Ceramics International 45 (2019) 18167–18188

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Ceramics International
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Review article

Synthesis, structure, properties and applications of MXenes: Current status T

and perspectives
Rodrigo Mantovani Ronchi, Jeverson Teodoro Arantes, Sydney Ferreira Santos∗
Universidade Federal do ABC, Av. dos Estados 5001, Santo André, SP, CEP: 09210-580, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: Researches on new 2D materials have been intensively performed over the years, strongly motivated by gra-
2D materials phene's outstanding properties. One of the most promising classes of 2D materials under investigation is the
MXenes MXenes, which are compounds obtained through chemical delamination of ternary (or quaternary) layered
MAX phases carbides or nitrides. MXene family possesses unique properties derived from their complex bonding (a mixture of
Exfoliation
metallic and covalent bonds) and electronic structures, atomic stacking, synthesis routes and surface terminal
groups. Despite the growing interest in these materials, there is a lack of systematic information on MXenes. This
manuscript aimed to review and comment the most relevant fundamental and technological aspects of MXenes,
ranging from structural and electronic characteristics of these compounds, their relevant properties and potential
applications and devices. The main properties and features described in the following sections, assessed by both
experimental and theoretical approaches, allow a critical analysis of the current status, trends, and potentialities
of MXenes, such as their use in energy related applications, electronic and photonic devices, reinforcements of
composites, and biomedical applications.

1. Introduction materials, as shown by the recently published reviews [3,11–21].

However, their majority is focused on energy-related applications and
Since the exfoliation of graphene [1,2], a significant amount of re- from the best of our knowledge, none of the reviews papers on MXenes
search has expanded to other 2D layered materials, due to their ex- available covers such a wide range of topics, ranging from fundamental
traordinary electronic, mechanical and optical properties [3,4]. Beyond aspect (synthesis procedures, structure and properties) to several
graphene, transition metals dicalcogenides [5], phosphorene [6], and MXenes applications. Thus, this review aims to offer to the Materials
their derivatives are examples of the most investigated 2D materials. Science community a comprehensive critical overview on the experi-
Recently [7], the discovery of a 2D-layered compounds family, namely mental and theoretical advances of MXenes research, indicating their
“MXenes”, has brought enormous attention of the scientific community, current status, trends, and challenges. First, there is a brief introduction
motivated by their peculiar structural and electronic characteristics, to the MXenes precursors (i.e., MAX phases) and their synthesis pro-
allowing their use on several potential applications. cedures and processing. Then, MXenes structures and stability are dis-
MXenes is the denomination of several transition metal carbides, cussed focusing on the effect of synthesis and termination upon their
nitrides or carbonitrides tipically obtained by chemical delamination of surface chemistry. After describing their electronic structures, the most
3D ternary (or quaternary) compounds known as MAX phases. relevant properties are detailed, including electric, mechanical, thermal
However, MXenes can also be obtained from other layered compounds, and magnetic ones followed by some of the most promising applica-
such as Zr3Al3C5 [8] and Mo2Ga2C [9,10]. MXenes have as general tions, such as energy-related, electronic, reinforcements of composites,
formula Mn+1XnTx (n = 1–3), where M represents a transition metal and biomedical. Finally, an outlook for future research is proposed from
(such as Sc, Ti, Zr, Nb and others), X is carbon and/or nitrogen and Tx the current research challenges. We hope that future theoretical and
represents the hydroxyl, oxygen or fluorine terminations derived from experimental studies use this review as a valuable guide to compare,
the synthesis procedures [11]. Since the discovery of Ti3C2Tx 2D com- discuss, and expand MXenes knowledge.
pound in 2011 [7], nearly thirty compounds have already been syn-
thesized and many more were predicted theoretically.
Due to their unique properties, there is a growing interest in these

∗
Corresponding author.
E-mail address: [email protected] (S.F. Santos).

https://doi.org/10.1016/j.ceramint.2019.06.114
Received 1 March 2019; Received in revised form 7 May 2019; Accepted 12 June 2019
Available online 21 June 2019
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
R.M. Ronchi, et al. Ceramics International 45 (2019) 18167–18188

Fig. 1. MAX phases Mn+1AXn forming elements.

2. MAX phases step for MXenes synthesis [42]. In fact, because of this removal of A
atoms layer from the MAX phases, this family of 2D metal carbides and
MAX phase is the MXenes precursor defined stoichiometry as nitrides synthesized was named MXenes [34].
Mn+1AXn, with n = 1, 2 or 3, in which “M” is a d-block transition The pioneering synthesis procedure used fluoridric acid (HF) under
metal, “A” represents group 13 and 14 elements (e.g., Si, Al, Ge or Sn) constant agitation and the multi-layered structures were exfoliated
and “X” is carbon, nitrogen, or both, as presented in Fig. 1. These phases through ultrasonication in methanol or isopropyl alcohol [11]. The
have a hexagonal structure (space group P63/mmc), where the layers chemical reactions between the MAX phase Ti3AlC2 and the rich
“M” and “A” are intercalated. The “X” atoms are located into the oc- fluorine aqueous environment [7] proposed at this first study are de-
tahedral sites formed by “M” elements [22–26]. There are more than 70 scribed below.
known MAX phases (such as Ti2AlC and Ti3AlC2 [27,28]), and new ones
have been constantly discovered [3,22–26] (for example, the qua- Ti3 AlC2 + 3HF → Ti3 C2 + AlF3 + 3 2 H2 (1)
ternary ordered MAX phases [29–31]) and similar materials, such as the
“MAB phases” [32,33]. Ti3 C2 + 2 H2 O → Ti3 C2 (OH )2 + H2 (2)
Their distinctive properties, derived from the unusual combination
of ceramic and metallic behaviors, attract great interest. From ceramics, Ti3 C2 + 2 HF → Ti3 C2 F2 + H2 (3)
MAX phases present low density, high hardness and excellent corrosion They represent the removal of aluminum atoms (reaction 1) and
resistance, while high thermal and electrical conductivities and good MXene termination with hydroxyl and fluorine atoms (reactions 2 and
machinability are similar to metallic materials [22–26]. As a con- 3, respectively). Later, oxygen terminations were also observed in
sequence of their unique properties, MAX phases are promising mate- MXenes [43]. In other words, the Ti–Al bonds are substituted by Ti–F,
rials for high-temperature structural applications (e.g. heating ele- Ti–OH, or Ti–O [44]. The prepared MXene samples consisted of mul-
ments, nozzles and heat exchangers), heating elements, rotating tilayer flakes stacked by weak interlayer interactions, which can be
electrical contacts and bearings, wear and corrosion protection mate- exfoliated through ultrasonication [21].
rials [22–26]. All experimentally synthesized MXenes present these terminations
These revolutionary properties result from the primary bonds: while (–O, –OH and –F) due to the greater thermodynamic stability of the
M-X bonds have a mix of ionic, metallic and covalent contributions, M- terminated compounds when compared with their pristine counterparts
A ones are purely metallic [22–26]. Thus, differently from the other 3D [35,38,45–50]. The most stable functionalization, however, is yet not
layered materials, such as graphite and transition metal dicalcogenides, well established in theoretical and experimental researches and may
which are bonded through weak Van der Waals interactions, MAX depend on the different compounds and synthesis procedures. Theore-
phases present strong bonds, preventing their cleavage through tical studies have pointed out that the termination stability increases
shearing or other mechanical methods [11,34–36]. Therefore, for the from –OH to –F to –O in several MXenes, such as Ti4N3Tx [51], Ti3C2Tx,
first time, chemical exfoliation approach made possible the synthesis of Nb4C3Tx [52] and M2CTx (M= Ti, Zr and Hf) [53] compounds. This
2D materials (MXenes) from primary bonded solids (MAX phases) lower stability of OH terminations is credited to the replacement of
[34,37]. hydrogen atoms by alkali or transition metals and also to its conversion
to –O at high temperatures [54]. However, –F termination was found to
3. Synthesis be more likely at M2CTx compounds [35,38,48]. Experimentally, the
order of termination stability –F > –O > –OH was verified for the HF-
As mentioned before, the M-X and M-A bond strengths are the major technique, while thermal treatments and HCl–LiF method results in
differentials of MAX phases. However, if compared to M-X, the M-A –O > –F > –OH [43,55]. Nevertheless, the majority of simulation
bonds are weaker and can be broken [11,38–40]. Thus, the basic studies do not consider the etching solution and, consequently, it is not
synthesis idea is to obtain carbides, nitrides, or both through the re- clear why they diverge on the functionalization order.
moval of weakly bonded layers of A atoms [41], which is the crucial Several parameters may influence MXenes etching parameters, for

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example MAX phase quality, composition and particle size, intercala- (TBAOH, choline hydroxide, or n-butylamine) resulted in the sub-
tion agent, etching solution, temperature and time [3,56–61]. For in- stantial reduction of fluorine atoms on the surface [70]. Moreover, the
stance, higher “M” atomic numbers require more time or higher acid detrimental effects of fluorine terminations on different applications
concentration (i.e., M4AX3 MAX phases require more aggressive etching (see Properties and Applications) persuaded the research of fluorine-
conditions than M3AX2 and M2AX) [7,34,42,62]. reduced and fluorine-free synthesis protocols [86–90]. More recently,
Among the main advantages of MXenes etching through HF solu- solvothermal treatment [91] produced both Ti3C2Tx and Nb2CTx with
tion, its versatility (most MXenes can be produced by it) and simplicity five times greater surface areas compared to the HF-etching protocol.
stand out, making this route extensively applied [3]. In addition, recent Finally, ultra-small MXenes nanosheets (e.g., quantum dots) have been
studies showed the applicability of this pioneering procedure for other pursued especially for biomedical and optical applications, but are still
carbide precursors which do not belong to the MAX phases group, such in early developments [58,92,93]. Fig. 3 shows the general synthesis
as Zr3Al3C5 [8] and Mo2Ga2C [9,10]. However, HF procedures employs procedure for all these discussed routes, indicating the most usual
hazardous chemistry solutions, which hinders its use in scaled-up pro- etching and intercalation agents.
cesses [63–65], and the HF-etched MXenes are not monolayer mate- Due to the unsuccessful attempts to produce nitride-based MXenes
rials, but multilayer flakes stacked together by weak Van der Walls by HF and HCl–LiF approaches, the first nitride MXene was obtained
bonds [7]. only in 2016 through the reaction of the MAX phase precursor with
In order to enhance the MXenes exfoliation, due to the primordial molten salts at high temperatures [51]. More recently, a salt-templated
influence of the interlayer distances to several applications, such as route was able to produce W2N(Tx) and V2N(Tx) through the reduction
electrochemical performance in 2D materials [66], researches focused of their oxide precursors in ammonia [94]. This difficulty is derived
on the weakening of interlayer Van der Waals bonds. Mashtalir and co- from the less cohesive and higher formation energies of Tin+1Nn com-
workers have verified the possible use of different substances, such as pounds compared to the Tin+1Cn. While the former represents the lower
urea [67], dimethyl sulfoxide (DMSO) [68] and isopropylamine [69] as structural stability, the latter implies a higher energy requirement to
intercalating substances. DMSO was successfully used for Ti3C2Tx and nitride-MXenes formation [11,51,95]. One solution could be the de-
isopropylamine for Nb2CTx, Nb4C3Tx and Ti3C2Tx [69]. Other inter- velopment of bottom-up strategies, such as the one applied for the non-
calating substances, such as NH4HF2 [63], tetrabutylammonium hy- MXene MoN compound [96].
droxide (TBAOzH) [70–72], tetramethylammonium hydroxide Moreover, the expansion of MXenes family has been hindered by the
(TMAOH) [73] and aryl diazonium salts in water [74] were also in- synthesis procedures of MAX phases with aluminum. Up to now, only
vestigated, reaching interlayer distances increases up to three times 10 of the 47 predicted MAX phases were successfully exfoliated
[75]. (Table 1) [39] and many other MXenes might also be synthesized. In
Later, Ghidiu and his co-workers [76] explored the reaction be- fact, 53 pristine MXenes were predicted by DFT [3,31,97] and con-
tween Ti3AlC2 and a solution containing chlorhydric acid (HCl) and a sidering only oxygen terminated compounds (e.g., Ti3N2O2, V4N3O2 and
fluoridric salt (e.g., LiF, NaF and KF), which generates HF in situ: Cr4N3O2), other 38 are predicted to be experimentally produced [98].
Consequently, new efforts regarding efficient and scalable synthesis
LiF (aq) + HCl (aq) = HF (aq) + LiCl (aq) (4)
development is crucial to the expansion of the MXenes family.
The advantages of this route are: (i) less aggressive reactants in However, some researches indicated possible encouraging solutions.
comparison with HF; (ii) lower sonicating times (i.e., at least four Substitutional solution of MAX phases weakened the M-X bond strength
times), (iii) high exfoliation yield, with approximately 70% of the flakes and facilitated the selective etching, such as evidenced by silicon on
with one or two layers, (iv) lower amount of vacancies, and (v) highly Hf3[Al(Si)]4C6 [99] and the second metal atom addition in the qua-
shapeable and flexible clay-like MXenes [65]. In other words, due to the ternary yttrium and scandium MAX phases, such as in (Mo2Sc)AlC2 [29]
high exfoliation yield, no exfoliation agent (such as DMSO or TBAOH) is and (W2/3Y1/3)2AlC [82]. Recently, Alhabeb and his co-workers [73]
needed in the HCl + LiF method, differently from the pioneer HF- produced the first Ti3C2Tx synthesis from a Ti3SiC2 phase through HF/
procedure. H2O2 solution, which points towards the MXenes synthesis from other
This HCl – LiF synthesis route lower defect content was corrobo- 13 and 14 group elements such as Cd, Si, and Hf [3,46,99,100].
rated by Hope et al. [43] and verified for the Mo2CTx MXene [10]. Conversely to the other routes previously discussed, which involved
Moreover, the MXene morphology changed from an accordion-like (HF) chemical etching, a bottom-up approach to produce MXenes was re-
structure to a more compact in the HCl–LiF route, without visible de- ported by Xu et al.19. They synthesized high-quality Mo2C [101] crys-
laminations. Finally, the increase of “c” lattice parameter (at least 25%) tals through chemical vapor deposition (CVD). This compound was the
and oxygen terminations were also [43] (however, the surface area only one produced without any termination until now and through a
remained similar to the HF one [77]). In addition, the change of re- bottom-up strategy. Despite the complex synthesis protocols and high
actants molar ratio from 1.0Ti3AlC2:5.0 LiF:11.7 HCl to 1.0:7.5:23.4 energy consumption, it is not clear why other compounds have not been
resulted in a safer route, called minimally intensive layer delamination synthesized through CVD technique, considering its versatility and
(MILD), which was successfully applied in Ti3CNTx and Ti3C2Tx ex- applicability for both carbides and nitrides. Furthermore, CVD can also
foliation and may be extensively used in the future [64,78,79]. Some be useful for evaluating the influence of the MXene terminations, lateral
influences of the reactants molar ratio in both processes and the com- size and their properties, comparing to the predicted ones (see Prop-
parison with the HF route can be seen in Fig. 2. Also, the best practices erties).
of these different routes, procedures of MXenes storage and deposit can Until today, MXenes were produced as powders, flakes, colloidal
be found in Alhabeb et al.’ [80] work. solutions and epitaxial thin films [102]. All synthesis routes presented
The expansion of HCl–LiF methods is indicated by their application inherit advantages and disadvantages and, consequently, its choice
to obtain several compounds, for example, Ti3CNTx [64], Ti3C2Tx depends on several factors, such as the compound which will be ex-
[65,81], Mo2CTx [10] and Mo1.33CTx [82]. However, despite promising foliated and the desired properties. The synthesis conditions for all
for optical, electronic and energy storage applications due to lower MXenes found are presented in the Supplementary Information (Tables
defects and increased oxygen terminations [83], this route is not always S1–S3) The achievement of scale-up processes with better surface
desirable. For example, in catalytic applications, the HF route may be chemistry is imperative to extend MXenes applications since defects and
beneficial (see section Applications) [20,84,85]. functional groups greatly influence their properties (see Properties and
Posteriorly, improvements upon MXenes synthesis were pursued Applications sections). In fact, the synthesis of different Ti2CTx
considering all steps. For example, the exfoliation of HF-etched V2CTx morphologies was achieved recently through the selective surfactant
and Ti3CNTx MXenes using high molecular weight organic basis intercalation agent (p-phosphonic calix[n]arenes) during the

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Fig. 2. Synthesis condictions influences on MXenes. (a, b) HCl–LiF exfoliation of Ti3C2Tx indicating that higher LiF concentration results in bigger MXene flakes.
(c–e) Atomic resolution STEM images obtained using a high angle annular dark field detector, where the vacancies in a MXene crystalline plane can be observed after
the HCl – LiF route and (f) relation between the defect and hydrofluoric acid (HF) concentrations in the pioneer route. Reprinted by permission from Ref. [3].
Copyright Nature Publishing Group: Nature Reviews Materials, 2D metal carbides and nitrides (MXenes) for energy storage, Anasori, B. et al. (2017).

Fig. 3. Schematic representation of MXenes synthesis procedures. MAX phase etching under acidic solutions remove the metallic “A” element (e.g., Al). In order
to obtain few MXenes layers, the obtained multi-layered compound is exfoliated through manual or mechanical agitation. An intercalation stage can be applied in
order to enhance the exfoliation.

Table 1
MAX phases predicted to be successfully exfoliated [39].
M2AC Ti2CdC Ti2InC Ti2GeC Ti2InN Ti2SnC Ti2GaC Ti2TlC Ti2SiC Ti2PbC
V2GaC Cr2GaN Cr2GaC Zr2AlC Zr2InC Nb2GaC Nb2InC Mo2GaC
Hf2SnC Hf2AlC Hf2InC Hf2TlC Hf2PbC Ta2GaC Ta2AlC
M3AC2 Ti3AuC2 Ti3SiC2 Ti3GeC2 Ti3IrC2 V3AlC2
M4AC3 Ti4GaC3 Ti4SiC3 Ti4GeC3 V4AlC3
M5AC4 Ti5AlC4 Nb5AlC4 Ta5AlC4

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indicated the typical six-coordination of transition metals due to the six

chemical bonds between M and X atoms, forming M2XT2 compounds
[21]. In addition, it was found that the most stable configuration
usually occurs when the terminations “T” atoms are placed in different
positions than the “M” and “X” ones [11,38,109–112]. However, in
some compounds (specially ordered double-M elements), “T” atoms are
above the “X” ones, in order to enhance their electronic interaction
[113,114]. Experimentally, it was indicated the random distribution of
termination groups in Ti3C2Tx and V2CTx compounds
[43,55,97,115,116] as foreseen by DFT [35], but more experimental
researches focused on the surface characterization and control are re-
quired to a complete corroboration of the simulation predictions
[49,117].
Experimentally, studies have evaluated MXenes structure through
atomic-resolution scanning transmission electron microscopy (STEM),
high-resolution transmission electron microscopy (HRTEM) and elec-
tron energy-loss spectroscopy (EELS) [44,78,87,118–122]. These tech-
niques may provide information regarding MXenes atomic structures,
intrinsic defects and surface terminations [16,21,44]. In addition, X-ray
photoelectron spectroscopy (XPS) is commonly used to identify their
chemical composition and elemental stoichiometric ratio [16,21]. Fi-
nally, some studies [43,116] used nuclear magnetic resonance (NMR)
spectroscopy in order to obtain information regarding MXenes surface
Fig. 4. Different MXenes morphologies. Schematic illustration and SEM functionalization and the influence of the different synthesis routes
images of different Ti2CTx morphologies through the ultrasonication in the
(e.g., HF and LiF–HCl) [16,21].
presence of p-phosphonic acid calix[n]arenes (PCXn). Figure with permission
Finally, their stability under storage and applications must be
from Ref. [103]. Copyright Wiley‐VCH Verlag GmbH & Co. KGaA Publishing
Group: Chem. Eur. J, Selective Calixarene-Directed Synthesis of MXene Plates,
highlighted, since researches indicated that MXenes degradation might
Crumpled Sheets, Spheres, and Scrolls, Vaughn, A. et al. (2017). take place upon exposure to moisture or high temperatures [79,123].
For instance, a detailed Nb2CTx MXene study showed that the Nb
adatoms positioned at hcp surface sites bond to ambient oxygen during
ultrasonication stage, in which the surfactant ring size defined the
exposure, destabilizing and eventually degrading the compound struc-
MXene morphology (plates, crumpled sheets, spheres, and scrolls re-
ture (Fig. 6) [118]. In addition, a Ti3C2Tx FET exposed to air for 70 h
spectively with n = 4, 5, 6, or 8, as shown in Fig. 4) [103]. However,
showed approximately 20% decrease of its initial conductivity [79].
more researches are urgent in order to find a controllable morphology,
After their synthesis, in order to enhance their stability, it is re-
architecture, lateral sizes and termination group synthesis procedure.
commended to store the colloids in an oxygen-free environment with
low light exposure [3,123], in a strong polarity solvent (e.g., DMSO and
4. Structure and stability n-methyl-2-pyrrolidinone – NMP) [124], or apply solution filtration
procedures (i.e., MXenes films) [123]. Moreover, optimized etching
Computational simulations are extensively used to understand procedures which reduces adatoms on the MXene surfaces may also
MXenes’ structures and to point out new possible stable compounds, improve their stability [118]. However, evaluation of MXenes devices
aiding experimental developments [7,11,104]. Through these studies, it after long-term applications, similarly to the research of Lipatov and co-
has been indicated that MXenes can be found in six possible structures: workers [79], are still to be explored.
(i) mono-M elements (for example Ti2C e Nb4C3), (ii) solid solutions, In the first experimental study regarding MXene thermal stability
such as (Ti,V)3C2 and (Cr,V)3C2; (iii) ordered out-of-plane double-M [37], it was observed three stages of the Ti3C2Tx mass loss at argon
elements, in which one transition metal occupies the external layers atmosphere: (i) 0.38% from ambient temperature to 200 °C, (ii) 4.48%
(usually Cr and Mo [105,106]), while the central ones are filled by between 200 and 800 °C and (iii) 2.47 from 800 up to 1000 °C. The first
another metal (e.g., Nb and Ta), for example MXenes Mo2TiC2 and stage represents the loss of adsorbed water and HF molecules
Mo2Ti2C3 [31]; (iv) ordered in-plane double-M elements, wherein the [125–128], while the second is a result of OH groups removal. Lastly,
different M elements are ordered in the basal plane, such as (Mo2/3Y1/ fluorine atoms are released in the third stage. Similar behavior was
3)2AlC [107]; (v) Vacancies ordered, for example Mo1.33CTx [84] and observed by other studies [8,63,129–133] and corroborated by ther-
W1.33CTx [82]) and (vi) vacancies randomly distributed (Nb1.33CTx mogravimetric coupled to mass spectrometry (TG-MS) analysis [134].
[71]). Schematic representations of MXenes structures are shown in Therefore, these studies indicate that thermal treatments could be an
Fig. 5. effective approach to remove OH/F terminations since each one is re-
Similarly to the MAX phases, the “M” atoms are arranged in a moved in a specific temperature range [55,85,131–135]. However, the
compact hexagonal structure, in which the octahedral sites are filled resulting material is not a pristine MXene, but an oxygen-terminated
with the “X” atoms [3,108]. However, the atoms pattern can alter with one. Recently, exposure of Ti3C2Tx at 750 °C under vacuum removed
the stoichiometric parameter “n”. While M2X compounds have AB the majority of O-terminations, implying the use of this approach to
stacking (hexagonal), M3X2 and M4X3 have ABC one (face-centered obtain pristine MXenes [122]. Consequently, new routes for synthesis
cubic). This stacking difference may explain some of the MXenes in- and/or conversion to pristine MXenes are still a major challenge.
stabilities with high “n” indexes. For instance, while Mo2C is stable However, practical applications require the understanding of
[9,10] both Mo3C2 and Mo4C3 are not [31], due to the Mo and C atoms thermal properties in air [133] and oxygen atmospheres [37,132]. In an
hexagonal arrangement [31]. oxygen atmosphere, despite rutile crystals formation at 500 °C, MXenes
Due to the intimate relation of properties and terminations, it is phase transformation happens at much higher temperatures (for in-
imperative to understand the terminated-MXenes stabilities and struc- stance, Ti3C2Tx to TiC conversion temperature is above 1000 °C for at
tures. Consequently, several studies have evaluated configurations and least 2 h) [37,132]. Recently, Mo-based ones showed thermal stability
influences of different functional groups. Computational calculations up to 530 °C (H2/N2 atmosphere) [72] and Zr3C2Tx showed better

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Fig. 5. Different MXenes structures.

5. Electronic structure

Pristine MXenes possess metallic conductivities with high electron

densities near the Fermi level [7,11,41,136,137], due to the d-electrons
from the “M” transition metals [38,41]. In ordered double-M structures,
it must be highlighted that the outer transition metal layers have in-
creased influence upon the electronic properties if compared with the
metal inner layer [16,31].
However, with the insertion of the functional groups, the electronic
properties need to be analyzed case by case. The terminations can
significantly reduce the density of states (DOS) and may lift the d band
above the Fermi level, creating a band gap [21]. This happens due to
the hybridization between the functional groups p orbitals with d ones
from the transition metal “M” [19]. DFT studies on the functional group
effects indicated that most M2XT2 compounds are semiconductors
(especially the oxygen-terminated ones) [38,138,139] and their band
gap values normally increase with the metal “M” atomic number [140].
Noteworthy, Ti2CTx surface group modification has altered its band gap
without any reduction in the carrier mobility, differently from graphene
[135].
While –F and –OH groups exhibit similar effects on MXenes elec-
tronic structures, oxygen terminations result in different behavior (O
can accept two electrons, differently from F and OH, which allow only a
single electron) [21]. Thus, the MXenes electronic structure depends on
Fig. 6. MXenes stability upon ambient oxygen exposure. (a) Fresh Nb2CTx the “type” of “M” and “X” atoms and their terminations [54]. Some
monolayer overview and STEM images and FFT patterns (insets) along the c- band gaps predicted through DFT using HSE06 hybrid functional,
axis from (b) fresh, (c) 5 and (d) 6 days after synthesis Nb2CTx. Reprinted by which provides relatively accurate values, can be seen in Fig. 7. Note-
permission from Ref. [118]. Copyright The Royal Society of Chemistry: Na- worthy, the first and unique bare MXene to be predicted as semi-
noscale, On the Structural Stability of MXene and the Role of Transition Metal conductor was TiCr2C2 [139], is presented in the inset.
Adatoms, Palisaitis, J. et al. (2018). Recently, it was pointed out that the band gap is also related to
modulation strain [112,145] and material doping [112,143]. For in-
thermal stability than Ti3C2Tx, being promising for high-temperature stance, doping Sc2CO2 with niobium atoms reduces its band gap from
applications [8]. 2.0 to 1.8 eV, which can be further decreased to 1.4 eV with 3% uniaxial
As previously stated, the synthesis route and parameters can alter strain [112]. In addition, some MXenes are topological insulators
the properties substantially. The only study found comparing the in- [16,114,146] as evidenced by the Sc2C(OH)2 compound, in which the
fluence of two different synthesis processes on the thermal properties of transformation from a trivial to a topological insulator and to a metal is
MXenes showed that Ti3C2Tx produced through NH4HF2 intercalation induced by electric field amplitude [146]. Finally, the C/N ratio can be
present transition temperatures about 150 °C higher than the one ob- used to tailor the MXenes band gaps and develop novel compounds, as
tained through HF-technique [63]. However, specific comparisons be- shown in the Sc3(CN)F2 carbonitride [144].
tween the other synthesis routes still need to be explored. However, higher “n” indexes compounds (e.g., Ti3C2, Zr3C2, Ti4C3,
Nb4C3 and Ta4C3) remain metallic regardless of the presence of

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Fig. 7. Comparison of oxygen-terminated MXenes band gaps. The effect of Fig. 8. Experimental electrical conductivities of different MXenes. In the
different functional groups can be seen in the inset for selected compounds. inset, the influence of different etching protocols can be seen in Ti3C2Tx com-
Compiled from Refs. [53,112,114,137,139,141–145,185]. The data can be pound. Compiled from Refs. [10,65,78,79,90,129,151,153,160,163–167]. A
found in Supporting Information 2. survey with the MXenes electrical conductivities reported is shown in the
Supporting Information 3.

functional groups [8,38,41,137,147–150]. For instance, Ti3C2Tx has

electron densities of 1022 cm−3 [95,151,152]. Thus, experimentally Ti3C2Tx measured electrical conductivities varied from 850 [165] to
synthesized Ti3C2Tx presented metallic character and promoted sig- 9880 [163] S.cm−1 (Fig. 8 insert), due to differences on the (i) defect
nificant increases of electrical conductivities in polymer [153–156] and concentration (ii) surface functional groups, (iii) delamination yield,
ceramic matrixes [157]. (iv) d-spacing between MXenes flakes and their (iv) lateral sizes in-
It must be highlighted that, compared to carbide-MXenes, the duced by each etching procedure. In general, lower HF concentrations
overall higher DOS of MXenes nitrides and carbonitrides originated and etching times generate MXenes with fewer defects and larger lat-
from the stronger Ti–N bonding (compared to Ti–C) and the extra ni- eral sizes, rendering higher electronic conductivity [54] (e.g., higher
trogen electron, can result in higher electrical conductivity. Thus, they flake sizes resulted in five times greater conductivities than small sized
may be considered more promising for applications such as nanoelec- MXenes [168]). Moreover, environment humidity might also influence
tronic devices and sensors [12,158]. However, experimental studies of their conductivities [125], pointing towards applications of relative
nitride MXenes are extremely scarce, if compared to their carbide humidity sensing material [169,170].
counterparts. A useful approach to enhance electrical properties is surface mod-
ification through thermal and alkaline treatments. They show con-
ductivities increase up to two orders of magnitude, such as presented in
6. Properties
Fig. 9. This increase is derived from the alteration and/or removal of
functional groups (especially –F) and intercalated molecules
Among the unique MXene properties, high Young modulus, thermal
[10,72,121,132,165,171,172]. More information about MXenes elec-
and electric conductivities and the adjustable band gap are remarkable.
tronic structures and related properties can be found in a recent review
Noteworthy, the hydrophilic surfaces with high metallic conductivities
of Hantanasirisakul et al. [16].
of MXenes, distinguish themselves from the majority of 2D materials,
including graphene [80,107,159]. Lastly, their properties and applica-
tions performances may be tuned through (i) composition (e.g., solid
solution formation and different transition metals “M” and “X” ele-
ments), (ii) surface functionalization (through chemical and thermal
treatments) and structure/morphology alterations [3,71,133,160]. The
main properties of MXenes family are detailed below.

6.1. Electronic and electric

Two of the main properties of interest of MXenes, electronic and

electric properties, can be tuned by functional groups alteration, stoi-
chiometry or solid solution formation. Experimentally, electric con-
ductivities of MXenes pressed discs were similar to multi-layered gra-
phene (resistances from 22Ω to 339Ω, depending on the “n” index and
its chemical formula) and higher than carbon nanotubes and reduced
graphene oxide materials [11,161]. Fig. 8 presents experimental values
of electrical conductivities of different compounds. In addition, it was
observed that resistivity values increase with the number of layers and
the presence of functional groups [34,68,132]. Because of this, the si-
mulated conductivities have generally larger values than the ones ob- Fig. 9. Thermal annealing effect on electrical conductivities of different
served experimentally [109,162]. MXenes. Compiled from Refs. [72,164].

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The presence of terminations drastically reduces the values of c11 (in

the following order: O, F and OH [141], as presented in Fig. 11), but
increases their critical deformations. These values are much higher than
the graphene ones, which is an important feature for flexible electronics
[153,177,178]. For instance, while Ti2C can deform up to 9.5, 18 and
17% at biaxial tensions, Ti2CO2 can reach 20, 28 and 26,5% (graphene:
15, 24 and 20%) [153,177–179]. More recently, the mechanical prop-
erties between the layers were verified along the [0001] direction. The
Ti3C2(OH)2 Young Modulus was 158 and 226 GPa to the SH and Bernal
stacking, respectively [36]. Lastly, a somewhat rare negative Poisson
ratio was predicted for W2C, which may find applications in advanced
technical fields, such as fracture resistance components in automobiles
and aircrafts [180].
While several mechanical testing methods exist for bulk materials
characterization, the evaluation of 2D materials mechanical properties
remains challenging. Most of the experimental data of 2D nanomater-
ials mechanical properties were determined by nanoindentation tech-
Fig. 10. MXenes elastic constants c11. Comparison of carbides and nitrides
nique, in which, normally, an AFM tip applies force at the center of a 2D
and their relation with the stoichiometric index “n”. Compiled from Refs. material film [181]. This technique was used recently [182] to provide
[8,141,149,158,173]. the only experimental Ti3C2Tx monolayer Young Modulus of
333 ± 30 GPa. The value is close to the previous 300 GPa simulated
value for Ti3C2(OH)2 [7] and 386 GPa of Ti3C2O2 [181] and still ap-
6.2. Mechanical
proximately 60% higher than MoS2 and graphene oxide [182].
However, despite the associated difficulties of measurement tech-
As the M-C and M-N are among the strongest bonds, mechanical
niques, the lack of MXenes surface terminations control, presence of
properties of MXenes also attracted great interest. The first simulation
structural defects (e.g., vacancies) and weak composites interfaces are a
study has suggested elastic constants (c11) at least two times greater
significant challenge to be surpassed and still hinders MXenes me-
than MAX phases [173] and other 2D materials, such as MoS2. How-
chanical evaluation [175–177,181–183]. Thus, new experimental stu-
ever, despite the c11 values 2 to 4 times lower if compared to graphene,
dies should focus on the development of more controllable synthesis
1060 GPa [136,174], their bending stiffness is higher [7,11,173,175],
protocols in order to manipulate its defect content and compare their
which points towards their use as reinforcements in composites. In
different functional groups, including pristine compounds [181,182].
addition, due to the functional groups, MXenes have better interaction
All in all, complete theoretical and experimental evaluations of me-
with polymeric matrixes than graphene for composite applications
chanical properties with the different functionalization groups are still
[7,34,176]. Thin discs of titanium–based MXenes showed hydrophilic
to be performed.
behavior, with contact angles between 27 to 41° [34] (Ti3C2Tx had a
contact angle of 35° [153]).
6.3. Thermal
Further studies [176,177] have validated the mechanical properties
values reported in Ref. [173]. One important tendency is that the Young
Essential for electronic and energy-related heat dissipation devices
Modulus of both MXene carbides and nitrides decrease with increasing
due to their continuous size miniaturization [13,184], thermal con-
number of layers (“n”) [158,176]. In addition, nitride-based com-
ductivities and thermal expansion coefficients of MXenes are still
pounds possess higher values than carbides MXenes (Fig. 10) [158].
scarce. Simulation studies predicted low thermal expansion coefficients
[144,184] and higher thermal conductivities than phosphorene and
MoS2 monolayer [184,185]. For example, the predicted thermal con-
ductivities of Ti2CO2, Zr2CO2, Hf2CO2, and Sc2CF2 at room temperature
varied from 22 to 472 Wm−1K−1 [184,185].
Similar to other 2D hexagonal materials, MXenes present two high-
symmetry routes (armchair and zigzag directions). From the MXenes
top-view, the x-axis is parallel to the zigzag direction, while the y-axis
coincides with the armchair (Fig. 12a). MXenes are anisotropic con-
sidering armchair and zigzag directions (Fig. 12b) and can be tailored
through flake length manipulation [184–186]. For example, the
thermal conductivity of Sc2CF2 increases from 298 to 722 Wm−1K−1
when the flake lengths vary from 1 to 50 μm [184]. Regarding the
oxygen–terminated compounds, it was found that their thermal con-
ductivities increase with the metal “M” atomic number [184–186].
Experimentally, only Ti3C2Tx thermal conductivity was evaluated
and thus, other compounds should be tested. Finally, the relation of
particle size and thermal conductivity highlights the importance of
MXenes synthesis morphology control and optimization.

6.4. Magnetic

Fig. 11. MXenes predicted elastic constants c11. The detrimental effect of Due to the magnetization possibility, differently from MAX phases,
surface terminations can be observed. Compiled from Refs. studies extended evaluations to MXenes magnetic properties
[8,141,149,158,173]. A survey of the predicted c11 and Young Modulus can be [39,51,95,110,147,187,188]. Several pristine compounds are predicted
found in the Supplementary Information 4. to possess magnetic moments, such as Ti4C3 [51], Ti3CN [189], Fe2C

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Fig. 12. MXenes predicted thermal con-

ductivities. (a) Indications of armchair and zigzag
directions on the Sc2CT2 (T = F or OH) top-view.
Reprinted by permission from Ref. [184]. Copyright
The Royal Society of Chemistry: Nanoscale, Pro-
mising electron mobility and high thermal con-
ductivity in Sc2CT2 (T = F, OH) MXenes, Zha, X.-H.
et al. (2016). (b) Thermal conductivities of different
MXenes on the armchair and zigzag directions,
compiled from Refs. [144,162,184,185]. Some of the
predicted thermal conductivities values can be found
at the Supplementary Information 5.

[190], Cr2C [66], Ti3N2 [95,110], Ti2N [187], Zr2C and Zr3C2 [150]. 7. Applications
Upon terminations, however, an individual analysis must be made
regarding each MXene and functionalization groups. For instance, MXenes’ versatility are attractive to several applications. Their high
Ti3CNTx and Ti4C3Tx become non-magnetic with the functional groups Young Modulus, good electrical conductivity and surface chemistry
[51,110,189], while Cr2CTx and Cr2NTx remain ferromagnetic at room alteration appeal to composites, while chemical stability, ion inter-
temperature with OH and F groups attached [38,46,191] and Mn2NTx is calation, and adjustable bang gaps point towards catalysis and energy
ferromagnetic regardless of the surface terminations [192]. However, storage applications, such as fuel cells, hydrogen storage and lithium-
the reported magnetic moments (Table S12–Supplementary Informa- ion batteries (LIBs) [3,11,83,197]. Promising results were achieved in
tion) are still only computational predictions and were not yet observed completely diverse areas, from opto-spintronics [129,187,190,192] and
experimentally. This is accredited to the lack of surface chemistry flexible/wearable electronics devices [166,183,198,199] to environ-
control [83,189] and limited synthesis of MXene compounds (especially mental [45,200,201] and biomedical [92,195,202–205] ones.
pristine ones). In some of these, MXenes presented performances similar or better
than any other material used nowadays, such as electromagnetic in-
terference shielding in aerospace and electronic components
6.5. Optical [151,206,207], surface-enhanced Raman scattering substrates [208]
and energy storage systems [65,197,209,210]. The latter received the
The visible and UV light absorption are important for photo- majority of studies since it is essential for clean and renewable energy
catalytic, photovoltaic, optoelectronic and transparent conductive generation and used in electronic systems, such as electric vehicles
electrode devices. Ti3C2Tx films could absorb light in the UV–vis region [21,47,211].
from 300 to 500 nm and 5 nm thicknesses film showed transmittance up
to 91.2% [163,193]. In addition, it may present a strong and broad
absorption band at around 700–800 nm, depending on the film thick- 7.1. Energy storage
nesses, which results in the pale greenish films color [193,194] and is
important for photothermal therapy (PTT) applications [195]. Note- Fossil fuel depletion and rising energy consumption led to the in-
worthy, the transmittance values could be optimized through alteration creasing interest in renewable energy sources, storage and conversion
of its thickness [172] and ion intercalation [193]. For instance, while systems [21], such as batteries and supercapacitors. While the former
hydrazine, urea and DMSO reduced Ti3C2Tx film transmittance, tetra- present large specific capacities, ideal for compact volume use (in-
methylammonium hydroxide (NMe4OH) increased it from 74.9 to tegrated into portable electronics, such as smartphones and tablets), the
92.0% [193]. latter have large power densities and fast charge–discharge rates, being
First principles simulations pointed out that the presence of func- applicable in mobile applications (e.g., electric automotive industry
tional groups also influences the optical properties of these 2D com- power sources) [15,21].
pounds [196]. In fact, fluorinated and hydroxyl terminations present
similar characteristics, contrasting with oxygen ones. For instance, in 7.1.1. Batteries
the visible range, –F and –OH terminations reduce absorption and re- Li-ion batteries (LIBs) are widely used in feed portable electronic
flectivity, while in the UV region, all terminations enhance the re- devices due to their high energy densities, good cycling performances,
flectivity if compared to the pristine MXene [196]. More recently, it was and environmental friendliness [15,212]. Nowadays, the system gra-
indicated that lower absorbance values are achieved with the lateral phite anode/LiCoO2 spinel cathode remains the most used electrode
flake size reduction of MXene flakes [168]. couple in commercial lithium-ion batteries [21]. However, graphite
Due to their optical transparency in the visible region and metallic anodes have relatively low storage capacities for the future energy
conductivity, MXenes are potential candidates for flexible transparent demand (theoretically 372 and experimentally 330 mAhg−1)
electrode applications, while their high reflectivity in the ultraviolet [21,54,211,213]. Consequently, the development of higher energy
region points towards anti-ultraviolet rays coating materials [196]. density electrode materials is urgent for next generation of lithium-ion
Finally, it was indicated outstanding light-to-heat conversion efficiency batteries [21,54,211,213]. Evaluated since their discovery in 2011,
(∼100%), useful for biomedical and water evaporation applications MXenes and their composites are considered great promises for this
[161]. Nonetheless, some optical related features, such as luminescence application [110,214], because of their high electronic conductivities,
efficiency, emission colors, plasmonic and non-linear optical properties specific surface areas and Li storage capacities with a low circuit vol-
still need to be elucidated in order to further develop MXenes appli- tage. In fact, the lithium ions diffusion barrier of Ti3C2 is at least five
cations [16,159]. times smaller than TiO2 anatase and graphite, commonly used materials

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performances [211].
However, electrode MXenes application still has some challenges to
overcome. The two major limitations are their re-stacking during
electrode manufacturing and the termination control, which decreases
their ion storage capacities. Several routes have been pursued towards
their enhancement, such as alteration of surface termination [220,221],
increase of interlayer spaces [59,222–224]; presence of vacancies
[48,225], synthesis of open/porous structure architectures [226–229],
addition of other storage capacity materials [212,230–232] and com-
bination of these solutions [233].
The improved capacities obtained were attributed to: (i) higher
charge storage due to their delaminating layers; (ii) improved electro-
lyte ions accessibility and diffusion pathways to MXene layers; (iii)
metal hybridization with large capacity and excellent conductivity and
(iv) lower interfacial charge transfer and (v) faster ion diffusion [13].
For example, novel structured MXenes-carbon nanotubes (CNTs) as-
semblies [10,234] and porous Ti3C2Tx produced by freeze-drying [228]
hindered MXenes re-stacking and resulted in outstanding performance
(even compared to MoS2/graphene) [10,234].
It must be highlighted that MXenes can also be intercalated by other
metallic ions such as K+, Na+, Mg2+ [224] and Al3+ [97,210,216].
Fig. 13. Predicted gravimetric capacities of different MXenes for Li-ion Thus, they could be used in non-lithium ion batteries (NLiBs), which
batteries. Compiled from Refs. [110,211,216–218]. The survey can be found in have their use currently limited by appropriate electrode performances
the Supplementary Information 7. [216]. Ti2C theoretical capacities for Al3+ and Mg2+ were among the
highest ever predicted for both types of ion batteries (992 mA h g−1 and
in this application [110]. 687 mA h g−1, respectively) and the possibility of sodium ions multi-
In addition, Ti3C2Tx experimental thin film gravimetric capacities, layer adsorptions [223] further attracts interest. Moreover, recent stu-
i.e., charge amount stored per material gram (410 mAhg−1), similar to dies also demonstrate promising properties as conductive anchoring
Mo2CTx (423 mAhg−1) [10], was higher than the one obtained for materials in Li–S batteries [235–238]. This is a promising battery
graphite [68,83,211]. Despite the experimentally synthesized candi- system that provides theoretical energy densities up to 1675 mA h g−1
dates, such as Nb2CTx and V2CTx [209], other MXenes are theoretically [236], but is hindered by their fast capacity degradation due to poly-
predicted to present excellent capacities values, such as manganese sulfide shuttle and dissolution, large volume expansion and poor elec-
[215], chromium [66] and zirconium-based [150] (Fig. 13) ones, ap- trical conductivity of sulfur cathodes [15,236,238]. Thus, MXenes de-
pealing to the exfoliation of different MAX phases in the future. velopment could lead to new pathways on the NLiBs electrodes. The
However, despite the robust Ti3C2Tx research, it was indicated that performance of different MXenes upon batteries application is compiled
the theoretical gravimetric capacities increase with lower stoichio- in Table S16.
metric indexes (i.e., M4X3, M3X3 and M2X) [211]. For example, Ti2C
showed approximately 50% higher Li+ gravimetric capacity than Ti3C2, 7.1.2. Supercapacitors
as shown in Fig. 13 [62,68]. However, considering the same index, no MXenes were also found attractive for supercapacitors, which are
trend behavior could be observed regarding mass elements [209,211]. considered alternatives to energy storage devices, because of their
Moreover, monolayers are preferred over multilayer structures, due to longer cycling stability and higher rate of charge/discharge than bat-
the higher number of lithium layers intercalated (1 for multilayer and 2 teries [21,54]. For instance, multilayered Ti3C2Tx presented perfor-
for monolayer MXenes, one on either surface) [110,211,217]. mances of 340 F/cm3 in KOH basic solutions, which is similar or even
Nonetheless, the metallic ions adsorption, intercalation chemistry, better than commercial carbon and activated graphene electrodes (re-
storage capacity, and the operating potential are related to the presence spectively, 180 and 200–350 F/cm3) [65,153,210,239]. When exposed
of functional groups [97,110,215,216,218]. Generally, their presence to acidic solutions (H2SO4), the Ti3C2Tx film synthesized for Lu-
increases the diffusion barrier, especially the hydroxyl and fluorine katskyana et al. (i.e., HCl – LiF route) showed excellent volumetric
ones [110,214,215,219]. For example, the theoretical Li-ion capacity capacitances (900 F cm−3 at 2 mVs−1 rate) without degradation after
for Ti3C2Tx was increased almost five times with the removal of OH− 10,000 cycles [65].
terminations [110]. In addition, computational screening This different behavior upon basic and acidic electrolytes derives
[211,214,218] have indicated that –O termination may even enhance from the difference in charge-discharge mechanisms. While Ti3C2Tx was
MXenes storage capacities and, thus, oxygen functionalization is pre- considered pseudocapacitive in an acid solution (H2SO4), only electric
ferred for energy storage applications. Consequently, the most pro- double layer capacitance is produced in neutral or alkaline electrolytes,
mising MXene anode materials are pristine or O-terminated M2C com- which reduces their performances [15,240]. Noteworthy, pseudocapa-
pounds with light transition metals [54]. Experimental researches citive behavior is related to the reversible surface redox reactions at or
corroborate these computational studies. Vacuum calcination, which close to the electrodes surfaces, which provides high energy density,
removes OH and F terminations, resulted in materials with better anode while the double-layer capacitor is based on the reversible accumula-
performances for LIBs [133,171]. tion of electrolyte ions without redox reactions (i.e., charge via physical
Therefore, it can be concluded that, regarding electrochemical ap- reversible ion adsorption mechanism) [15,21]. Consequently, over-
plications, the HCl–LiF synthesis route developed by Ghidiu et al. [76] coming their reduced electrochemistry performance on alkali [12,13]
is preferred over the pioneer HF one [43], since it presents a lower and organic electrolytes [15,241] are critical steps towards practical
amount of F and OH terminations and structural defects (e.g., va- applications. In addition, their charge storage mechanisms over dif-
cancies). Moreover, HCl–LiF route results in better delamination ratio, ferent electrolyte media are yet to be fully understood [3,240,242,243].
which further enhances MXenes capacities [64]. However, it must be It must be highlighted that surface chemistry also influences volu-
highlighted that novel synthesis routes with better surface chemistry metric capacitances. The replacement of –F atoms for –O terminations
control can still significantly enhance their electrochemical can enhance MXenes performances (i.e., HCl – LiF synthesis route [76]

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Fig. 15. Supercapacitor applications. Electrode performances of some

MXenes compositions (electrolyte 3 M H2SO4). Their respective synthesis routes
Fig. 14. Effect of Ti3C2Tx synthesis conditions on gravimetric capaci- under brackets. Compiled from Refs. [160,164,168,248].
tances. HF [245], HCl–LiF [65] and fluorine-free [86] indicates that lower
contents of –F terminations are preferred for this application. electrocatalysts for HER were evaluated, such as conventional noble
metals (e.g., platinum) and the metal-free catalysts phosphorene and
is preferred) [240]. Different Ti3C2Tx synthesis routes/conditions graphitic carbon nitride. However, these materials still exhibit poor
[126], chemical modifications (N2H4 [130], DMSO [210,216] or KOH charge transfer, low active sites accessibility and high manufacturing
[134] solutions) and heat treatments [134,244] have substantially in- prices, which hinder their practical uses [21]. Therefore, the develop-
creased their capacitances, with a more pronounced effect under acidic ment of highly stable, conductive, active and low-cost catalysts for HER
electrolytes. For instance, a Ti3C2Tx fluoride free synthesis [86] pre- remains an active topic of research [21].
sented gravimetric capacitance higher than HCl–LiF [65] technique, The interest in MXenes to catalysis is derived from their metallic
and approximately three times greater than HF procedure [57,210] character, high carrier mobility and large surface area/active sites,
(Fig. 14). which facilitates the electrocatalytic reactions as a result of the fast
Other compounds, such as Mo2CTx [10] and Mo1.33CTx [84] also electron transport [85,256]. Moreover, due to their ultralow work
showed promising performances as supercapacitors. Despite the bene- function, they can be used as supporting materials, tuning the proper-
ficial effect of vacancies to Mo1.33CTx capacitance (approximately 65% ties of multicomponent electrocatalyst systems [13].
higher [84] than Mo2CTx, 700 Fcm−3) [10], their influence on elec- Computational studies of HER electrocatalysts performances eval-
trochemical performance still need to be further studied [107]. In ad- uated, mostly, oxygen-terminated compound. Some studies [257,258]
dition, it was recently demonstrated that the flake size is intimately indicated several potential MXenes candidates to this application, such
related with the capacitance performances [160]. Finally, Nb3C2 pre- as Mo2CO2, Zr4C3O2, Nbn+1CnO2,Tin+1CnO2, Ta3N2O2, Wn+1CnO2
dicted quantum capacity was higher than graphene [246], but neither (n = 1, 2, 3) [257] and Cr-based ones [47], including double-ordered
this MXene nor its MAX phase precursor (Nb3AlC2) have been synthe- M2’M’’C2O2 compounds [106], appealing to their experimental synth-
sized yet, despite their predicted stability [246,247]. esis and characterization. Previously, a screening study of 2D layered
Nevertheless, MXenes have a strong tendency of aggregation via van M2XTx indicated promising HER catalyst candidates, including func-
der Waals attraction and hydrogen bonding, like the majority of 2D tionalized carbides Mo2C and nitrides V2N and Hf2N [259]. Moreover,
materials. This impairs their performances mainly because of the loss of nearly ideal Gibbs free energy of hydrogen adsorption can be achieved
surface area and the accessibility and exchange of ions limitation. Thus, through the addition of transition metal adatoms (e.g., Ir–Sc2CO2 and
alternatives have been pursued in order to mitigate these problems, Ag–Nb2NO2) [260]. Some of the adsorption energy at different hy-
such as tailored architectural designs (i.e., macroporous structure drogen coverage can be found in Table S19.
[248], hydrogel [160,241,248] or vertically aligned liquid-crystallines Experimental evaluations of catalytic performance are still rela-
[249]), use of interlayer spacers [164,250], decoration with conductive tively scarce, despite the notable potential of MXenes [85,261] and the
particles (e.g., Nb2O5 and NiO) [251,252] and combination of these evidence of intercalated molecular hydrogen between their layers
approaches [253]. In fact, Ti3C2Tx-polypyrrole nanocomposite [262]. Experimentally, Ti2CTx [85] and Mo2CTx [255,259] nanosheets
(1000 F cm−3) can almost reach the “new” (Mo2/3Y1/3)2CTx and exhibited low onset overpotential and a large exchange current den-
Ti3C2Tx hydrogels [160,248] performances (∼1500 F cm−3) [107], sities, in which the latter compound was considered more active HER
which are among the best reported volumetric capacitances for any catalyst, especially after delamination [255,259]. Fig. 16 compares
capacitive material (Fig. 15) [250]. Experimental gravimetric and vo- different MXenes overpotentials and Tafel slopes found in previous
lumetric capacitances in different electrolytes can be found in Tables researches. The former is a measure of the potential required to over-
S17 and S18. Finally, despite several synthesized MXenes, only tita- come the thermodynamic barriers to complete the reactions (the lower,
nium, molybdenum and, recently, vanadium [254] based-compounds the better), while the former is a measure of the reaction kinetics
were investigated. Thus, other compounds must be evaluated in order [21,263,264].
to expand and develop new supercapacitors electrodes. Doping MXenes with transition metals such as Co and Ni [13] to
produce solid solutions [143], and the architectural design to hinder
their sheet aggregation [265,266] are potential pathways to use
7.1.3. Hydrogen evolution reactions (HER) catalysts
MXenes as alternatives to Pt in HER, due to improvements on ag-
The search for more efficient and renewable forms of energy pro-
gregation-resistant properties, porous structure, higher surface area,
duction and storage for mobility and transport uses led to increasing
and interconnected conductive network for fast and continuous charge
researches in molecular hydrogen (H2). This carbon-free molecular fuel
transfer [265].
(non-fossil fuel) can be produced, for instance, through hydrogen evo-
However, not all MXenes are favored by oxygen terminations. Pan
lution reactions via electrocatalysis, for instance Refs. [21,255]. Several

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made and still need to be pursued. Moreover, Ti3C2Tx synthesized

membranes presented H2/CO2 selectivity better than state-of-the-art
membranes, with possible uses at hydrogen production, H2 purification
and carbon dioxide capture (Fig. 17) [269]. However, further en-
hancements can be achieved with architectured porous structures,
doubling salt adsorption capacity (118 mg/cm3) when compared to the
HF-etched compound and is amongst the best values ever reported
[228]. Finally, MXenes conversion to hydrophobic membranes allowed
higher stability for solar evaporation and seawater desalination,
maintaining similar performances of the hydrophilic surfaces [273].
MXenes were also evaluated as sensors with wide potential appli-
cations in environmental analysis and biomedical detection, such as
relative humidity [169,170], enzymes [274], gases (N2 [200], NH3
[275,276], NH4 [57], SO2 [275], H2O2 [277], ammonia and acetone
[278]), phenol [274], macromolecules and cells (dopamine neuro-
transmitters) adsorption [18], cancer biomarkers [279], neural activ-
ities [280], adrenaline [281] and others. The interest derives from their
Fig. 16. Experimental HER performance of different MXenes. The data was metallic conductivity, biocompatibility, abundant adsorption sites and
compiled from Refs. [82,85,255,259,261] and measurements can be found in good dispersion in aqueous phase [274,278], which can result in low
the Supplementary Information 9. electrical noise, low detection limit and high signal, primordial re-
quirements of high sensitivity sensors [274,278].
[258] evaluations showed that while oxidation improves significantly For instance, simulations showed that Mo2CO2 and V2CO2 present
HER performances of Mo2X monolayers, it degrades W2C monolayers good selectivity towards NO, while NH3 is preferred for Nb2CO2 and
and, consequently, need to be avoided in this latter compound. Ti2CO2 [275,276]. Moreover, studies also demonstrate promising
Therefore, more comprehensive simulations evaluating different func- properties for hydrogen [197,262], methane [57] and CO2 [122,282]
tional groups (–F, –OH and pristine compounds) in different MXenes is adsorption/storage at ambient conditions. Theoretical [282] and ex-
still to be achieved in order to guide future experimental developments. perimental papers showed CO2 uptakes up to ∼12 mol CO2/kg [122],
The effect of surface functionalization is still inconclusive and need even better than others currently investigated materials for this appli-
to be understood. While fluorine terminations increased catalytic per- cation. A first principle study [275] indicated that O-functionalized
formance in Ti2CTx (reduced charge transfer resistance) [85], they have MXenes present better gas selectivity than bare compounds, similar to
decreased Ti3C2Tx [255] and W1.33Tx [82] HER activities on the syn- membranes.
thesized compounds [255]. Moreover, in the same study, DFT simula- Recently, MXene-based strain sensors (hydrogel [283], piezo-
tions indicated that the partial substitution of O with F terminations in resistive [284] and surface-agnostic [194]) performances exceeded
Ti3C2, Ti2C, Mo2C, Mo2TiC2 and Mo2Ti2C3 is detrimental to their cat- previously reported hydrogel and MoS2 ones. They exhibited high
alytic performance [255]. Thus, this contradiction needs to be further sensitivity, fast response, good stability and excellent conformability
investigated and elucidated, aiming to clarify the experimental synth- with applicability for subtle human activities detection (e.g., eye
esis route more adequate to this application. blinking, throat swallowing and handwriting) in wearable devices and
Finally, despite electrocatalysts, MXenes were also promising in electronic skin [283–285]. Consequently, they could be used in anti-
photocatalysis (e.g., solar hydrogen production) addition [267] and counterfeiting applications and be an opportunity to “hear” vocally
carbon dioxide hydrogenation [21]. In summary, MXenes family is impaired people [283]. For instance, Ti3C2Tx MXene/CNT strain sensor
promising to energy production and conversion applications. This work presented gauge factors of 4.4–772.6 and a sensing range of 30–130%,
focused on three of the most important fields in clean and renewable compared to the low gauge factors (GF ≈ 2) and range of strain
energy-related applications (batteries, supercapacitors and electro- (ε < 5%) of conventional metal and semiconductor-based strain gauge
catalysis), but more information of other MXenes uses in electro- sensors [285]. Some examples of sensors application can be found in
chemical storage devices can be found elsewhere [3,12–15,21,54]. the Supplementary Material (Table S21).
One important indication is that the layered MXene showed better
sensitivity compared with the partial exfoliated one [284]. More ex-
7.2. Sensors and membranes amples can be found at the recent review from Sinha et al. [19].
However, the researchers are still limited to a couple of MXenes (mainly
The use of MXenes in membranes is also in its infancy [268]. Ti3C2), and consequently, new compounds must be evaluated, such as
Through the charge-selective ionic transport, MXenes membranes re- Hf3CO2, which had a promising relation between electrical conductivity
spond to intercalating ions altering their layer distances (molecule/ion and applied strain predicted in first principles simulations [145].
sieving mechanism) [269,270]. Here again, functional groups are im-
portant to this response: this expanding/contracting behavior is not 7.3. MXenes polymetric matrix composites
observed in pristine Ti3C2, while it is more pronounced at –O termi-
nated compounds, comparing to fluorine ones [271]. Experimental in- One of the main MXenes advantages in comparison to graphene is
vestigation on Ti3C2Tx coatings reported excellent bactericide perfor- their hydrophilic behavior with high conductivity, which provides
mances against E. coli and B. subtilis, especially after the membrane better interaction with polymeric matrixes and favors its use in com-
oxidation [201]. posite materials [153,154,156,286–288]. Moreover, these composites
Their hydrophilic behavior also favors water treatment and se- can be fabricated through simple and low-cost methods (e.g., solution
paration processes such as desalination [201,228,268,270,272]. mixing), into a variety of shapes, including films, fibers and 3D struc-
MXenes membranes presented high water flux (85.4 Lm−2h−1) with tures [289–292]. The wide range of Ti3C2Tx dispersions rheological
excellent salt rejection (∼99.5%), exceeding polymer, inorganic and properties is suitable to nowadays industrial techniques, such as elec-
2D graphene oxide (GO) membranes [268]. It is worth to highlight that trospraying, emulsion [293], extrusion printing, wet spinning [290],
these studies used different etching procedures (HF [270] and HCl–LiF and ink-stamping [291]. Due to these characteristics, the number of
[269]), and thus, a direct comparison between the MXenes cannot be studies in this area is increasing and several polymer matrixes were

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Fig. 17. MXenes sensors. (a) Single-gas perme-

abilities of MXene membranes at 25 °C and 1 bar
(inset: selectivity of H2 relative to other gases); (b)
H2/CO2 separation performances compared to state-
of-the-art gas separation membranes. Figures rep-
rinted by permission from Ref. [269]. Copyright
Nature Publishing Group: Nat. Commun., MXene
molecular sieving membranes for highly efficient gas
separation, Ding, L. et al. (2018).

investigated, including polydiallyldimethylammonium chloride (PDDA) tribological efficiencies improvements could reduce 500 million tonnes
[153], polyvinyl alcohol (PVA) [153,294,295], poly(vinylidene of CO2 emission in 10 years [306,307].
fluoride) [296], polyacrylamide (PAM) [156], polyethylene [287], In order to reduce friction and wear of different applications, from
epoxy [288], polyurethane [293] and polyfluorenes [286]. gears to medical implants for joint replacement, layered materials, like
Among this field, MXenes were mainly used to improve the me- graphite, MoS2 and hexagonal boron nitride, have been used [298].
chanical properties and electrical conductivities of polymer matrixes. More recently, the exfoliation of these materials resulted in extensive
For example, Ti3C2Tx – PDDA [153], PVA [153] and PAM [156] based researches of nanomaterials use as lubricants, such as graphene and 2D
composites presented excellent values of electrical conductivity. MoS2 [297,298,308]. MXenes present several important features to
Moreover, V2C-based smart composites, promising for biocompatible tribology, such as high surface area, graphene-like morphology and
applications, presented a 10 fold increase in electrical conductivity with excellent mechanical properties [179,287,309,310]. In addition, MAX
temperature increases from 15 to 45 °C [154]. Regarding mechanical phases also presented promising tribological properties in lubricating
properties, Ti3C2Tx-PVA-CNC (cellulose nanocrystals) fibers increased oils, even better than graphite [311–313]. However, their application in
the Young Modulus from 392 to 855 MPa [294] and epoxy-Ti2CTx this field remain relatively underexplored [179,287,309,310]. In fact,
composites presented storage modulus and impact strength enhance- the MXenes tribological research has been restricted only to Ti3C2Tx
ments of 38 and 76%, respectively [288]. More recently, the addition of [287,309,310,314–319] and Ti2CTx [288] compounds. Therefore, it is
0.5 wt% Ti3C2Tx increased the yield stress by approximately 70% in imperative the study of other MXenes in this field.
polyurethane matrix [293]. Further information on MXenes polymer In these applications, MXenes were incorporated to oils or polymer
composites can be found in the review from Ng and his co-workers [20]. matrixes. In the former, Ti3C2Tx addition enhanced the oil lubricant
Nonetheless, it must be noted that MXenes incorporation influences properties (optimum concentration ∼1 wt%), significantly reducing the
the structure and crystallization rate of the polymer matrix [81,287]. coefficient of friction (COF) as can be seen in Fig. 18
For instance, Huang et al. [81] studied the Ti3C2Tx-polyethylene oxide [309,310,314,315]. This was attributed to the tribofilm formation,
matrix, which is commonly used in solid polymer electrolytes. They which avoids the direct contact between the two rotating surfaces, and
have indicated two competing effects upon the crystallization rate: at also bear the indenter load due to the MXene good mechanical prop-
low concentrations, there is an increase due to the increase in sites erties [309,310,314,315]. In these researches, it was indicated that
available to heterogeneous nucleation, while at high ones, MXenes form higher MXene exfoliation degree (i.e., lower number of layers) results in
a rigid network, restricting the spherulites growth and crystallization lower COF and wear [315], as previously observed with graphene
rate. [308]. The authors proposed that the monolayers assist in the tribofilm
More recently, the experimental comparison of polyfluorenes- formation, protecting the surfaces from direct contact. Finally, the ad-
MXenes with different functional groups (i.e., one nonpolar, one polar dition of other nanomaterials, such as TiO2 [314] and potassium tita-
and end-charged group alkyl chains) indicated that the polarity induced nate [319], may further optimize friction and wear properties.
by the nitrogen-containing functional groups favors the polymer in-
tercalation between the Ti3C2Tx layers produced through HCl–LiF
[286]. However, in spite of the promising results presented above, the
research of MXenes as reinforcements in polymer matrixes require more
in–depth comprehensive studies. Lastly, there was not found any de-
tailed investigations between the matrix and MXenes interactions. This
fact is noteworthy since the nanomaterial/matrix interface is critical to
composite properties [297–299] and it is one of the major challenges in
this field [299].

7.4. Tribology

The study of interacting surfaces in relative motion, in special

friction and wear, received increased attention since the pioneer Jost
report in 1966 [300], due to its significant impact on the efficiencies of
mechanical systems and the economy of several countries [301–304]. It
is estimated that 1/3 of the world energy resources are used to over-
come frictional processes and that better tribological performances
could save from 1.3 to 1.6% of Gross Domestic Product in industrialized
countries per year [303–305]. More recently, the environmental con- Fig. 18. MXenes in tribology (oil lubricants). Comparison of oil friction
cern further improved tribology researches, since better performances coefficients with MXenes addition. Compiled from Refs.
could reduce gases emissions. Transportation researches indicated that [309,310,314,315,319].

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MXenes applicability (Ti2C e Ti2N) to spintronic components was

evaluated through First Principles simulations, motivated by their
half–metallic magnets-like behavior and the complete spins polariza-
tion near the Fermi level. The intrinsic half-metallicity of these com-
pounds must be remarked since this behavior is different from graphene
and other similar materials, which requires doping or external electric
fields [187]. Moreover, exceptional optoelectronic properties were
observed in conductive transparent films, similar or better than mate-
rials used nowadays, due to their low resistivity and high transmittance
and electrical conductivity [129,163,321].
Extraordinary results were obtained in electromagnetic interference
shielding (EMI) of aerospace and electronic components [151,206,207].
Flexible Ti3C2Tx films presented the best EMI performance compared to
any other synthetic material with similar thickness, and far superior to
the used commercial materials (graphite and other carbon materials)
[151]. Further improvements of approximately 30% were achieved
more recently changing its structure to a hydrophobic foam [207].
Fig. 19. MXenes in tribology (solid lubricant). Comparison of friction coef- Parafine–Ti3C2Tx composites presented two times higher EMI efficiency
ficients with MXenes addition in solid lubricant applications. The data was than the recommended one to commercial electronic components (39.1
compiled from Refs. [287,288,317,318] and measurements can be found in the x ∼20 dB, respectively) [206]. In addition, studies have indicated the
Supplementary Information 11. use of MXenes as terahertz detector [322] and shielding [323] and
microwave absorption [324], which could be used in photothermo-
Despite the applications of MXenes as base oil additives, to our electric detectors and aeronautical applications, respectively. It is im-
knowledge, only few studies as solid lubricants were realized in MXenes portant to note that stacked Ti3C2-MXenes were indicated to achieve
based composites and this topic remains relatively unexplored. The better performances as THz detection material compared to monolayer
addition on the ultra-high molecular weight polyethylene (UHMWPE) Ti3C2 [322]. More recently, MXenes were also promising to wireless
[287] and epoxy [288] resulted in enhanced wear resistance and lower communication between portable, flexible and wearable radio-fre-
COF values compared with pure matrixes (e.g., reduced by half with quency (RF) electronic devices [166].
2 wt% of Ti2CTx addition into epoxy matrix [288]), as presented in The thermoelectric industry also has a growing interest, due to the
Fig. 19. clean energy search, but it is currently limited by the low efficiency of
The enhancement of wear resistance and COF reduction was at- commercial thermoelectric devices (approximately 10%) [109,325].
tributed, respectively, to improvements of the composite mechanical Good thermoelectric performances were predicted in MXenes semi-
properties, which results in better plowing and scratching resistance conducting materials, such as Cr2CF2 [66], Mo2CF2 [66,109] and
and also the tribofilm formation, which results in lower contact area for Ti2CO2 [325], because of their extremely low thermal conductivities
plastic deformation between the composite and the counterbody (similar to MoS2 and much lower than graphene), and high electric
[287,288]. Similar behaviors were also found in copper matrix studies conductivity [140]. For instance, Cr2CF2 and Mo2CF2 showed Seebeck
[317,318] and accredited to the tribofilm formed in the sliding inter- coefficients superior to the reported for SrTiO3, which were high even
face, hindering the direct contact of friction pairs and facilitating the at temperatures up to 500 K (above 200 μV/K) [66]. However, despite
interface shearing. their promising behavior through First Principles calculations, experi-
Only recently, the first simulations and screening of MXenes tribo- mental thermoelectric properties are essentially unexplored [102]. In
logical properties were published [179,316]. Both articles demon- the only experimental research found, which compared different Mo-
strated MXenes promising features to tribological applications, such as based MXenes (Mo2CTx, Mo2TiC2Tx, and Mo2Ti2C3Tx), Mo2TiC2Tx pre-
low coefficient of friction, extremely low barrier for interlayer sliding sented the higher power factor for thermoelectrical devices [72].
and the possibility of superlubricity effect through the uniaxial strains. MXenes were also evaluated in biomedical applications, such as
It was found that bare M2C MXenes possess much higher sliding re- tissue engineering [326], cancer therapy and antibacterial materials,
sistance than the oxygen-functionalized ones due to their strong me- because of their outstanding biocompatibility reported for in vitro and in
tallic bonds between the stacked layers [179]. However, –F and –OH vivo tests and no noticeable toxicity [92,195,202–205]. Moreover,
terminations were not considered in this study, in spite of the predicted tunable morphology/structure, specific biodegradation and relatively
two times lower static friction coefficient of Ti3C2OH2 (∼0.10) against high physiological stability are interesting features for this field [93].
the oxygen-terminated compound [316]. In addition, it was found that For instance, tantalum (MnOx/Ta4C3Tx) [202], titanium [195,204,205]
larger lattice constants result in larger resistance to sliding with n = 2 and niobium-based composites (Nb2C−PVP) [203] nanosheets were
(i.e., Ti2CO2 presented the lowest) [179], but no screening study was considered promising to high-performance contrast-enhanced com-
realized with n = 3, which possessed lower friction coefficients. puted tomography and, most important, photothermal tumor ablation.
Moreover, vacancies tend to increase the COF [316], indicating that Furthermore, combining anticancer drug doxorubicin hydrochloride
more controlled synthesis routes could tailor the lubricant properties in (DOX) further increases the tumor treating efficacy, achieving better
tribological applications. results than either PTT or chemotherapy [195].
However, both experimental and theoretical research still lacks a Moreover, Ti3C2Tx was considered a promising matrix for mediator-
comprehensive evaluation of all the possible functionalization effects free biosensors [277] and fluorine-free quantum dots presented a
on the tribological properties and direct comparisons regarding the photothermal conversion efficiency of 52.2%, one of the best values
exfoliation degree and the tribological properties. reported so far [92]. A comparison of extinction coefficient and pho-
tothermal conversion efficiency of different MXene-based compounds is
presented in Fig. 20. While the former indicates the light absorption
7.5. Others ability, the latter measures the material performance to convert the NIR
laser energy into heat [203]. More recently, a PLA-Ti3C2Tx based
MXenes were also studied in diverse areas, ranging from opto/ composite has shown as promising material for guided bone regenera-
spintronic [129,187,193] to environmental applications [45,200,320]. tion due to its enhanced cell adhesion, proliferation, and osteogenic

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made upon MXenes synthesis, structures, and several promising appli-

cations, with constant discoveries of new compounds. However, several
challenges must be overcome to promote further developments.
Regarding their synthesis, there are three main barriers.
The first is to extend MXenes family. Up to now, only around 1/8 of
the MAX phases were experimentally exfoliated, and 37 more are pre-
dicted to be possible [39]. Noteworthy, just 9 from the expected 44 in-
plane MAX chemical ordering quaternary phases [30] were synthesized
so far and, consequently, new MAX and MXenes are expected in the
near future. This is mainly derived from the limited production of ni-
tride compounds and the restricted synthesis procedures of MAX phases
with aluminum (e.g., etching of Ti3SiC2 with HF resulted in TiC, rather
than MXene Ti3C2Tx [332]), highlighting that Mo2Ga2C [9,10] and
Hf3[Al(Si)]4C6 [99] are not MAX phases. Finally, the MXene synthesis
routes may be applied to similar materials, such as the MAB phases,
discovering new 2D nanomaterials with novel properties.
The second is the development of routes with better control of
surface chemistry functionalization, including the production of pris-
tine MXenes. However, other challenges such as controllable MXenes
Fig. 20. MXenes and MXenes-based compounds in photothermal tumor morphologies, architectural design and lateral sizes (e.g., ultra-small/
ablation applications. Compiled from Refs. [92,202–205,327]. A comparison quantum dots) still need to be pursued in order to tune their properties
of PTT-application performances of MXenes can be seen in Supplementary In- for specific applications [12,17,58,103,160,168]. It worth highlighting
formation 11. that experimental characterization of functional groups is still chal-
lenging, especially their direct image observations [102].
differentiation with MXene addition, even higher than GO [326]. More Theoretically, due to the different MXenes compounds (depending
detailed information of MXenes biomedical applications can be found in on their composition and functional groups), accurate modeling the
the recent papers of Lin [93] and Huang [159] and their co-workers. complex mixed experimental terminations and screening techniques for
It is worth to highlight that the recently lateral size reduction of different applications are still lacking, since they assume uniform sur-
MXene sheets (i.e., quantum-dots) promoted longer circulation time in face terminations, which has not been realized experimentally in
biological systems and induced luminescence [159]. However, these MXenes [16,102,257]. Moreover, classical Molecular Dynamics and
researches are still incipient and further investigations and optimiza- Finite Elements modeling are still rare in MXenes simulation studies
tions of in vitro and in vivo toxicity tests are necessary, such as re- [175].
productive toxicity and long-term biocompatibility/biosafety, which However, the number of theoretical studies are much greater than
are needed to employ MXene-based substances in biomedical applica- experimental ones, and several topics still need to be addressed
tions [93,159]. Moreover, researches are still lacking in some biome- [11,79,83]. For instance, some properties were obtained through si-
dical fields, such as immunological therapy, regenerative medicine, mulation and not experimentally confirmed (e.g., mechanical and
target drug delivery and gene therapy [19,93,204]. magnetic properties) [7,98,100,309,333]. In addition, some applica-
Lastly, due to their high surface area to volume ratio, 2D materials tions such as composites (especially with metallic and ceramic matrixes
can also be used to heavy metal ions separation [45,328], removal of [157,334]), thermoelectrical, optical and magnetic-related applications
contaminated solutions/dies [329], radionuclide adsorption (i.e., nu- need to be extensively evaluated.
clear waste pollution) [328] and hazardous molecules (e.g., for- Finally, considering their industrial applications, two main aspects
maldehyde) [330]. Moreover, high electrical conductivity, environ- hinder MXenes practical use: high cost and structural/properties in-
ment-friendly characteristics, hydrophilic nature, and surface active stability. The former is influenced by the high cost of MAX phase pre-
functional sites are important features for effective adsorbents in en- cursor (∼$550 per 150 g power, Y-carbon Ltd., Ukraine) plus MXenes
vironmental pollutant purification and nuclear waste treatment [17]. synthesis, delamination and manufacturing prices [14]. Thus, cheaper
Among them, MXenes are more promising than graphene and MoS2 synthesis procedures must be pursued, including the MAX phase pre-
because of their strong bonds and adsorption affinity between Ti and V cursors and product/device manufacturing, such as the novel im-
and the heavy metal ions [45], such as Pb(II), Cr(IV), Hg(II), Cd(II) and pressive stamping strategy which created all-MXene micro-super-
Cu(II) [17]. Computational studies indicated exceptional lead and capacitors through the combination of 3D printing technology and
copper theoretical adsorption capacities of pristine M2X, reaching ten viscous MXene aqueous inks [291]. Regarding the latter, MXenes may
times greater than graphene oxide [45]. More information can be found present oxidation during the storage period and degradation over dif-
at the Zhang [17] and Zhu [18] reviews. It is important to highlight that ferent application conditions [3,79,123]. Therefore, MXenes stability
their hydrophilic surfaces and the interlayer distance increase are characterizations must be expanded to different solvents and evaluated
beneficial polar and/or ionic species adsorption [17]. However, it was for several applications of technological interest [14,17].
shown that fluorine terminations are not desirable if compared to –OH
and –O groups [214,328] and thus, the HF synthesis route [7] may not Appendix A. Supplementary data
be used to these applications [17]. However, up to now, it was not
corroborated by any experimental research. Finally, the Pb ion ad- Supplementary data to this article can be found online at https://
sorption is favored in nitride-based M2X(OH)2 MXenes in comparison doi.org/10.1016/j.ceramint.2019.06.114.
with carbide counterparts [331], appealing to the still scarce experi-
mental synthesis and applications of these compounds. References

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