Tx remain hitherto elusive
(f) as nanosheets of Ti4AlN3 are collected instead after immersion
in HF solution at RT.33 Two factors have been conjectured for
the above phenomenon. Firstly, more energy may be necessary
for extraction of the strongly-bound Al from Tin+1AlNn than from
Tin+1AlCn as indicated by the higher formation energies of
Fig. 2 (a) Schematic for Ti3C2Tx ‘clay’ synthesis by HCl/LiF etching and Tin+1Nn than that of Tin+1Cn. Secondly, Tin+1Nn is less stable as
preparation into free-standing and desired shape electrode. (b) XRD
plots of Ti3AlC2 and Ti3C2Tx. (c) SEM image of cross-section of rolled compared with Tin+1Cn as suggested by the lower calculated
Ti3C2Tx. TEM images of (d) several flakes of Ti3C2Tx with lateral sizes cohesive energies of Tin+1Nn, so that the as-prepared Tin+1Nn
up to a few hundred nanometres, (e) single-layered Ti3C2Tx, and (f) could have probably been dissolved in concentrated HF
double-layered Ti3C2Tx [reprinted with permission from ref. 30. solution.10, 34 Urbankowski et al. reported an ingenious
Copyright 2014 Nature Publishing Group]. synthesis of multi-layered Ti4N3Tx by thermally treating a

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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.

Journal of Materials Chemistry A Accepted Manuscript


% NaF, was purposefully selected.36
Expectantly, some differences were observed between the
different preparation routes (using HF or solution of HCl with
LiF). For instance, accordion-like Ti3C2Tx samples are obtained
from HF treatment, whereas laterally larger flakes of Ti3C2Tx (c) (d)
with negligible nanoscale defects are yielded by using HCl plus
LiF.30
Published on 13 December 2016. Downloaded by Freie Universitaet Berlin on 14/12/2016 01:13:30.

A complete transformation from Mn+1AXn phases to multi-


layered Mn+1XnTx could be identified by the remnant (000l) X-ray
diffraction (XRD) peaks, while all other peaks are weakened or
vanish. Evidence of small quantity of unreacted Ti3AlC2 has been
picked up by XRD, in addition to the shift in (0002) peak to lower
angles, a consequence of the crystal structure parameter that is
directly proportional to the distance between individual MXene Fig. 3 (a) Side view schematic of a M3X2Tx structure showing various
layers, with c lattice parameter of ca. 25 Å, for the HCl/LiF- M atoms and their terminations. I refers to a M atom bonded to an
derived multi-layered Ti3C2Tx as compared with the HF-etched O atom; II, to OH; III, to a M atom directly bonded to a F-atom; IV, to
an M atom bonded to OH, that, in turn, is strongly bonded to a H2O
counterpart (c lattice parameter of ca. 20 Å).37 A number of molecule; M atoms only bonded to C atoms are designated, M*.
caveats that concern the validity of quantifying unreacted Yellow, black, red, white and blue circles (not to scale) represent M,
Mn+1AXn phases for XRD intensities tend to fade with increased X, O, H and F atoms, respectively [reprinted with permission from
degree of exfoliation and coexistence of Mn+1AXn phase peaks ref. 38. Copyright 2016 Elsevier]. (b) 1H NMR (11.7 T) spectra of HF
with Mn+1XnTx (000l) peaks.10 Correspondingly, exfoliated Ti3C2Tx and HCl/LiF etched Ti3C2Tx recorded at 60 kHz MAS. (c) 19F NMR (11.7
T) spectra of HF and HCl/LiF etched Ti3C2Tx recorded at 60 kHz MAS.
stacks by etching Ti3AlC2 at 35 °C for 24 h with 6 M HCl with LiF (d) Graphical comparison of the differences in composition of the
have persistent Mn+1AXn phase peaks in the XRD patterns, even Ti3C2Tx surface functional groups when synthesized by HF and HCl/LiF
though they readily are delaminated upon sonication.30 etching respectively [reprinted with permission from ref. 37.
X-ray photoelectron spectroscopy (XPS) characterizations Copyright 2016 the Owner Societies].
are generally able to identify the presence of negatively- groups to Ti3C2Tx surfaces. Furthermore, quantitative NMR
charged =O, –OH and –F terminations, indicative of Mn+1Xn experiments demonstrated that majority of the surface
surfaces having a fixed net positive charge, as an overall terminations are present as an intimate mixture of –O and –F,
neutrality has to be maintained.31, 38 In fact, the distribution of while –OH is in the minority. More importantly, it is established
these surface terminations (Fig. 3a) are dependent on that the proportion of the surface terminations is highly
parameters such as the number of layers, the identity of M and sensitive to the synthesis route adopted (Fig. 3b-c). For
X element and so on. For instance, in Ti3C2Tx, Ti2CTx and Ti3CNTx, example, there are about fourfold of –F termination in HF-
with varying number of layers, n, or X element, the proportion etched Ti3C2Tx as compared with that in the HCl/LiF-prepared
of –F terminations remain invariant while the –O to –OH ratio Ti3C2Tx (Fig. 3d).37
increases as n is increased. Conversely for Nb2CTx and Nb4C3Tx, These results are significant because they highlight useful
the –O to –OH ratio decreases as n is increased.38 strategies towards manipulating morphologies and surface
Energy-dispersive X-ray spectroscopy (EDS) experiments chemistries; choice of etchant solution, etchant concentration,
have been employed to quantify their proportions, although temperature and duration of immersion. For electronic and
EDS is unable to differentiate –O and –OH, because various optical applications, where defect-free and large sheets are
factors, such as the presence of adsorbed water and etching by- more desirable, the use of HCl/LiF etchant solution may be more
products, could complicate the signal collection.1, 30 preferential to HF solution. Conversely, for energy storage and
Nuclear magnetic resonance (NMR) spectroscopy, with high catalysis applications, where higher ion accessibility and edge
sensitivity towards 1H and 19F nuclei, has been employed in two effects may be more valued, the route with HF solution which
recent studies to determine sample compositions with produces defective and nanoporous/pitted flakes may be of
increased confidence and to provide insights to surface more relevance. Evidently, more work is needed to develop a
functionalisation of V2CTx and Ti3C2Tx respectively.37, 39 In the fluoride-free MXene synthesis protocol as well.
study of HF-etched V2CTx, Harris et al. through 1H NMR
experiments distinguished that –OH groups are directly bonded 2.2 Single/Few-layered MXenes
to V2CTx, with a layer of -H (from H2O) bonded to the –OH
With the strong M-A bonds to be replaced with weak bonds,
surface; while 19F NMR experiments evidently indicated that the
such as hydrogen and van der Waals forces, intercalation and
–F groups are indeed directly bonded to V2CTx surfaces.39 Hope
delamination of multi-layered stacked MXenes into single or
et al. reaffirmed direct connection of both the –OH and –F

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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

Journal of Materials Chemistry A Accepted Manuscript


intercalated water and possibly cations between the multi- 7.5:1) in 6 M HCl solution at 35 °C for 24 h.42 Exfoliated Ti3C2Tx
layered MXenes acting as spacer and lubricant that facilitated flakes, with molar ratio of LiF to Ti3AlC2 to be 5:1, are observed
shearing. It is noted that although etching Ti3AlC2 at higher to be 200‒500 nm in diameter, have uneven edges decorated
temperature for longer duration (40 °C for 45 h) yields Ti3C2Tx with TiO2 nanoparticles and numerous pin holes (Fig. 4a),
with lower Al content as verified by EDS, the ease of whereas exfoliated Ti3C2Tx flakes, with molar ratio of LiF to
delamination and dispersion by mere sonicating are not as Ti3AlC2 to be 7.5:1, are 4‒15 μm laterally, have well-defined and
readily as that of Ti3C2Tx ‘clay’ obtained under reaction clean edges and no visible pin holes (Fig. 4b) under high
Published on 13 December 2016. Downloaded by Freie Universitaet Berlin on 14/12/2016 01:13:30.

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

Journal of Materials Chemistry A Accepted Manuscript


for 6 h.31 Other organic intercalants such as thiophene, ethanol,
acetone, tetrahydrofuran, formaldehyde, chloroform, toluene
and hexane, were found to be unsuitable with the exceptions of
hydrazine monohydrate (HM), N2H4.H2O, dissolved in N,N- (c) (d)
dimethylformamide (DMF) and urea as evident by the observed
shift in major XRD peaks towards lower angles. This same group
in a later study utilized inelastic neutron scattering (INS)
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analysis, highly sensitive to 1H atom, to characterize pristine and


HM intercalated HF-etched multi-layered Ti3C2Tx. It was
concluded that HM intercalation into Ti3C2Tx led to substantial
reduction of water content, as well as the quantity of –OH and
–F terminations.44 However, the prospect of intercalating DMSO
is severely limited by its exclusive effectiveness towards
delaminating Ti3C2Tx, probable difficulty with thorough removal Fig. 5 (a) TEM image of an individual Ti4N3Tx flake. Inset shows the
SAED pattern of the Ti4N3Tx flake, inheriting the hexagonal basal
of high boiling point solvents used. Furthermore, lamellar
plane symmetry of the parent Ti4AlN3 phase. (b) Raman spectra of
thickness can be undesirably increased by remnant DMSO Ti4AlN3 (red curve) and delaminated Ti4N3Tx (blue curve), with
molecules, which joined the delaminated sheets together. Till corresponding vibrational peaks identified through fitting with a
date, the exact mechanism to explain how and why DMSO only product of Gaussian and Lorentzian functions [reprinted with
interact with multi-layered Ti3C2Tx remains unclear. permission from ref. 35. Copyright 2016 The Royal Society of
Chemistry]. XRD patterns of (c) Ti3CNTx before TBAOH intercalation,
Naguib et al. introduced another simple and scalable
and after mixing with TBAOH for 2, 4, and 21 h (black, red, blue and
approach towards delamination of HF-etched multi-layered green curves, respectively); (d) V2CTx before TBAOH intercalation,
Ti3CNTx, V2CTx and Nb2CTx via intercalation of relatively large and after mixing with TBAOH for 2, and 4 h (black, red, and blue
basic organic molecules such as tetrabutylammonium curves, respectively). The peaks denoted by * are from remnant
hydroxide (TBAOH), choline hydroxide or n-butylanime at RT Mn+1AXn phases. Insets are schematics of the Mn+1XnTx unit cells prior
to, and after, TBAOH intercalation accompanied by the
over some duration, followed by mechanical agitation (shaking
corresponding change in the c lattice parameter [reprinted with
or sonication) (Fig. 5c-d).45 The surface chemistry of these permission from ref. 45. Copyright 2015 The Royal Society of
MXenes was concomitantly altered, since most of the –F Chemistry].
terminations were eliminated. Similarly, by using TBAOH as the
intercalant, with the aid of sonication, Urbankowski et al. sonication.48 The intercalation of Na+ is essential, as it further
managed to delaminate multi-layered Ti4N3Tx into a mixture of weakens the interlayer cohesive forces and allows the
single- and few-layered sheets (Fig. 5a-b).35 accommodation of aryl diazonium salts. Unreacted diazonium
Mashtalir et al., on the other hand, delaminated HF-etched salts, being water-soluble, are relatively easier to remove as
multi-layered Nb2CTx by first intercalating isopropylanime (i- compared with the unreacted organic precursor(s) as used in
PrA) between the layers in DI water at RT for 18 h and then other methods. Dispersing of Ti3C2Tx in water can be improved
mildly sonicating in deaerated DI water. The HF-etched multi- with the grafting of aryl groups, while further surface
layered Nb2CTx, which is negatively charged at the surface and modifications are made possible by the increased active sites on
acidic, is expectedly intercalated with ammonium cation (R- the surface, due to the attached reactive functional groups p-
NH3+) in i-PrA dissolved in water, presumably due to the phenyl-SO3H from the aryl diazonium salts.48, 49 However, the
electrostatic forces.26, 46 Increase in efficiency of delamination applicability of this method towards other MXenes remains to
of Nb2CTx layers is anticipated as i-PrA molecules, having three be demonstrated.
alkyl groups, are sufficiently small to overcome the steric Zhang et al. first demonstrated the feasibility of a
hindrance, so as to push the Nb2CTx layers apart, thus further substitutional solid solution based exfoliation to obtain parent
weakening the interlayer interactions. When applying to Ti3CTx Mn+1AXn nanosheets, about 4 nm thick and 100 to 200 nm wide,
and Nb4C3Tx, it is noteworthy that, prior to sonication, multi- with ultrasonication in various organic solvents. It is suggested
layered Ti3CTx has been already found to partially delaminate that only when the A layer in Mn+1AXn phases consists of
after 18 h; which is in contrast to the lengthy (up to two weeks) different atoms and is in accordance to the Hume-Rothery rules,
period of immersion required for Nb4C3Tx.47 the effectiveness of breaking the bonds between A and MX
Wang et al. developed another alternative method that layers can be significantly enhanced.50 However, it is necessary
involved addition of dilute NaOH and maintaining stirring at RT to reemphasize that this low yield approach produces doped
for 2 h to intercalate Na+ between HF-etched multi-layered Mn+1AXn nanosheets but not MXenes. Thus, further treatments
Ti3C2Tx, followed by using sulfanilic acid diazonium salts as could be inclined towards complete conversion from these
surface modifier in an ice bath for 4h and finally mild Mn+1AXn nanosheets to MXene and/or composite nanosheets, in

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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

Journal of Materials Chemistry A Accepted Manuscript


standing Ti3C2Tx/polyvinyl alcohol (PVA) composite by using bands’ intensity of PEI in Ti3C2Tx/PEI composite. Intuitively,
vacuum filtration of colloidal solutions of delaminated HF- these fillers hinder polymer chain motion and enhance
etched multi-layered Ti3C2Tx with DMSO as the intercalant, in structural stability and solvent resistance of the PAN/PEI-Ti3C2Tx
the presence of varied amount of PVA (Mr = 115, 000). The membrane. Consequential of their large lateral area and small
Ti3C2Tx/PVA composite was established, because the PVA matrix thickness, most Ti3C2Tx nanosheets are horizontally-aligned and
had a strong interaction (hydrogen bonding) with the negatively well dispersed within the PEI matrix, as observed with scanning
charged surface of the Ti3C2Tx fillers. Because of the film electron microscopy (SEM). With 2 wt. % Ti3C2Tx, the rejection
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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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with aligned and doped pyrrole (PPy), C4H4NH, confined


View Article Online
(a) (b) between the Ti3C2Tx single layers (Fig. DOI: 6c).10.1039/C6TA06772G
The solution for
vacuum filtration to obtain the composite film was prepared by
adding the as-received PPy to a dispersion of HCl/LiF etched
Ti3C2Tx, and constant stirring at 1000 rpm for 12 h at RT.

Journal of Materials Chemistry A Accepted Manuscript


Exploiting the acidic nature of Ti3C2Tx, PPy molecules may be
protonated and proceed to form longer chains. Similarly, with
the presence of =O, –OH and –F terminations on Ti3C2Tx
surfaces, hydrogen bonds may be established with the N-H
group in PPy oligomers, so that the polymerized chains are self-
aligned instead of being randomly aggregated. Concurrently,
(c) (d)
the PPy chains can be doped by –F to become conductive.
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Simultaneous intercalation, alignment, and metal free


polymerization of PPy on Ti3C2Tx were demonstrated. By
optimizing the content of PPy, which provides directional paths
for charge percolation between the Ti3C2Tx layers, the obtained
composites with enhanced electronic conductivity
demonstrated exceptional performance as electrodes of
supercapacitors.56
Fig. 6 (a) Schematic for the preparation of free-standing, sandwich-
like Ti3C2Tx/CNT paper. (b) Cross-sectional SEM images of Xie et al. proposed another electrostatic self-assembly
Ti3C2Tx/MWCNTs [reprinted with permission from ref. 55. Copyright method to prepare flexible free-standing composite films of 90
2014 John Wiley & Sons, Inc.]. (c) Cross-sectional TEM images of wt. % Ti3C2Tx/MWCNTs and Mo2CTx/MWCNTs from negatively
aligned PPy chains (bright) between Ti3C2Tx layers (dark) [reprinted charged delaminated HCl/LiF etched Ti3C2Tx and Mo2CTx and
with permission from ref. 56. Copyright 2015 John Wiley & Sons, positively charged MWCNTs as spacers. Self-assembly was only
Inc.]. (d) Zeta potential of HCl/LiF etched Ti3C2Tx nanosheets, CTAB-
grafted CNTs (CNT-CTAB), and self-assembled Ti3C2Tx/CNT-CTAB possible with MWCNTs grafted with cetyltrimethylammonium
(Ti3C2Tx/CNT-SA). Inset shows digital photographs of pristine Ti3C2Tx bromide (CTAB), a cationic surfactant (Fig. 6d). If the MWCNTs
suspension, CNT-CTAB in water, and Ti3C2Tx/CNT-SA composites were modified with an anionic surfactant, such as SDS, the self-
[reprinted with permission from ref. 57. Copyright 2016 Elsevier]. assembly was not successful and Ti3C2Tx and MWCNTs would be
randomly mixed Ti3C2Tx/CNT composite. This elucidates the randomly and separately deposited on the filter paper, while
effect of CNT dispersion conditions during the preparation and restacking of single- and few-layered Ti3C2Tx flakes remained
the implication on the arrangement of fillers, electronic unresolved. Consequently, the 90 wt. % Ti3C2Tx/MWCNTs-CTAB
percolation threshold and subsequent enhancement of overall composite displays encouraging volumetric capacity and rate
electronic transport properties as noted in the superior performance as Na-ion storage, because the CTAB-modified
conductivity of sandwich-like Ti3C2Tx/CNT composite (385 S cm- MWCNTs efficiently reduced the restacking of the single and
1) than that of randomly mixed Ti C T /CNT composite (286 S
3 2 x
few-layered Ti3C2Tx, thus improving the accessibility of
cm-1). It was generally observed that the inclusion of CNTs electrolyte to the active material, Ti3C2Tx. The CTAB-modified
enlarged interlayer space (i.e., c lattice parameter revealed by MWCNTs also formed a conductive network and enhance
XRD) between the Ti3C2Tx flakes, prevented the restacking of overall electronic conductivity of the composites.57
delaminated Ti3C2Tx sheets (Fig. 6b) and improved both the Lin et al. alternatively improved the electronic conductivity
overall conductivity and available active surface area within the of HF-etched multi-layered Ti3C2Tx, by growing conductive
composites and thus electrochemical performance in carbon nanofibers (CNFs) within the spaces of each accordion-
electrochemical capacitors (ECs), as compared with those of the like Ti3C2Tx particle and between the particles (Fig. 7a). The CNFs
pure Ti3C2Tx film.55 This alternating vacuum filtration method is within the void of Ti3C2Tx provide conductive pathways to
also advantageous for its simplicity, because no enhance charge transportation in the vertical-to-layer direction
functionalization of the materials is required. It could be used of each individual Ti3C2Tx particle and maintain the open
to quickly fabricate several micrometres thick film, though it accordion-like structure which is favourable for electrolyte ions
lacks the more controlled structures that can be realized by to access. Isolated Ti3C2Tx particles are connected by conductive
using the layer-by-layer (LBL) deposition method. network of CNFs, thereby drastically reducing contact
Similarly, Mashtalir et al., used i-PrA as the intercalant to resistance between the adjacent sheets.58 By using liquid-phase
delaminate HF-etched multi-layered Nb2CTx, and produce a impregnation, a cobalt (II) nitrate (Co(NO3)2 catalyst precursor
flexible and free-standing randomly mixed 90 wt. % and poly(vinyl pyrrolidone (PVP) dispersant were introduced
Nb2CTx/MWCNTs composite “paper”. A suspension of MWCNTs into the multi-layered Ti3C2Tx, while the succeeding heat
dispersed by 0.03 mol L-1 sodium dodecylsulphate (SDS) was treatment at 600 °C in Ar for 0.5 h led to the carbonization with
added into the colloidal mixture of mono- and few-layered acetylene as the carbonaceous source, and synchronous
Nb2CTx, followed by direct vacuum filteration.47 passivation of surface functional groups of Ti3C2Tx. The growth
Boota et al. introduced a simple strategy to prepare free- of CNFs followed the tip growth mechanism as evidenced by a
standing but brittle film of a self-assembled layered structure,

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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

Journal of Materials Chemistry A Accepted Manuscript


etched multi-layered Ti3C2Tx into 1 M of lithium hydroxide oxidation of HF-etched multi-layered Nb2CTx at 150 °C for 2h
(LiOH), the interlayer spaces could be enlarged and the –F yielded a hybrid structure of Nb2CTx, coupled with feather-like
surface terminations were converted to –OH ones. Through a non-crystalline Nb2O5, with a low content of amorphous
subsequent liquid-phase impregnation of a tin (IV) chloride carbon.60 Amongst these three synthesis routes, hydrothermal
(SnCl4) precursor with PVP dispersant, Sn4+ ions were anchored synthesis offers the most convenient control over morphology
on negatively charged Ti3C2Tx surfaces as an amorphous Sn (IV) of the oxide particles, together with the requirement of
complex, due to ion exchange and electrostatic interactions generally low temperatures albeit longer duration. Ghassemi et
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(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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etched multi-layered Ti3C2Tx, different amount ofView titanium (II)


Article Online
(a) 69 Through an in
sulfate (TiSO4) and DI water at 180 °C forDOI: 10.1039/C6TA06772G
18 h.
situ hydrolysis of tetrabutyl titanate (TBOT) within a mixture of
HF-etched multi-layered Ti3C2Tx, followed by either a
microwave-assisted hydrothermal synthesis or heat treatment

Journal of Materials Chemistry A Accepted Manuscript


in vacuum, Wang et al. synthesized another two types of
TiO2/Ti3C2Tx composites for potential applications in
electrochemical biosensors and supercapacitor electrodes.70, 71
The organ-like and conductive Ti3C2Tx structure, with high SSA,
capably channels large quantity of enzymes towards the interior
(b) (c)
and immobilizes them between the interlayers. Additionally,
biocompatible TiO2 nanoparticles present a protective and
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conducive environment for these enzymes to remain active and


collide with each other for long period.
Another group hydrothermally synthesized rutile
TiO2/Ti3C2Tx composites with various contents of HF-etched
delaminated Ti3C2Tx but fixed amount of titanium (IV) chloride
Fig. 8 (a) Schematic for structure of Nb4C3Tx and its hierarchical (TiCl4) at 95 °C for 4 h. TiO2 strategically encapsulated the
composite structure after oxidation. (b) TEM image of oxidized Ti3C2Tx, and this intimate contact allowed efficient charge
Nb4C3Tx at 850 °C for 0.5 h under a CO2 flow rate of 75 sccm. Inset transfer from TiO2 to Ti3C2Tx. The variation of Ti3C2Tx content in
shows a higher resolution TEM image [reprinted with permission the composites was reportedly influential towards deviation in
from ref. 63. Copyright 2016 John Wiley & Sons, Inc.]. (c) Pore size
both optical properties and photocatalytic performance as
distribution comparison of Nb2CTx before and after CO2 oxidation at
800 °C for 1 h at a CO2 feed rate of 150 sccm, the formation of 1.0- excessive Ti3C2Tx scattered light and prevented TiO2 from
1.5 nm pores is indicative of the formation of voids between the efficiently capturing light. This synthesis was extended to
layers of Nb2CTx after CO2 oxidation [reprinted with permission from prepare TiO2/Ti2CTx and TiO2/Nb2CTx composites.72
ref. 64. Copyright 2016 American Chemical Society]. Exceptionally, without additional Ti source, Peng et al.
higher surface areas), thus leading to a favourable mesoporous fabricated an atomic scale interfacial heterojunction of
structure to allow more access of aqueous electrolyte. homogeneously distributed (001) TiO2 nanosheets inserted in
Noticeably, annealing in N2/H2 atmosphere removed more layered Ti3C2Tx (Fig. 9a-f), through delicately controlled
functional groups on Ti2CTx, as inferred from the highest carbon hydrothermal oxidation of HF-etched multi-layered Ti3C2Tx in
content and lowest fluorine concentration, than in Ar or N2, and the presence of directing agent, sodium tetrafluoroborate
consequently exhibited the highest specific capacitance.66 Lai et (NaBF4). This minimally defective and interfacial well-bonded
al. also reported the preservation of initial Ti2CTx layered (001) TiO2/Ti3C2Tx hybrid exhibited significantly enhanced
framework and modifications to surface functional groups and photocatalytic activity as the defect-induced electron-hole
carrier transport properties (from metallic to semiconducting) recombination was reduced and highly conductive Ti3C2Tx
after subjecting mechanically exfoliated Ti2CTx sheets to efficiently conducted photogenerated electrons away and
thermal annealing.67 increased the lifetime of photogenerated electron-hole pairs.73
Ahmed et al. demonstrated a scalable, cost efficient and Zhang et al. fabricated a sandwich-like, magnetic
rapid method at RT to obtain TiO2/Ti2CTx hybrid. By immersing Ti3C2Tx/magnetite (Fe3O4)/maghemite (Fe2O3) composite with
HF-etched multi-layered Ti2CTx in hydrogen peroxide (H2O2) enhanced phosphate sorption selectivity and capacity. A
with various concentrations for different durations at RT, the mixture of 1 M FeSO4, 2 M iron (II) chloride (FeCl3) and HF-
amount of anatase TiO2 nanoparticles formed and embedded etched multi-layered Ti3C2Tx was held isothermally at 80 °C for
on the surface of multi-layered Ti2CTx could be well controlled. 4 h to facilitate ion exchange reactions that resulted in Ti-Fe in
The surface defects of HF-etched Ti2CTx acted as nucleation sites place of Ti–H terminations as well as intercalate Fe2+ and Fe3+
for TiO2 formation. For instance, after a brief (5 min) immersion ions. This mixture was then added to a boiling 6 M NaOH
in 30 wt. % H2O2, TiO2 nanoparticles were formed at the expense solution, to convert remnant Fe salts to Fe-based hydroxides. By
of Ti2CTx and the Ti2CTx layers were swelled, thus leading to a maintaining at 100 °C for 5 h, the Fe-based hydroxides were
five-fold increment in specific surface area (SSA) and more then transformed into nanosized ferrites.74
active sites for Li+ ions to intercalate. This hybrid has a molar Ren et al. developed a chemical etching procedure to
composition of one Ti2CTx and four TiO2. Comparatively, for an prepare mesoporous Ti3C2Tx at RT (Fig. 9g). An aqueous solution
extended period of immersion of 5 h, Ti 2CTx was completely of copper (II) sulphate (CuSO4) was added to a colloid of
converted into TiO2.68 delaminated HCl/LiF etched Ti3C2Tx. Catalysed by Cu2+ ions, the
A myriad of particulate TiO2/Ti3C2Tx composites have been dissolved O2 in water partially oxidized the Ti3C2Tx flakes,
hydrothermally synthesized, with or without additional variant forming TiO2 nanoparticles that were removed by subsequent
Ti precursors, at various heating temperatures for various HF treatment to leave behind porous Ti3C2Tx flakes (Fig. 9h)with
durations. Gao et al. prepared TiO2/Ti3C2Tx composites with more defects, less –F, more =O and –OH terminations and larger
promising photocatalytic activity by heating a mixture of HF- exposed surfaces.75 These mesoporous Ti3C2Tx flakes are then

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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

Journal of Materials Chemistry A Accepted Manuscript


than commercial 20 wt. % Ag/C and previous reported Ag-based
catalysts.77 This group also evaluated a HF-etched Ti3C2/Ag
(d) (e) (f)
composite, synthesized without the NaOH-activation-
treatment of Ti3C2Tx and PVP addition, as a high rate anode
material for Li-ion batteries with excellent cyclability.78
Chen et al. initiated, in the absence of an initiator, grafting
of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA)
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onto HF-etched multi-layered V2CTx by using a facile method of


(g) (h) self-initiated photografting and photopolymerization (SIPGP) to
prepare V2CTx@PDMAEMA composite.79 The cationic-charged
PDMAEMA favourably interacted with the negatively charged
surface of V2CTx to form a composite. Consequently, V2CTx was
endowed with the versatile reversible hydrophilic to
hydrophobic behaviour of PDMAEMA when thermally
stimulated and the controlled conductivity as triggered by
Fig. 9 Schematic for (a) Charge-transfer process over (001)
carbon dioxide (CO2) stimulation, and such functionalized V2CTx
TiO2/Ti3C2Tx, (b) Band alignments and charge flow at {001}
TiO2/Ti3C2Tx interfaces. (c) Low resolution TEM image of hybrids may potentially find applications in biological field.
TiO2/Ti3C2Tx. High resolution TEM image of (d) the area highlighted Experimentally, in most MXene/polymer composites to
by yellow box labelled b in (c), shows the intimate proximity of date, in which MXene is the additive and polymer serves as the
layered Ti3C2Tx and a TiO2 crystal, (e) the growth of TiO2 matrix, DMSO-intercalated HF-etched Ti3C2Tx single/few-
perpendicular to the [001] direction of the Ti3C2Tx sheet, and (f)
layered fillers have been unanimously added to polymeric
small TiO2 crystal formed near the edge of Ti3C2Tx. The insets (f1) and
(f2) show the lattice fringes of TiO2 and Ti3C2Tx respectively matrices. Polymeric-based composites which incorporate other
[reprinted with permission from ref. 73. Copyright 2016 American MXenes, beyond DMSO-intercalated HF-etched Ti3C2Tx,
Chemical Society]. (g) Schematic for the chemical etching of Ti3C2Tx expectedly remain unexplored because of the trickle-down
flakes to produce porous Ti3C2Tx structure. (h) TEM image of porous effect from the bottleneck in effective preparation of other
Ti3C2Tx after chemical etching in 0.2 M CuSO4 solution at RT
single/few-layered MXenes. Gradually, as more other exfoliated
[reprinted with permission from ref. 75. Copyright 2016 Wiley].
used together with MWCNTs to prepare electrode materials
(a) (b)
with promising performances.
Ma et al. combined delaminated HF-etched Ti3C2Tx and
exfoliated graphitic carbon nitride (g-C3N4) nanosheets through
vacuum filtration to form a robust free-standing hybrid film. It
exhibited outstanding performance in catalysing oxygen-
evolution reaction (OER) due to this novel coupled Ti-Nx motifs
acting as electroactive sites, high surface area from
hierarchically porous structure contributed to a high
electrochemical double layer capacitance. Additionally, its (c) c-1 (d)
hydrophilic and porous nature allowed good wettability of
active surfaces with aqueous electrolyte and rapid transport of
reactants to the active sites and fast removal of reaction
products, such as O2.76
Zhang et al. synthesized an urchin-shaped alkalization- c-2
intercalated HF-etched Ti3C2/Ag/Ag0.9Ti0.1 bimetallic nanowire
composite (Fig. 10a-d) by mixing 30 mM of AgNO3, 100 mg of 6
M NaOH-activation-treated Ti3C2Tx and 100 mg of PVP in DI Fig. 10 FESEM image of the HF-etched Ti3C2/Ag/Ag0.9Ti0.1. A and B
water at room temperature. It was proposed that the NaOH- represent a Ag nanowire and a Ag nanoparticle, respectively. (b)
activation-treatment of Ti3C2Tx substituted –F groups with –OH TEM image of the Ti3C2/Ag/Ag0.9Ti0.1. (c) HRTEM image of nanowire
groups and increased the c lattice due to ion exchange forming A. Inset (c-1) shows the width of Ag0.9Ti0.1 nanowire ∼42 ± 5 nm.
–ONa groups from some –OH groups. The presence of activated Inset (c-2) shows the SAED fringe confirming the nanotwinned Ag
structure. (d) HRTEM image of nanoparticle B with a 5-fold twin; the
low-valence Ti species on Ti3C2Tx was ascribed to Ag self- inset corresponds to the SAED of nanoparticle B [reprinted with
reduction while addition of PVP induced the formation of 5-fold permission from ref. 77. Copyright 2016 American Chemical
nanotwin Ag seeds (Fig. 10d), which subsequently grew into Society].

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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

Journal of Materials Chemistry A Accepted Manuscript


consideration its solubility in solvent(s) during processing, in Various as-synthesized MXenes are endowed with the rare
addition to having the polymer favourably interact with combination for 2D materials of good electronic conductivity
negatively-terminated MXene surface. Generally, mechanical comparable to multi-layered graphene and high hydrophilicity
properties of polymeric composites are enhanced with the with small contact angles measured.14 Intercalated epitaxial
addition of MXene fillers, although the orientation or how the MXene thin films (< 20 nm) are highly transparent with about 90 %
fillers are randomly stacked is influential towards if the transmittance (T) in the visible-to-infrared region.25 Weak coupling
enhanced mechanical properties are anisotropic or isotropic.52 between stacked MXene layers, spontaneous intercalation of a
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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

Journal of Materials Chemistry A Accepted Manuscript


(b)
H2, leaving behind Ti3C2 that strongly bond to –OH and –F. Density
of state and electron localization function calculations identified that
the functionalization of Ti3C2 was motivated by the formation of
strong bonds. Gibbs free energy (ΔG) calculations indicated that the
formation of fully fluorinated or mixed functionalized Ti3C2 were both
(d) (e)
thermodynamically favourable and conferred the random,
uncontrolled and mixed functionalization of Ti3C2. Consistent with a
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recent NMR study, more of –F terminations were observed due to


the preference of higher electronegativity of F ions and associated
greater stability to the overall structure.37 The random and non-
uniform distribution of surface termination groups on MXenes is
consequential of the chemical exfoliation process itself, and re-
emphasizes the need for development of alternative preparation
routes to achieve controlled functionalization of MXenes.
Early theoretical models predicted Ti3C2Tx configurations, in Fig. 12 Comparison between experimental high-resolution HAADF-
which surface termination groups were energetically favoured to be STEM images and simulated HAADF-STEM images for Ti3C2Tx MXene
from a single layer at two different off-tilt orientations: (a) α = 0 and
located either above the hollow sites between three neighbouring C
β = 0 mrad; (b) α = 0 and β = −189 mrad. Insets show the projected
atoms or above the C atoms on both sides of the Ti3C2 or a arrangement of Ti atoms for each case. (c) Atomic-scale HAADF-
combination of the aforementioned.97, 98 However, later STEM images of defects in single-layer Ti3C2Tx. Comparison between
computational studies revealed the complexity in the locations and experimental HAADF-STEM image, defect crystal structure
orientations of surface groups for they depended on the species (n determined from DFT, and simulated HAADF-STEM image of VTi.
HAADF-STEM images from single-layer Ti3C2Tx MXene flakes
values) and elemental compositions.100, 101 Xie et al. suggested that
prepared using etchants with different HF concentrations: (d) 2.7
=O and/ or –OH terminated MXenes were the most stable, because wt. % HF and (e) 5.3 wt. %. Single VTi vacancies and vacancy clusters
–F terminations were readily replaced by –OH groups, which could VTiC are indicated by red and blue circles, respectively [reprinted
occur when they were washed and/or stored in H2O; and –OH was with permission from ref. 108. Copyright 2016 American Chemical
converted to –O terminations during the high temperature Society].
treatments and/or metal adsorption processes.102 defects on the surface chemistry and electronic properties of Ti3C2Tx
Karlsson et al. investigated the structural, elemental and and derived at insensitivity of Ti3C2Tx’s conductivity to defect
chemical properties of single and double sheets of Ti3C2Tx (prepared concentration. Experimentally, with 2.7 wt. % HF etchant, vacancy
by immersion of 2.5 g of Ti3AlC2 1 M NH4HF2 for 5 days) by aberration- clusters were rarely observed in Ti3C2Tx single layer, however with
corrected atomic-resolution scanning transmission electron 5.3 wt. % HF etchant, vacancy clusters became more of a common
microscopy (STEM)-electron energy loss spectroscopy (EELS). Under sight (Fig. 12d-e).108
high angle annular dark-field (HAADF)-STEM imaging, with Ti-sites as Coinciding with DFT calculations, the electronic properties
reference, the inherited close-packed structure of Ti3C2Tx was (metallic or semi-conductive), thermodynamic stability, intercalation
observed as atomic positions of two Ti3C2Tx sheets remained laterally mechanisms and energy storage capability of MXenes are also found
aligned (Fig. 11b) even after the removal of Al layers. Non-uniform to be dependent on defects and surface terminations. Beyond =O, –
coverage of O-based surface groups on Ti3C2Tx, native point defects OH, and –F, there could exist other stable and viable surface
such as Ti vacancies and oxidized titanium adatoms (TiOx) (Fig. 11c) terminations, such as methoxy (–OCH3).1, 84, 94, 100, 102, 104
were also observed.107 Magne et al. investigated the site-projected electronic structure
Sang et al. similarly adopted STEM-EELS to characterize single of multi-layered (both HF-etched and HCl/LiF etched) Ti3C2Tx by using
layer Ti3C2Tx (using 7.5:1 molar ratio of LiF to Ti3AlC2, in 6 M HCl at 35 a combination of TEM-EELS and DFT calculations. The electron
°C for 24 h). The prevalence of different point defects (single Ti energy-loss near edge structures (ELNES) at the carbon (C) and
vacancies, Ti vacancy clusters) in the monolayer flakes and the surface element (O or F) K edges are shown to be highly sensitive to
importance of etchant concentration in defect formation was the identity and location of the surface groups (Fig. 13b), and can be
elucidated. The experimental HAADF-STEM image of Ti3C2Tx flake indirectly used to probe the Ti d density of states and subsequently
was ascertained to be that of a single layer through comparison with the electronic properties (Fig. 13c). Tx groups were revealed to above
similarly oriented simulated HAADF-STEM images calculated by using the hollow sites of three neighbouring C atoms (C1) and not directly
multislice algorithm (Fig. 12a-b). Additionally, DFT simulations were above the C atoms (C2) (Fig. 13a).109
performed to provide insight on the energetic costs associated with Hui Pan theoretically calculated the electronic properties of
Ti defect formation, and the influence of different functional groups transition metal nitride monolayers and their applicability as anode
on the stability of the vacancies. Ab initio molecular dynamics (AIMD) material for LIBs. Metallic and anti-ferromagnetic bare Ti2N
simulations were adopted to theoretically study the influence of the monolayers were predicted to have an open circuit voltage of 0.53 V

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(Fig. 14c), while zigzag nanoribbons become conducting View(no or Online


Article little
(a) (b) band gaps) (Fig. 14d) and this is in accordanceDOI: 10.1039/C6TA06772G
with previous
calculations.114 By combining nonequilibrium Green’s function with
DFT calculations, armchair and zigzag nanoribbon systems exhibit
different current-voltage curves, with no onset bias for most of the

Journal of Materials Chemistry A Accepted Manuscript


zigzag nanoribbons. Nonlinear features and weak negative
differential resistance behaviours were observed in some armchair
and zigzag nanoribbon systems.
(c) Zhang et al. computed the acoustic phonon limited carrier
mobility of Ti2CO2 monolayers and nanoribbons by using DFT and
deformation potential theory. The hole mobility along the x direction
(104 cm2 V-1) was derived to be thrice as large as the value along the
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y direction, while the electron mobility was about two orders of


magnitude lower (102 cm2 V-1). By controlling its width and
engineering its edge, the Ti2CO2 nanoribbons, with drastic difference
between the electron and hole mobility, were anticipated to be
useful for photocatalysis and field-effect transistors.115
Different MXenes have been predicted with varying high in-plane
elastic moduli.85, 91 According to theoretical investigations by Fu et
Fig. 13 (a) Side view of a Ti3C2T2 single sheet with the two T surface al., the enhancement in strength by highly stabilising oxygen
group locations labelled C1 and C2. (b) Comparison between the functional groups of Ti3C2O2 was attributed to the charge transfer
experimental C-K edge and calculations performed considering the from inner Ti-C bonds to the external Ti-O surface bonds, hindering
–OH group (Tx) in configurations C1 or C2. (c) Comparison between irreversible deformation and subsequently a high critical stress was
the simulated F-K edge in C1 (bold black line), the unoccupied p-DOS
needed for lattice failure.116 Guo et al. studied the tensile stress-
of the excited F atom (F* – thin black line), the surface titanium (Tis)
d-DOS (red line) and the volume titanium (Tiv) d-DOS (blue dashed strain relations of Tin+1Cn (n = 1, 2, or 3) and surface functionalized
line). The Tis and Tiv DOS were divided by 500 and 250 respectively Tin+1CnTx under different loading directions and unravelled the
to be plotted on the same scale as the F* DOS [reprinted with corresponding deformation mechanisms using first-principles
permission from ref. 109. Copyright 2016 The Royal Society of calculations (Fig. 15a-b). Under biaxial and tensile strains, up to
Chemistry].
critical point, Ti–C bonds are gradually stretched resulting in stress
and a high specific capacity of 487 mAh g-1, due to low adsorption induced strengthening; and beyond critical strain, the surface Ti layer
energy and long bonding distance with Li atoms. Although –OH
surface groups could reduce the diffusion barrier to 0.005 eV, unlike
=O and –F terminations, the lithiation process required more effort (a) (b)
for its positive adsorption energy and overall detrimental to its
performance as anode. Additionally, other metallic Mn+1Nn (M = Ta,
Ti and V; n = 1 and 2) monolayers were computed and identified as
non-magnetic with the exception of Ti3N2 being ferromagnetic.110
More interestingly, according to computations by He et al., Mn2CF2,
a yet-to-be-synthesized but stable MXene was predicted to room-
temperature ferromagnetism (high Curie temperature of 520 K),
wide half-metallic gap (0.9 and 2.5 eV at PBE+U and HSE06 levels, (c) (d)
respectively) and a substantial magnetic anisotropy (24 μeV) and its
potential application in spintronics was highlighted by Hu et al..111, 112
Although various Cr2XTx have also been predicted to retain its
ferromagnetism even with surface terminations unlike other
MXenes, to date none of these MXenes have been experimentally
synthesized and examined to verify the validity of the calculations.100
Experimentally, most MXenes are hitherto characterized to have
inherent metallic behaviour except for a semiconducting oxygen-
Fig. 14 Optimized atomic configurations of Ti2CO2 nanoribbons. (a)
terminated Ti2COx and Mo2CTx.32, 67 Zhou et al., using ab initio Top and side view of armchair Ti2CO2 nanoribbon monolayer with
calculations, examined the electronic structures and electron the width parameter of 10. (b) Top and side view of zigzag Ti2CO2
transport properties of Ti2CO2 nanoribbons and revealed that the nanoribbon monolayer with the width parameter of 10. The red,
energy gaps in patterned (armchair- (Fig. 14a) and zigzag-terminated gray and white circles represent O, C and, Ti atoms, respectively.
edges (Fig. 14b)) Ti2CO2 nanoribbons were tunable by appropriate Total density of states (TDOS) and projected density of states
(PDOS) on atomic orbitals of Ti, C, and O atoms of (c) asymmetric
crystallographic orientation and widths.113 At width parameter armchair; and (d) zigzag Ti2CO2 nanoribbons, respectively. The Fermi
beyond six, the armchair Ti2CO2 nanoribbons remain semiconducting energy is at zero [reprinted with permission from ref. 113. Copyright
(although band gaps decrease with increasing width of nanoribbons) 2016 American Chemical Society].

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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

Journal of Materials Chemistry A Accepted Manuscript


Tin+1Cn. Young’s modulus of Tin+1Cn is also observed to slightly with application of either a critical tensile strain or external electric
decrease as n increases.117 field.92, 96, 126 Using DFT tight-binding method, Zhang et al. examined
Beyond the stable and superconductive (under 2.5 K) Mo2C (> the stability and electronic properties of Sc2C monolayers, nanotubes
100 µm) without surface functional groups prepared by Xu et al. and their functionalized counterparts. Sc2CH2 and Sc2C(OH)2
through the traditional vapour deposition (CVD) method and the first nanotubes were found to be stable and increasing so as their radii
Mo2CTx recently synthesized by Halim et al. as a potential Li-ion increased; semiconducting and with band gaps tunable by changing
battery anode, most intrinsic physical properties of Mo2CTx remained their radii.127 Yang et al. identified that magnetic Sc2CT2 could be
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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)

Fig. 16 Structural representation of (a-c) HF10 and (d-f) HF48


MXenes. The Ti, C, O, F, and H are in blue, black, red, green, and pink
spheres, respectively. Hydrogen bonds are as black/white dashed
Fig. 15 Calculated stress–strain curves of (a) Ti2C; and (b) Ti2CO2. (c) lines for O···H and F···H. All other bonds are as solid lines. Plots (a)
Variations of bond lengths (Ti–C) and the out-of-plane heights, h, of and (d) are viewed along the crystallographic c* axis (i.e., the
Ti atoms in Ti2C. The arrows indicate the onset strains of instability. stacking direction). Plots (b) and (e) are top view (the a*–b* surface)
Inset shows atomic structure of Ti2C. (d) Variations of the out-of- of a single isolated sheet, illustrating random occupation of
plane heights, h-Ti of Ti atoms in Ti2CO2 and the out-of-plane −O/OH/F groups. Plots (c) and (f) highlight the formation of
heights, h-O, of O atoms. Inset shows the atomic structure of Ti2CO2 interlayer hydrogen bonds (attractive force) and repulsive
wherein the surface groups are located at the most energetically interactions when alike terminating atoms are facing each other. All
favorable positions. Bond lengths and out-of-plane heights are hydrogen bonds shown in the plot are with the lengths of ≥1.5 Å and
normalized by their equilibrium values [reprinted with permission ≤2.3 Å [reprinted with permission from ref. 129. Copyright 2015
from ref. 117. Copyright 2015 The Royal Society of Chemistry]. American Chemical Society].

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Perdew-Burke-Ernzerhof (PDE) functional, Heyd-Scuseria-Eznzerhof intercalation/deintercalation of Ti3C2Tx films View (Fig.


Article17d),
Online
(HSE06), a hybrid functional, was recommended to be included in suggested potential application in sensors DOI:
and10.1039/C6TA06772G
electrochromic
calculations of electronic properties for more accurate band gap applications.138
predictions.97, 101 Mariano et al. detailed the increment of superimposed
These inherently complex MXenes, with nanocrystalline Mn+1XnTx Ti3C2Tx flakes with reduction of spin casting rate, i.e. 800 rpm

Journal of Materials Chemistry A Accepted Manuscript


layers, short-range ordering of surface structure and randomly produced a 3 flake overlap, 600 rpm gave a 4 flake overlap and
stacked monolayers, have shown immerse potential applications as 400 rpm resulted in a 5 flake overlap. It was noted that with
transparent conductive films, environmental remediation, additional overlapping layers may help to improve the
electromagnetic interference (EMI) absorption and shielding, interconnectivity between nanosheets while retaining high VIS-
electrochemical applications, such as Li-ion batteries (LIBs), NIR region transmission, as evidenced by the low sheet
supercapacitors, other electrochemical storage systems and resistance of 437 Ω sq−1, high 77 %T for films (5 flake overlap,
electrocatalysts. Other prospective applications, include hydrogen 7.4 ± 0.5 nm) deposited at 400 rpm. Thicker films were found to
Published on 13 December 2016. Downloaded by Freie Universitaet Berlin on 14/12/2016 01:13:30.

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.].

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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

Journal of Materials Chemistry A Accepted Manuscript


indium tin oxide (ITO) thin film of identical thickness. More issue.46
significantly, with a mere 0.25 wt. % of graphene incorporated, Using photodegradation of methyl orange under UV
the measured conductivity and Hall mobility doubled and irradiation as a representative model, Gao et al. assessed that a
tripled respectively. An optimized 30-fold reduction in resistivity hydrothermally synthesized TiO2/Ti3C2Tx nanocomposite
as compared to its electrosprayed pristine Ti3C2Tx counterpart possessed enhanced photocatalytic activity (electron-hole
was achieved by incorporating a low content of 2.5 wt. % separation) as compared with pure anatase TiO2 or HF-etched
graphene (indicative of a low electrical percolation threshold) Ti3C2Tx. Due to the presence of heterojunction in TiO2/Ti3C2Tx,
Published on 13 December 2016. Downloaded by Freie Universitaet Berlin on 14/12/2016 01:13:30.

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].

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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

Journal of Materials Chemistry A Accepted Manuscript


other oxidant agents such as K3[FeCN]6], KMnO4 and NaAuCl4 by barriers for ions of different charge to be intercalated between
delaminated HF-etched Ti3C2Tx nanosheets. Additionally, its the layers.146
reducing activity in aqueous solution was reaffirmed by the Additionally, Rasool et al. evaluated the suitability and
observation that white rutile TiO2 nanoparticles were slowly applicability of such Ti3C2Tx membranes for ion separation,
precipitated from black delaminated Ti3C2Tx aqueous dispersion water purification, antimicrobial coatings and related
over the course of 3 months under atmospheric conditions. 143 applications, through the investigations of their interaction
Consequently, these dispersions, containing high surface area mechanisms and bactericidal activity in two bacterial models
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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

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(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

Journal of Materials Chemistry A Accepted Manuscript


resulted in fundamentally different Ti3C2Tx, in terms of the degree of
exfoliation and delamination (number of atomic layers) and the
proportion of surface terminations, and consequently EMI
absorption or shielding performance. More interestingly, surface
modification to the MXene, use of other members in the MXenes
family or MXene-based composites remains a promising possibility
to be further explored.
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3.4 Energy storage


Fig. 19 (a) Permittivity (real (ε′) and imaginary (ε″) and the loss
tangent (tan δ) versus frequency for composites of the Ti3AlC2 MAX 3.4.1 Lithium-ion batteries (LIBs). LIBs, as a ubiquitous cornerstone
phase, Ti3C2Tx, and annealed Ti3C2Tx in a wax matrix with 50 wt % of portable consumer electronic era and de facto front-runner
loading. (b) Schematic for Proposed EMI shielding mechanism. incorporated in commercial battery packs for electric vehicles (EVs),
Incoming EM waves (orange arrows) strike the surface of a MXene are still limited in terms of energy density, due to the incumbent
flake. Because reflection occurs before absorption, part of the EM commercial graphite anodes. MXenes are promising LIB anode
waves is immediately reflected from the surface owing to many
charge carriers from the highly conducting surface (magenta arrows), materials, since they have excellent electronic conductivity, low
whereas induced local dipoles, resulting from termination groups, operating voltage range of (-0.2 to 0.6 V vs. Li/Li+), low diffusion
help with absorption of the incident waves passing through the barriers which are favourable for high rate performance and
MXene structure. Transmitted waves with less energy are then exceptional mechanical properties that are invariant to Li adsorption.
subjected to the same process when they encounter the next MXene Unlike typical diffusion limited battery electrode materials,
flake, giving rise to multiple internal reflections (dashed black
arrows), as well as more absorption. Each time an EM wave is intercalation of ions in MXenes can paradoxically occur at a high rate,
transmitted through a MXene flake, its intensity is substantially without significantly depreciating their energy storage capacities.
decreased, resulting in an overall attenuated or eliminated EM wave Levi et al. explained that the rapid electrochemical cationic
[reprinted with permission from ref. 151. Copyright 2016 American intercalation between partially swollen MXene layers, resembling ion
Chemical Society]. adsorption at the solid-liquid interface, was facilitated by the
structures by amorphous carbon and low permittivity anatase and presence of water molecules and resulted in significant structural
rutile TiO2, dielectric dipole interactions and accompanying deformation (expansion and contraction). It was conjectured that
relaxation at these multiple interfaces enhanced the dissipation of this electrochemical capacitive paradox was made possible by the
the EM wave. A minimum reflection coefficient of -48.4 dB at 11.6 presence of both shallow and deep cationic adsorption sites, filled
GHz was attained by a 50 wt. % annealed Ti3C2Tx/wax composite of with ions and water molecules.152 As mentioned earlier, MXene
1.7 mm thickness. Contrary to EM absorbing materials, increased sheets with more =O terminations are suggested to possess the
loading of Ti3C2Tx (between 60 wt. % to 90 wt. %) in wax composites highest capacity as compared to other surface groups.102, 104 It seems
were also examined for their EMI shielding performance. that HCl/LiF etching may be the most preferred method to prepare
Counterintuitively, majority of the total shielding effectiveness (SE) MXenes for LIBs although it has a relatively lower yield and
of Ti3C2Tx/wax composites was contributed by EM wave absorption controlling surface chemistry of MXenes can be pivotal to
and not EM wave reflection (Fig. 19b) even though Ti3C2Tx possessed performance enhancement.37, 94, 99
metal-like free electron density.151 Based on DFT calculations, Tang et al. predicted a high theoretical
Shahzad et al. adopted a higher LiF to Ti3AlC2 molar ratio (7.5 to Li-ion capacity of 320 mAh g-1 for a hypothetically bare Ti3C2
1) to prepare delaminated Ti3C2Tx without sonication and films of monolayer whereas if fully terminated by either –OH or –F, a
these pristine HCl/LiF-derived delaminated Ti3C2Tx and its composite drastically reduced theoretical capacity of 67 or 130 mAh g-1 would
with 10 wt. % sodium alginate (SA) at recorded exceptional EMI SE be obtained instead.97 Based on X-ray Absorption Near Edge
performance at 92 (45 µm thickness) and 57 dB (8 µm thickness) Structure (XANES) data, Xie et al. proposed the formation of extra Li
respectively. It was proposed that in addition to polarization losses layers on the already-lithiated O-terminated Ti3C2 to account for the
from the induced dipoles by the surface terminations, the abundance exceptional capacity of 410 mAh g-1, as reported by Mashtalir et al.
of Ti3C2Tx surface free electrons partially reflected some incident EM for a DMSO-intercalated HF-etched Ti3C2Tx, which exceeded its
waves, the high electron density Ti3C2Tx absorbed and caused a theoretical capacity (320 mAh g-1).31, 102 Eames et al., in a later DFT
decrease in energy of the remaining waves due to ohmic losses and study, reaffirmed surface termination by oxygen (=O) presented the
the 2D nanolamellar structure of Ti3C2Tx provided the necessary highest capacity than those terminated by either –OH or –F.104 Xie et
reflecting surfaces for internal multiple reflection phenomenon that al. and Er et al. had separately conducted ab initio DFT calculations
scattered EM waves and dissipated energy in the form of heat. to derive the theoretical lithium and sodium capacity of Ti3C2Tx, and
Unprecedentedly, this 90 wt. % Ti3C2Tx-SA composite encompasses it was noted that storage capacities were enhanced by larger

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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)

Journal of Materials Chemistry A Accepted Manuscript


slightly lowered under high strain.103 The diffusion barriers of
bilayer structure of oxygen-functionalized Ti- and V- based carbide
MXenes, as computed by Ashton et al., were significantly higher (c) (d)
than that of corresponding monolayers, thus reiterating the
importance of having dispersed MXene single layers to attain high
LIBs anode performance.153
Encouraged by the first application of HF-etched multi-
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layered Ti2CTx as anode material in LIBs, where a reversible


capacity of 70 mAh g-1 was recorded even after 200 cycles at
10 C in a half-cell configuration, other MXene materials, such Fig. 20 (a) Rate performance of TiO2/Ti2CTx hybrid obtained by
as Ti3C2Tx, Mo2TiC2Tx, Nb2CTx, V2CTx, Nb4C3Tx, and Mo2CTx, partially oxidizing Ti2CTx with H2O2 (ca. 5 minutes of contact time) at
have also been examined as potential anode for LIBs.15, 17, 31, 32, various current densities [reprinted with permission from ref. 68.
63, 154 By combination with transition metal oxides (TMOs) Copyright 2016 The Royal Society of Chemistry]. (b) Cycling stability
of Ti3C2Tx at 1 C and the Ti3C2Tx/CNFs composite at 1 C and 100 C.
which have higher Li+ capacity but poor conductivity, Inset shows the electrochemical impedance spectroscopy (EIS) plots
synergistic effect of TMO and Ti2CTx leads to much improved of Ti3C2Tx and Ti3C2Tx/CNFs composite [reprinted with permission
performance (Fig. 20a) as compared with either individual from ref. 58. Copyright 2015 The Royal Society of Chemistry]. (c) CV
TMO or Ti2CTx.68, 155 curves of PVP-Sn4+@Ti3C2Tx at a scan rate of 0.1 mV s–1 [reprinted
Mashtalir et al. prepared a mixture of narrow sized with permission from ref. 59. Copyright 2016 American Chemical
Society]. (d) Schematics of synthesis processes for the fabrication of
distributed single and few-layered Ti3C2Tx by intercalation of free-standing and flexible Ti3C2Tx/TMO hybrid films through
DMSO between the HF-etched multi-layered Ti3C2Tx at RT for sandwich-like assembly by alternating filtration or spray coating
18 h under constant stirring, followed by sonication in DI water methods or an in-situ growth method [reprinted with permission
for 6 h. A free-standing, binder-free Ti3C2Tx electrode was then from ref. 157. Copyright 2016 Elsevier].
assembled by filtering the mixture through a membrane. electrical conductivity. This composite electrode recorded a
Reportedly, this Ti3C2Tx electrode demonstrated excellent rate reversible capacity of 310 mAh g-1 at 1 C (320 mA g-1) after 800
performance of 410 mAh g-1 at 1 C and 110 mAh g-1 at 36 C, both cycles, 260 mAh g-1 at 10 C after 1000 cycles and 150 mAh g-1 at
after 700 cycles. This elucidated the possible formation of 50 C after 5000 cycles. It was inferred that the Ag species had
additional Li layers on the already lithiated and surface important catalytic roles for the increase of more efficient and
terminated Ti3C2Tx, resulting in capacity exceeding the conductive Ti (III) species from Ti (II) species in Ti3C2/Ag
theoretical value.31 Despite its inherent moderate gravimetric composite after 2000 cycles (discharge-charge), whereas a
capacity (320 mAh g-1), Kim et al. showed that by cold-pressing pristine Ti3C2Tx displayed negligible Ti species variation after
HF-etched multi-layered Ti3C2Tx with conductive agent, carbon cycling.78
black (CB), a high-density and practical Ti3C2Tx electrode with an To overcome its inherent moderate gravimetric capacity,
areal capacity of 5.9 mAh cm-2 at C/3 exceeding that of Luo et al. synthesized a PVP-Sn4+@Ti3C2Tx nanocomposite,
commercial graphite anodes could be achieved.156 which exhibited a synergistic “pillar effect”, whereby
In bid to improve the electronic conductivity between layers spontaneous expansion of anchored Sn when alloying with Li+,
of HF-etched Ti3C2Tx sheets, reduced contact resistance concurrently pushed the Ti3C2Tx interlayers further apart to
amongst the sheets and increase ion accessibility by preventing allow more Li+ intercalation and when tested in a half-cell
restacking, Lin et al. grew conductive CNFs to connect the configuration, it retained reversible capacity of 544 mAh g-1 at
isolated layers. Consequently, this 86.2 wt. % Ti3C2Tx/CNFs 500 mA g-1 after 200 cycles.59 However, it is also noted that the
retained a reversible capacity of 320 mAh g-1 at 1 C after 300 charge-discharge profiles of Ti3C2Tx resemble more of
cycles and 97 mAh g-1 at 100 C even after 2900 cycles (Fig. supercapacitors than that of LIBs (Fig. 20c), thus it is noteworthy
20b).58 Alternatively, Ren et al. improved ion accessibility by that they may be more compatible in Li-ion capacitors or hybrid
synthesizing porous Ti3C2Tx flakes and by incorporating 10 wt. % devices instead. Zhao et al. prepared freestanding delaminated
of MWCNTs as interlayer spacers and conductive agent, the as- HCl/LiF etched Ti3C2Tx/planar NiCo2O4 composite film using
prepared porous Ti3C2Tx/MWCNTs retained reversible capacity three different methods, namely alternating filtration, spray
of 800 mAh g-1 at 160 mA g-1 after 350 cycles. This exceptional coating and an in-situ growth process (Fig. 20d). The former two
reversible capacity is presumed to be consequential of more methods offered the flexibility to fabricate the hybrid films with
adsorption and storage of Li+ ions on the edges of pores in this different mass ratios of NiCo2O4 to Ti3C2Tx and it was noted that
porous Ti3C2Tx/MWCNTs composite.75 Zou et al. synthesized a the mechanical properties deteriorate with increasing NiCo 2O4
90 wt.% HF-etched Ti3C2/Ag composite, by reducing AgNO3 in content. The in-situ growth process, probably catalysed by Ni
the presence of Ti3C2Tx. The formation of well-dispersed Ag and Co cations, induced partial oxidation of Ti3C2Tx flakes and
nanoparticles on the layered Ti3C2Tx improved its overall

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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.

Journal of Materials Chemistry A Accepted Manuscript


mAh g-1 at 1 C after 100 cycles. This performance was attributed
to better electrolyte penetration with a higher degree of 3.4.2 Supercapacitors. Supercapacitors provide alternative energy
disorder in arrangement of Ti3C2Tx and planer NiCo2O4 storage with rapid power density but low energy density as
nanoflakes within the film due to spray coating and a large compared to batteries. Therefore, researches have targeted
amount of Ti3C2Tx (50 wt.%) to facilitate fast electron and ion primarily on improving their volumetric capacity, i.e. energy density
transfer.157 per volume. Per their charge-discharge mechanisms, supercapacitors
The next most studied MXene after Ti3C2Tx is Nb2CTx, are classified as either electrical double-layer capacitors (EDLCs) or
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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].

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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

Journal of Materials Chemistry A Accepted Manuscript


average Ti oxidation state in Ti3C2Tx, by first approximation, is stacks by means of a Ti3C2Tx hydrogel film and recorded a
closer to +2 than +4 (Fig. 21b).159 gravimetric capacitance of 62 F g-1.163 Dall’Agnese et al.
Xu et al. adopted a classic molecular dynamic simulation to extended the capacitance testing of Ti3C2Tx/MWCNTs in organic
examine a representative Ti3C2(OH)2 electrode, with a slit electrolyte, and attained a moderate capacitance of 245 F cm-3
nanopore, in room temperature ionic liquid and ascertained at 2 mV s-1.164 Yan et al. alternatively measured the capacitance
that charge storage is a combination of fast counter-ion of Ti3C2Tx/MWCNTs in an alkaline electrolyte of 6 M KOH and
insertion and counter-ion/co-ion exchange. Electrolyte ions are recorded a capacitance of 393 F cm-3 at 5 mV s-1.165 Through
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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

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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

Journal of Materials Chemistry A Accepted Manuscript


capacitance than Ti3C2Tx, Ti3C2Tx is still the most studied
pseudocapacitive MXene for its superior electronic conductivity
and chemical stability.14 There are growing interest in Nb- and
Mo-based MXenes as well for they potentially possess an even (d) (e) (f)
larger capacitance.17, 32, 64 Table S2 in Supplementary
Information summarizes the use of various MXenes in as
electrode material for supercapacitor.
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It is noteworthy that capacitance values are dependent on


various parameters, such as constitutes of composites,
electrolytes, scan rate, current load, mass ratio and cell
Fig. 22 Optimized geometries of Ti3C2X (a), NaxTi3C2X (b), AlxTi3C2X (c)
configuration, therefore mere numerical comparison of
from side view. The DFT calculations were performed with a modified
capacitance should be taken with a pinch of salt. model based on experimental results and indicated that the Na ions
can easily diffuse in Ti3C2X. (d) Annular bright-field (ABF) image of
3.4.3 Beyond LIBs and supercapacitors. As various cations (Li+, Na+, Ti3C2X observed along the a/b axis. Two C atomic layers (labelled with
Mg2+, K+, NH4+ and Al3+) have been observed to spontaneously purple arrows) interleave into three Ti-atomic layers (labelled with
blue arrows) with a sequence of Ti(s)–C–Ti(c)–C–Ti(s), forming an
intercalate in between Ti3C2Tx layers, Ti3C2Tx has been earmarked as
edge-shared TiC6 octahedral stacking. The functional groups such as
potential Na-, K-, Mg-and Al-ion batteries/capacitors.26, 87, 99, 104 O and/or F atoms (labelled with red arrows) prefer to stay on top of
Beyond Li, other elements offer more abundancy and possibly the Ti(c) atoms, instead of the topmost sites of the C atoms on both
greater gravimetric capacity due to multi-electron redox chemistry. sides of the Ti3C2 layer. (e) ABF image of Ti3C2X electrodes upon Na
Yang et al. predicted the theoretical Na+ storage capacity of various intercalation with cutoff potential of 0.0 V. Inset shows that Na ions
are intercalated into Ti3C2X from the surface, fully occupying the
M2CTx via DFT computations and derived at capacities from 190-288
interlayers and remained on top of the C atoms rather than on top
mAh g-1. Wang et al. assessed HF-etched multi-layered Ti2CTx as a of the Ti(s) or Ti(c) atoms in the Ti3C2X layer. Moreover, double Na-
negative electrode for Na-ion hybrid capacitor and recorded a atomic layers (labelled with double yellow arrows) are observed in
reversible capacity of 175 mAh g-1 at 20 mA g-1 at the end of 100 one interlayer of the fully intercalated sample. (f) ABF image of Ti3C2X
cycles in a half-cell configuration and configured it into a prototype upon Al intercalation. Intercalation of the Al ions (labelled with green
arrows) induces horizontal sliding of the Ti3C2X monolayer [reprinted
Na-ion full cell as well.172
with permission from ref. 174. Copyright 2015 American Chemical
Xie et al. first reported Ti3C2Tx to have an experimental Society].
reversible capacity of 80 mAh g-1 at 100 mA g-1 after 120 cycles Zhao et al. loaded HF-etched multi-layered Ti3C2Tx via an
in a Na-ion half-cell configuration as well as calculated its impregnation process at 155 °C for 24 h, and evaluated its
theoretical capacity to be 268 mAh g-1, assuming single Na performance as a lithium-sulfur (Li-S) battery cathode. This
adsorption layer.99 Evidently, with a different interlayer pioneering Li-S cathode retained a high reversible capacity of
distance input, Er et al. derived at a different theoretical 970 mAh g-1 at 200 mA g-1 even after 100 cycles.177 Interestingly,
capacity of 351.8 mAh g-1 for Na+ on Ti3C2Tx; and Yu presented a Liang et al. loaded 70 wt. % of sulfur into delaminated HF-
theoretical value exceeding 367.7 mAh g-1.87, 173 Wang et al. etched Ti2CTx and measured a reversible capacity of 723 mAh g-
recorded HF-etched Ti3C2Tx with a reversible Na+ ion storage 1 at C/2 after 650 cycles. The strong interaction between

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

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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

Journal of Materials Chemistry A Accepted Manuscript


electrochemical performance was attributed to effective
trapping of LiPSs by active hydrophilic surfaces of Ti3C2Tx
surfaces as well as delay of outward diffusion of LiPSs due to
strong physical adsorption by the mesoporous matrix of the
nanocomposite.180
(c) (d)

3.5 Electrocatalysts
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Electrolytic/solar water splitting, involving oxygen evolution


reaction (OER) (2H2O → 4 e- + 4H+ + O2) and hydrogen evolution
reaction (HER) (2H+ + 2e- → H2), is one important clean energy
technology. However, like oxygen reduction reaction (ORR) at
the cathode of fuel cells which requires the use of expensive
noble metal catalyst, its commercial uptake is limited, hence
there are extensive efforts towards the development of highly Fig. 23 (a) Polarization curves, (b) Tafel plots of TCCN, IrO2/C, Ti3C2,
efficient and cost-effective non-precious metal and g-C3N4 in an O2-saturated 0.1 m KOH solution (scan rate: 0.5
electrocatalysts. mV s−1). Inset in panel a) optical image of TCCN directly used as the
Ma et al. assembled a robust free-standing hybrid film of OER electrode operating at 1.70 V with generated bubbles on the
surface indicating the formation of O2 gas. Dash line in (a)
delaminated HF-etched Ti3C2Tx and exfoliated graphitic carbon Polarization curve of TCCN after 5000 potential cycles (scan rate:
nitride (g-C3N4) nanosheets by vacuum filtration. As a working 100 mV s−1). (c) Chronoamperometric response at a constant
electrode for OER, this Ti3C2Tx- g-C3N4 hybrid exhibited a sharp potential of 1.65 V (Ej=10 of TCCN). Inset shows
onset potential at 1.44 V (vs. reversible hydrogen electrode chronopotentiometric response at a constant current density of
(RHE)) and a low operating potential of 1.65 V to deliver a 10.0 10.0 mA cm−2 of TCCN as compared to that of IrO2/C [reprinted with
permission from ref. 76. Copyright 2015 John Wiley & Sons, Inc.]. (d)
mA cm-2 in 0.1 M KOH (Fig. 23a-c). Its excellent performance Schematic for formation of Schottky Barrier at the MXene/TiO2
was attributed to Ti-Nx motifs acting as electroactive sites, its interface [reprinted with permission from ref. 72. Copyright 2016
high surface area from hierarchically porous structure John Wiley & Sons, Inc.].
contributing to a high electrochemical double layer capacitance Seh et al. presented a combined theoretical and
and its hydrophilicity and high porosity enabling good experimental study of Ti2CTx and Mo2CTx as independent
wettability of active surfaces to allow rapid transport of electrocatalysts for HER. First, the hydrogen adsorption free
reactants and removal of reaction products. This freestanding energy (ΔGH) of various M2XTx was derived by DFT calculations
hybrid film was also examined as a trial air cathode in and presented as a volcano plot. Mo2C and Ti2C, both with =O
rechargeable zinc (Zn)-air battery and at current density of 20 on the basal plane as catalytically active sites, were calculated
mA cm-2, it registered discharging (ORR) at 0.87 V and charging to have a theoretical overpotential of 48 mV and 358 mV
at 2.55 V.76 respectively. Experimentally, HF-etched Mo2CTx, as evaluated in
Wang et al. hydrothermally synthesized rutile TiO2/Ti3C2Tx a three-electrode electrochemical cell using a rotating disk
composites at 95 °C for 4 h and identified an optimal Ti3C2Tx electrode apparatus at 1600 rpm in 0.5 M H2SO4, maintained a
content of 5 wt. % which recorded a 400 % enhancement in stable HER activity after ca. 30 cycles, reaching current density
photocatalytic HER at ca. 17.8 μmol h−1 gcatalyst−1 as compared to of 10 mA cm-2geo at an overpotential of 305 mV whereas HF-
pure rutile TiO2. By strategically encapsulating Ti3C2Tx with rutile etched Ti2CTx recorded an initial overpotential of 609 mV to
TiO2, the intimate contact allowed sufficient light absorption by reach 10 mA cm-2geo and its HER activity deteriorated further
TiO2, efficient charge transfer from TiO2 to Ti3C2Tx, formed a upon continued cycling. Expectedly, delaminated HF-etched
depletion layer at the Ti3C2Tx-TiO2 interface (Schottky barrier) Mo2CTx, with increased proportion of exposed basal planes,
(Fig. 23d) which facilitated electron-hole separation and recorded improved HER activity and supported the theory of
improved photocatalytic activity. Adopting an identical basal planes as the most probable surfaces for Mo2CTx’s
synthesis approach, TiO2/Ti2CTx and TiO2/Nb2CTx composites catalytic activity.181
with 5 wt. % loading of MXenes were prepared. TiO2/Nb2CTx Ling et al., using projector augmented wave method,
composite demonstrated the best performance as co-catalysts identified poor HER catalytic activity of pure V2CO2 was due to
for photocatalytic HER with the weakest photoluminescence high H binding strength and elucidated that through strain
emission peak because Nb2CTx has the highest work function engineering and introduction of high catalytic transition metal
amongst the MXenes used in this work whereas TiO2/Ti3C2Tx (Fe, Co, and Ni) onto the surface of V2CO2, the H–O binding
displayed the lowest hydrogen evolution rate.72 strength can indeed be weakened and thus improve the HER
performance.182

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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.

Journal of Materials Chemistry A Accepted Manuscript


for efficient water splitting to produce hydrogen.183 Importantly, clay-like (hydrated), HF-etched multi-layered
Zhang et al. synthesized an urchin-shaped alkalization- Ti3C2Tx can only be prepared when intercalant source, LiCl, is
intercalated HF-etched Ti3C2/Ag/Ag0.9Ti0.1 bimetallic nanowire present as part of the etchant solution—rather than as a later
composite by mixing AgNO3, NaOH-treated Ti3C2Tx and PVP at addition. Evidently, new reducing agents, etchants, and
room temperature. This nanocomposite, recorded exceptional intercalants, for fluoride-free MXene synthesis protocol, to
electrocatalytic activity for ORR, with onset potential of 0.921 V control desired chemical species to bind on the surface of
and half-wave potential of 0.782 V. The layered conductive MXene’s and fine-tune the properties and expand their
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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

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to our manuscript.

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