Chemosensors 09 00225 v3

chemosensors
Review
Preparation and Application of 2D MXene-Based Gas Sensors:
A Review
Qingting Li 1 , Yanqiong Li 2 and Wen Zeng 1, *
1 College of Materials Science and Engineering, Chongqing University, Chongqing 400030, China;
[email protected]
2 School of Electronic Information & Electrical Engineering, Chongqing University of Arts and Sciences,
Chongqing 400030, China; [email protected]
* Correspondence: [email protected]; Tel.: +86-023-65102466
Abstract: Since MXene (a two-dimensional material) was discovered in 2011, it has been favored
in all aspects due to its rich surface functional groups, large specific surface area, high conductivity,
large porosity, rich organic bonds, and high hydrophilicity. In this paper, the preparation of MXene
is introduced first. HF etching was the first etching method for MXene; however, HF is corrosive,
resulting in the development of the in situ HF method (fluoride + HCl). Due to the harmful effects of
fluorine terminal on the performance of MXene, a fluorine-free preparation method was developed.
The increase in interlayer spacing brought about by adding an intercalator can affect MXene’s
performance. The usual preparation methods render MXene inevitably agglomerate and the resulting
yields are insufficient. Many new preparation methods were researched in order to solve the problems
of agglomeration and yield. Secondly, the application of MXene-based materials in gas sensors was
discussed. MXene is often regarded as a flexible gas sensor, and the detection of ppb-level acetone
at room temperature was observed for the first time. After the formation of composite materials,
the increasing interlayer spacing and the specific surface area increased the number of active sites

of gas adsorption and the gas sensitivity performance improved. Moreover, this paper discusses
Citation: Li, Q.; Li, Y.; Zeng, W. the gas-sensing mechanism of MXene. The gas-sensing mechanism of metallic MXene is affected by
Preparation and Application of 2D the expansion of the lamellae and will be doped with H2 O and oxygen during the etching process
MXene-Based Gas Sensors: A Review. in order to become a p-type semiconductor. A p-n heterojunction and a Schottky barrier forms due
Chemosensors 2021, 9, 225. https:// to combinations with other semiconductors; thus, the gas sensitivities of composite materials are
doi.org/10.3390/chemosensors9080225 regulated and controlled by them. Although there are only several reports on the application of
MXene materials to gas sensors, MXene and its composite materials are expected to become materials
Academic Editor: Elisabetta Comini that can effectively detect gases at room temperature, especially for the detection of NH3 and VOC
gas. Finally, the challenges and opportunities of MXene as a gas sensor are discussed.
Received: 7 July 2021
Accepted: 3 August 2021
Keywords: MXene; gas sensors; gas sensitivity mechanism; HF etching
Published: 14 August 2021
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1. Introduction
published maps and institutional affil-
iations. In recent years, due to the development of industrial production and the emission of
automobile exhaust, environmental pollution has become particularly serious. Fortunately,
people have gradually paid attention to the impact of the emitted gas on the environment
and human health [1]. Nitrogen-containing gases, such as NO2 from fossil fuels and
Copyright: © 2021 by the authors.
automobile exhausts, can cause acid rain that is harmful to the environment and can cause
Licensee MDPI, Basel, Switzerland.
damage to human eyes and the respiratory tract [2–4]. NH3 is widely used in petroleum,
This article is an open access article
explosives, and other industries, but it will cause damage to the respiratory system, eyes,
distributed under the terms and and skin. According to the U.S. Occupational Safety and Health Administration (OSHA)
conditions of the Creative Commons regulations, the safe value of NH3 gas is only 35 ppm for 15 min and 25 ppm for 8 h. If it
Attribution (CC BY) license (https:// exceeds this value, NH3 will cause serious harm to the individual [5–7]. H2 S is a flammable,
creativecommons.org/licenses/by/ highly toxic, and dangerous gaseous compound. The inhalation of H2 S with concentrations
4.0/). >500 ppm will cause people to lose their breath in a short period of time. Long-term
Chemosensors 2021, 9, 225. https://doi.org/10.3390/chemosensors9080225 https://www.mdpi.com/journal/chemosensors

Chemosensors 2021, 9, 225 2 of 40
exposure to low concentrations of H2 S can cause serious harm to the eyes, respiratory
tract and central nervous system. Aiming at ensuring human health, the Association
Advancing Occupational and Environmental Health stipulates that the amount of H2 S
gas in the occupational environment shall not exceed 10 ppm [8,9]. H2 is an essential gas
in chemical experiments and the chemical industry, and it has a wide range of applications
in all aspects. However, H2 is a colorless and odorless flammable gas, rendering it difficult
to be detected. The concentration of H2 in the air over 4% can easily cause an explosion,
which poses a considerable safety hazard [10–12]. The “greenhouse effect” has always been
a hot topic in society, and the emission of CO2 and CO is the main reason for the greenhouse
effect. CO is colorless and tasteless, and humans can develop arrhythmia and respiratory
disorders after inhaling a large amount of CO [13,14]. The aforementioned gases are all
necessary in industrial production, but their potential threats are detrimental to humans
and the ecological environment. Therefore, the development of a gas sensor is of great
significance. Moreover, the goal of the development of gas sensors is to produce sensors
that possess high sensitivity, fast response and recovery speed, selectivity, and low working
temperature in order to realize real-time monitoring of gas concentration and to avoid
irreversible consequences.
Currently, many materials have been researched and developed for gas sensors, such
as metal oxides [15–24], carbon-based materials [2,25–28], conductive polymers [29–32],
metal organic frameworks (MOF) [33–35], and rare-earth oxides [36–38], etc. Metal oxides
are classified into n-type (such as TiO2 and SnO2 ) and p-type (such as CuO, ZrO2 , and WO3 ).
Researchers favor metal oxide as a gas sensor due to its excellent sensitivity, small size,
and low cost [39]. For instance, Wang et al. [40] used KIT-6 as the hard template to
synthesize WO3 modified with Au particles. The Au-WO3 sensor showed excellent gas
sensitivity for detecting trimethylamine (The response was 42.56% and the sensor only
took 1 s to respond under 100 ppm trimethylamine at 268 ◦ C). Chaloeipote et al. [41] used
3D printing technology to synthesize CuO. The CuO sensor showed a nice gas response
to the detection of NO2 (The response of detecting 200 ppm NO2 at room temperature
was 14.17%). However, sensors were made from metal oxides as gas-sensitive materials
usually achieve higher response in the range of 200 ◦ C to 500 ◦ C, which increases the cost
of gas detection and the potential safety hazards caused by high temperatures [34]. Carbon-
based materials (such as graphene (GO) and carbon nanotube (CNT)) are considered
room temperature gas sensors because of their excellent conductivity, large surface area,
and good mechanical properties [42]. CNT and GO are often used to fabricate gas sensors
due to their high carrier mobility, high specific surface area, and special structure [25].
For example, Yan et al. [43] used electrophoretic deposition to deposit multi-walled carbon
nanotubes (MWCNT) on porous silicon. The gas sensor showed excellent gas sensitivity
(When the sensor was exposed to 1 ppm NO2 at room temperature, the response was
8.5%, and the response time/recovery time was 37/34 s). Gupta et al. [44] synthesized
a reduced graphene oxide (rGO) film by chemical synthesis that was modified by high
edge-functionalization. The prepared gas sensor showed an excellent response to CO2 (The
response of 500 ppm CO2 at room temperature was 50% Hz/µg and response time and
recovery time was 26/10 s). Conductive polymers are favored because of their low working
temperature and high sensing performance, including polyaniline (PANI), polypyrrole
(PPy), and polythiophene (PTh) [29,30]. For example, polyaniline (PANI), which is easy to
synthesize, has adjustable conductivity, and possesses high stability under environmental
conditions. Thus, PANI is one of the most studied conductive polymers in gas sensors [31].
Polypyrrole (PPy) is widely used in gas sensors due to its controllable conductivity, ease
of manufacturing and low-budget [32]. Adhikari et al. [45] used sodium cholate micelles
as a soft template in order to synthesize ribbon-like nanostructured polypyrrole (PPy).
When the gas sensor detected 100 ppm ethanol at room temperature, the response of
the sensor was 87.64%, and the response and recovery time was 2/31 s. Metal-organic
framework (MOF) bridges organic connectors and metal centers, possessing a porous
structure [46]. MOF has received extensive attention from researchers owing to its porosity,
ultra-high surface area (~2000 m2 g−1 ), structural diversity and excellent adsorption affinity,
and it can be used as precursors to further derive various materials. Zeolite imidazole ester
frameworks (ZIF-8 and ZIF-67) have been studied in the direction of gas sensitivity [34,35].
Zhan et al. [47] successfully synthesized a series of polyhedral ZIF-8 nanostructures with
molar ratios by the solvothermal method. Due to the porosity of the ZIF-8 nanostructure
and the high free charge carrier density, when the ZIF-8 sensor was exposed to 100 ppm
NO2 at 350 ◦ C, the sensor showed a high gas response (118.5%) and a rapid response and
recovery time was observed (113.5 s and 111.5 s, respectively). Among many sensors,
two-dimensional (2D) nanomaterials (including black phosphorus (BP), transition metal
dichalcogenides (TMD), 2D MXene, etc.) are prominent in the gas sensor due to large
specific surface area and many adsorption sites [48,49]. Among them, MXene was a new
2D nanomaterial discovered in 2011.
In 2011, Naguib et al. mixed the Ti3 AlC2 powder and TiC powder for heating and
then they used HF to remove the Al layer in order to obtain a 2D multilayer nanostructure
Ti3 C2 Tx , which was called MXene [50]. The formula of MXene is Mn+1 Xn Tx (n = 1, 2, or 3),
where M represents early transition metals, such as Ti, V, Sc, Cr, etc.; X is carbon or nitrogen;
and T is surface functional groups such as –OH, –O and –F. MXene is mainly synthesized by
getting rid of the A layer of the MAX phase of the bulk, where A comes from the elements of
IIIA or IVA [51–53]. The MAX phase is a form of layered hexagonal ternary transition metal
(TM) carbides and nitrides with P63 /mmc symmetry [54,55]. Since the bond of the A layer
in the MAX is solid, it cannot be damaged easily by shearing force or mechanical cutting;
that is, it is hard to peel the MX layer from the MAX by these methods. Since, the connection
strength of the M–X bond is more robust than that of the M–A bond in MXene, etching is
the best method to remove the A from the MAX phase [56]. Nowadays, there are more
than 200 MAX phases based on various combinations, and a variety of MXene materials
have been synthesized, such as Mo2 C, Ta4 C3 , Nb2 C, TiCN, and V2 C [57,58]. For example,
Ghasali et al. [59] used microwaves to heat the Al–V2 O5 –C and it etched with HF to obtain
V2 C with very low defect density. Mei et al. [60] used UV-induced selective etching to etch
Mo2 Ga2 C in order to obtain Mo2 C. The flexible battery assembled with this Mo2 C achieved
excellent rate performance and cycle stability and exhibited excellent capacity retention
in the bent state. Since the advent of MXene and due to its rich surface functional groups,
large specific surface area, high conductivity, large porosity, rich organic bonds, and high
hydrophilicity, it can be used as a glucose sensor, electrode material, electromagnetic
shielding material, super capacitors, energy storage, and nanofluids, etc. [60–63].
MXene has played a significant role in supercapacitors and battery materials. However,
the studies conducted on gas sensors are far from sufficient. At the same time, there
are only a few reviews focusing on gas sensors made of MXene [64–67]. In this work,
we reviewed the synthesis method of MXene, the application of MXene in gas sensors,
and the mechanism of gas sensors. We aim to introduce MXene and gas sensors in detail
and to contribute to the body of research relative to MXene in gas sensors.
2. Synthesis of MXene
The synthesis of MXene include many aspects. This paper only reviews the synthesis
methods that may be beneficial to gas sensors. Firstly, the synthesis of MXene materials,
etching method, is discussed. Secondly, some subsequent preparation procedures will
optimize its performance after etching. For example, an intercalator is added in order to
increase the interlayer spacing. Finally, the preservation, use and yield of MXene are of
great significance to the practical application, so the synthesis methods which can improve
the dispersion of MXene and carry out large-scale production are discussed.
2.1. Etching
The synthesis method of MXene significantly affects the morphology and performance
of MXene. At present, scholars in various fields have conducted a lot of research on
MXene’s synthesis method. There are two methods for synthesizing 2D materials: one is
the bottom-up method, including physical vapor deposition and chemical vapor depo-
sition; the other is the top-down method, including peeling (micromechanical, solution
processing or ultrasonic processing) and selective etching [68]. The bottom-up method
must use a vacuum chamber and a substrate for growth. This method limits the final size
of the deposited material, while the top-down method does not have these limitations [68].
In this section, the etching of the top-down method will be discussed and other methods
will not be dwelt on.
According to previous reports, most Ti3 C2 Tx was prepared by etching Ti3 AlC2 using
high temperature and HF solution, which was the method used for the first discovery
of Ti3 C2 Tx [69,70]. The method to discover Ti3 C2 Tx for the first time was: (1) Ti3 AlC2
powder was prepared by ball milling Ti2 AlC and TiC; (2) Ti3 AlC2 powder was heated at
1350 ◦ C for 2 h under argon; (3) The calcined powder was immersed in a 50% HF solution
for 2 h; (4) The deionized water was used to wash the obtained solution, and products
were collected after centrifuged and dried [50]. The procedure is shown in Figure 1a.
The reaction mechanism of the etching is as follows [50]:
Ti3 AlC2 + 3HF = AlF3 + 3/2H2 + Ti3 C2 (1)
Ti3 C2 + 2H2 O = Ti3 C2 (OH)2 + H2 (2)

Ti3 C2 + 2HF = TI3 C2 F2 + H2 (3)
Reaction (1) is the reaction of Ti3 AlC2 in order to generate Ti3 C2 layer; Reaction
(2) and reaction (3) are the reactions of the generated Ti3 C2 layer with H2 O and HF,
indicating the formation of –OH and –F terminations on Ti3 C2 , also namely Tx . In the HF
etching process, MXene is affected by temperature, HF solution concentration, reaction
time, and ball milling time [71–73]. For example, Li et al. [71] discussed the effects of
time, temperature, Ti3 AlC2 source, and HF solution concentration on the synthesis of
Ti3 C2 . The research found that the low reaction temperature and the low HF solution
concentration would cause the MAX phase to remain after a long etching period. With
the increase in HF concentration and etching temperature, peeling off MAX was easier
and the more MXene was obtained. In addition, the longer the etching time, the better
the MXene stripping. Using 49% HF to peel off A at 60 ◦ C, it took at least 8 h to peel off
successfully. It was different from the effective peeling in 2 h that described in the previous
literature. This might be that the used Ti3 AlC2 was different. The higher the activity
of Ti3 AlC2 , the less reaction time was required. When the etching time was extended
to 24 h, a MXene sheet with completed stripping and a thickness of ~30 ± 5 nm can be
obtained. Su et al. [72] studied the effect of reaction temperature and ball milling time
on the synthesis of Ti3 C2 , and found that high etching temperature and longer ball milling
duration resulted in faster conversion of Ti3 C2 MXene. Using HF to etch MXene is the most
common and effective method. However, HF is highly toxic and corrosive, threatening to
individuals and unfriendly to the environment. So it is indispensable to exploit an effective
and harmless method to synthesize MXene [74].
Chemosensors 2021,
Chemosensors 9, 9,
2021, 225225 5 of5 of
4140
Figure
Figure (a) (a)
1. 1. Ti23TCx 2synthesized
Ti3C Tx synthesized
by HFbyetching
HF etching (Reproduced
(Reproduced with with permission
permission fromCopyright
from [50]. [50]. Copy-
2011, John
right 2011,Wiley
Johnand Wiley Sons);
and (b) Ti3C(b)
Sons); 2TxTi
synthesized
C
3 2 Tx by HCl
synthesized +
by LiF
HCl etching
+ LiF (Reproduced
etching with
(Reproduced per-
with
mission from from
permission [75]. Copyright 2020, 2020,
[75]. Copyright the Royal Society
the Royal of Chemistry).
Society of Chemistry).
Using
Using HCl HCl and
and LiF LiFtoto generate
generate HF HF instead
instead ofof directly
directly using
using HF,avoiding
HF, avoiding thethethreat
threat
ofof direct
direct useuse ofofHF,HF,this
thismethod
methodisiscalled calledthe the“in-situ
“in-situHF HFmethod”
method”[76]. [76].The
Thefirst
first“in-situ
“in-situ
HFHF method”
method” was was reported
reported inin 20142014 [77,78].
[77,78]. TheThe specific
specific method
method reported
reported inin theliterature
the literature
was: (1) Dissolving LiF in HCl;
was: (1) Dissolving LiF in HCl; (2) Adding Ti3AlC (2) Adding Ti AlC powder
3 2 powder
2 and heating the mixture at 40at
and heating the mixture
40 ◦ C for 45 h; (3) Rinsing it in order to get the clean MXene. The preparation of MXene
°C for 45 h; (3) Rinsing it in order to get the clean MXene. The preparation of MXene by
by +HCl
HCl LiF + is LiF
shown is shown
in Figure in Figure
1b [75].1b [75]. Compared
Compared with MXene withsynthesized
MXene synthesized
by HF, MXene by HF,
MXene synthesized
synthesized using LiF +using HCl had LiF + HCl lateral
larger had larger lateral and
dimensions dimensions and nodefects.
no nano-scale nano-scale Li+
defects. Li + and H O molecules were embedded, leading to the expansion of the interlayer
and H2O molecules were embedded, leading to the expansion of the interlayer spacing
2
spacing
and and the weakness
the weakness of the interaction
of the interaction between MXene between MXene
layers. Thelayers.
obtainedTheMXene
obtained MXene
showed
showed larger and more dispersed flakes and had higher
larger and more dispersed flakes and had higher yield, so LiF + HCl was widely used yield, so LiF + HCl was widely
to
synthesize MXene [77,79,80]. For example, Kim et al. [81] used LiF + HCl to synthesizeto
used to synthesize MXene [77,79,80]. For example, Kim et al. [81] used LiF + HCl
synthesize
MXene with MXene
low noise, withhighlow noise,
metal high metal conductivity,
conductivity, and functionalized
and functionalized surface. Itssurface.sig-
Its signal-to-noise ratio was much higher than that
nal-to-noise ratio was much higher than that of other two-dimensional materials, in- of other two-dimensional materials,
including
cluding blackblack phosphorus
phosphorus (BP), (BP),
MoS MoS 2 , and
2, and
reduced
reduced graphene
graphene oxide
oxide (RGO).
(RGO). TheThe lower
lower
detection limit of VOC gas (acetone, ethanol, and propionaldehyde)
detection limit of VOC gas (acetone, ethanol, and propionaldehyde) at room temperature at room temperature
was
was 50–100
50–100 ppb.
ppb. InIn addition
addition toto LiF,
LiF, there
there areare other
other fluoride
fluoride salts(such
salts (suchasas NaF,CaF
NaF, CaF , FeF ,
2, 2FeF3, 3
KF, NH
KF, NH4HF HF ,
4 2, NaHF
2 NaHF 2
2, KHF
, KHF 2
2, and
, and NH
NH4HF HF )
4 2) that
2 that can react with HCl to generate
can react with HCl to generate HF [82–88]. HF [82–88].
For example, Akinola et al. [82] used NaF and HCl to prepare Cr2 C MXene, which achieved
For example, Akinola et al. [82] used NaF and HCl to prepare Cr2C MXene, which
high yield, low by-products, fast etching time and large sheet area. The cations were
achieved high yield, low by-products, fast etching time and large sheet area. The cations
well embedded between the MXene sheets, which made MXene layers more spaced apart.
were well embedded between the MXene sheets, which made MXene layers more spaced
Wang et al. [83] used FeF3 and HCl to synthesize Ti3 C2 Tx for the first time. MXene prepared
apart. Wang et al. [83] used FeF3 and HCl to synthesize Ti3C2Tx for the first time. MXene
by FeF + HCl had a higher number of hydroxyl/oxygen terminal groups, which changed
prepared3 by FeF3 + HCl had a higher number of hydroxyl/oxygen terminal groups, which
the surface of MXene and resulted in a significant change in its hydrophilicity. Although
changed the surface of MXene and resulted in a significant change in its hydrophilicity.
HCl and fluoride are fewer harmful than HF, fluoride with etching effect is negative
Although HCl and fluoride are fewer harmful than HF, fluoride with etching effect is
to the device [89]. Fluoride etching of MXene normally results in abundant fluorine
negative to the device [89]. Fluoride etching of MXene normally results in abundant flu-
terminals on MXene, which are harmful to electronic conductivity, surface tunability,
orine terminals on MXene, which are harmful to electronic conductivity, surface tunabil-
and electrochemical performance [90].
ity, and electrochemical performance [90].
In recent years, there has been a lot of research on the synthesis of MXene by F-free etch-
ing,Insuch
recent years,etching
as alkali there has been electrochemical
[91–94], a lot of researchetching on the [95–97],
synthesis of MXene
halogen by F-free
etching [98,99],
etching, such as alkali etching [91–94], electrochemical etching
hydrothermal etching [90,100], and Lewis acid [74,101], etc. In theory, it is feasible [95–97], halogen etching
to use
[98,99],
alkali hydrothermal
as an etchant toetching etch Ti3[90,100], and Lewis
AlC2 . Because Al canacid
be [74,101],
dissolvedetc. byIn theory,
alkali owingit istofeasible
the high
toreactivity
use alkali of asAl.an etchant
Li et al. to etch
[91] Ti3AlC2. Because
successfully Al canTibeCdissolved
synthesized T using by thealkali owing to
NaOH-assisted
3 2 x
Chemosensors2021,
Chemosensors 2021,9,9,225
225 66 of
of 40
41
the high reactivity of Al. Li et al. [91] successfully synthesized Ti3C2Tx using the
NaOH-assisted hydrothermal method. The experiment temperature was 270 °C and the
the high reactivity of Al. Li etwas al. 27.5
[91] M. successfully synthesized Ti3CNaOH2Tx using the
concentration
hydrothermal of NaOH
method. solution
The experiment The high
temperature was 270 ◦ C andand
temperature the concentrationconcen-
NaOH-assisted
tration hydrothermal method. The experiment temperature was 270 °C and the
of NaOHwere conducive
solution was 27.5 to M.theThedissolution of Al (Figure
high temperature and NaOH2). Thisconcentration
was the firstwere timecon-
that
concentration
MXenetohas of NaOH solution was
only27.5 M. The highandtemperature andand NaOH concen-
ducive thebeen synthesized
dissolution of Al by (Figure alkali
2). Thisetching
was the firstmany
time –OH that MXene O hasterminals
been
tration were
could be produced conducive to
by this the dissolution
method. of Al (Figure 2). This was the first time that
synthesized by only alkali etching and Based
many –OH on alkali
and O etching,
terminals scholars
could be have developed
produced by
MXene
other has
methods been synthesized
thaton cooperate by only
with alkali alkali etching
etching. and many –OH and O terminals
this method. Based alkali etching, scholars haveZhangdeveloped et al.other
[92] successfully
methods thatsynthe- coop-
could
sizedwithbe3Cproduced
Ti 2(OH)2etching.
by this
-MXene method.with
nanobelts Based on alkalisurface etching, scholarsterminals
have developed
erate alkali Zhang et al. [92]abundant
successfully synthesized hydroxyl Ti3 C2 (OH)2 -MXene using a
other methods
small amount that cooperate
of H2O-assisted with alkali etching. Zhang et al. [92] successfully synthe-
nanobelts with abundant surfaceKOH. hydroxyl Theterminals
synthesisusingprocess is shown
a small amountinofFigure 3.
H2 O-assistedKOH
sized
and water
KOH.
Ti3C2contents
(OH)2-MXene
The synthesis were
process
nanobelts
essential
is shown towith
the abundant
etching
in Figure
surface
3. process
KOH and and hydroxyl
could
water affect
contents
terminals
the
were
using of
thickness
essential
a
small
MXene.
to amount
the etching of
The morphologyH 2O-assisted KOH. The synthesis process is shown in Figure 3. KOH
process and could of MXene affectcould be controlled
the thickness by KOH
of MXene. Theand water contents.
morphology of MXene Xue
and
et al.water
could be contents
[93]controlled
used were
by KOH
a chemical essential
and water
combined to the etching
contents.
ball milling process
Xue et al.and
method tocould
[93] usedTi
etch affect the thickness
a 3chemical
C2 MXene combined of
with tet-
MXene.
ball The morphology
milling method to hydroxide
ramethylammonium of MXene
etch Ti3 C2 MXene could
(TMAOH) be
withand controlled by
tetramethylammonium KOH
LiCl solution. Figure and water
hydroxide contents.
(TMAOH)
4 is the preparation Xue
et
and al. [93]
LiCl used
solution. a chemical
Figure 4 iscombined
the ball
preparation milling
process. method
The
process. The specific surface area of the F-free MXene reached 38.93 m /g due to to
specific etch Ti 3C22 MXene with tet-
surface area of theitsF-free
hier-
ramethylammonium
MXene
archicalreached
porous 38.93 hydroxide
structure 2
m /g and due (TMAOH)
thetoterminals and
its hierarchicalLiCl
which only solution.
porous were Figure
structure 4 is the preparation
and the terminals
oxygen-containing groups
process.
which
(O/OH). onlyThewerespecific
Rafieerad et surface
al. [94] area
oxygen-containing usedof the F-free
groups
HCl-assisted MXene
(O/OH).KOH reached
Rafieerad
alkaline 38.93
etetching
al. [94]min 2/g due to its hier-
used HCl-assisted
order to synthe-
archical
KOH
size Ta porous
alkaline
4C3Tx MXene.
structure
etching The and the
in order
biggest terminals
to synthesize
problem withwhich
C3 Tonly
Ta4alkaline were The
x MXene.
etching oxygen-containing
wasbiggest
that Al problem groups
with
and alkaline
(O/OH).
alkaline Rafieerad
mediumetchingformed was et al. [94]
that Al and
insoluble used HCl-assisted
alkaline
Al(OH) 3 and medium
AlO(OH)KOH
formed alkaline
insoluble
on the etching
surface Al(OH) in
of MXeneorder to synthe-
3 and AlO(OH)
to hinder
size
on Tasurface
the
further 4C3Tx MXene.
etching. of HCl
MXene The
wasto biggest
hinder
used toproblem
further
assist thewith alkaline
etching.
synthesis. etching
HClDuring
was used
thewasto that Althe
assist
synthesis and alkaline
synthesis.
process, alu-
medium
During
minum the formed
atomssynthesisinsoluble
passed process,
through Al(OH)
aluminum
HCl 3 and AlO(OH)
atoms passed
to quickly on the surface
through
chlorinated. HCl
It would of to MXene
quickly
produce to soluble
hinder
chlori-
further
nated.
aluminum Itetching.
would HCl (AlCl
produce
chloride was used
soluble to assist
aluminum
3), which might thechloride
synthesis.
reduce During
(AlCl 3 ), which
insoluble the might
aluminidesynthesis reduce
and process, alu-
insoluble
promote the
minum
aluminide atoms
and passed
promote through
the etching.HCl
etching. The synthesis process is shown in Figure 5. to
The quickly
synthesis chlorinated.
process is It
shown would
in produce
Figure 5. soluble
aluminum chloride (AlCl3), which might reduce insoluble aluminide and promote the
etching. The synthesis process is shown in Figure 5.
Figure2.2.The
Figure Thereaction
reaction between
between Ti3AlC
Ti3 AlC 2 and NaOH water solution (Reproduced with permission
2 and NaOH water solution, (a) Reaction at low temperature; (b)
from [91].
Reaction at Copyright 2021, John
high temperature and Wiley and Sons).
low NaOH concentration; (c) Reaction at high temperature and high
Figure 2. The reaction between Ti3AlC2 and NaOH water solution (Reproduced with permission
NaOH concentration (Reproduced with permission from [91]. Copyright 2021, John Wiley and Sons).
from [91]. Copyright 2021, John Wiley and Sons).
Figure 3. Schematic illustration of the synthesis of Ti3C2(OH)2 by water-assisted potassium hy-

droxide (Reproduced with permission from [92]. Copyright 2019, Elsevier).
Figure3.3.Schematic
Figure Schematicillustration
illustration of the
of the synthesis
synthesis of Ti3of
C2Ti 3C2(OH)
(OH) 2 by water-assisted
2 by water-assisted potassium
potassium hy-
hydroxide
droxide (Reproduced with permission from [92]. Copyright
(Reproduced with permission from [92]. Copyright 2019, Elsevier). 2019, Elsevier).
Figure
Figure4.4.
Figure Schematic
4.Schematic diagram
diagramofof
Schematicdiagram ofthethe
the preparation
preparation of
of3 Ti
of Ti
preparation C233C
Ti 2 by chemical-combined ball milling (Re-
by
C chemical-combined
2 by chemical-combined ballball
milling (Repro-
milling (Re-
produced
produced
duced with
withwith permission
permission
permission from
fromfrom [93].
[93].[93]. Copyright
Copyright
Copyright 2020,
2020,2020, American
American
American Chemical
Chemical
Chemical Society).
Society).
Society).
Figure
Figure5.5.
Figure Sketch
5.(a)
Sketch map
mapof
map
Sketch ofofthe
thepreparation
the preparationof
preparation of Ta
of Ta444C
Ta CC333T
TTxx xby
byHCl/KOH
by HCl/KOH;(Reproduced
HCl/KOH (Reproduced with permission
withequation
(b) The reaction permission
of
from [94]. Copyright
from [94]. Copyright 2021, John Wiley and Sons).
HCl/KOH to prepare 2021,
Ta4 C3John Wiley and Sons).
Tx (Reproduced with permission from [94]. Copyright 2021, John Wiley
and Sons).
There
There areare also
also related
related reports
reports using
using only
only HCl
HCl as as an
an etchant.
etchant. Wang
Wang et et al.
al. [90]
[90] usedused the
the
HCl hydrothermal
There are also method
related to obtain
reports fluorine-free
using only HCl Mo
as 2C etchant.
an MXene
HCl hydrothermal method to obtain fluorine-free Mo2C MXene with a productionused with
Wang a production
et al. [90] effi-
effi-
ciency
the HClof
ciency 98%.
98%. Since
Since there
ofhydrothermal was
was F-free
method
there etching,
to obtain
F-free the
the terminals
fluorine-free
etching, Mo2 Cof
terminals MXene
ofMXene
MXenewithwere
wereaonly chlorine
production
only chlorine
and oxygen-containing
efficiency of 98%. Since there
and oxygen-containing terminals.
was F-free
terminals. The surface
Theetching,
surfacethe functional groups
terminalsgroups
functional of MXenecould be adjusted
werebeonly
could chlorine
adjusted by
by
adding
and N source
oxygen-containing or S source to
terminals.the hydrothermal
The surface reactor
functional during
groupsthe etching
could
adding N source or S source to the hydrothermal reactor during the etching process. Un- be process.
adjusted Un-
by
like
like the
adding theNaccordion
source or structure
accordion S source toof
structure the
ofthe other
other MXene,
thehydrothermal the
the structure
MXene,reactor during of
structure theMo
of 2CTx that
etching
Mo obtained
process.
2CTx that obtained by
by
Unlike
the
the HCl hydrothermal
accordion structure method
of the showed
other a
MXene, clear
thelayered structure
structure of Mo
the HCl hydrothermal method showed a clear layered structure (Figure 6). This method(Figure
2 CT x 6).
that This
obtained method
by
the HCl2021,
provides
provides
Chemosensors hydrothermal
ideas
ideas
9, 225 for
for the method showed
the development
development of a clearF-free
of better
better layered
F-free structure (Figure 6). This
MXene.
MXene. 8 of method
43
provides ideas for the development of better F-free MXene.
Figure
Figure The SEM(a)
6. The (a)Figure
and6. TEM
The SEM (a) and TEM (b) of Mo2C synthesized by HCl-Based hydrothermal etching (Re-
(b) ofMo Mo C synthesized by HCl-Based hydrothermal etching
Figure 6.
6. The SEM and
and TEM
SEM (a)produced TEM (b)
(b) of
of Mo
with permission 2C2[90].
synthesized
2C synthesized
from by HCl-Based
byJohn
Copyright 2021, HCl-Based hydrothermal
hydrothermal etching
Wiley and Sons). etching (Re-
(Re-
(Reproduced
produced with
with permission
permission fromfrom [90].
[90]. Copyright
Copyright 2021,
2021, JohnJohn Wiley
Wiley andand Sons).
Sons).
produced with permission from [90]. Copyright 2021, John Wiley and Sons).
Halogen etching can also be used as an etching method for MXene. Jawaid et al. [98]
used halogens (Br2, I2, ICl, IBr) to synthesize Ti3C2Tx MXene successfully. Choosing dif-
ferent halogens for etching led to different terminals on MXene. The process is shown in
Figure 7. For reaction by-products, the inert gas was continuously circulated in the puri-
fication system to remove volatile by-products in order to obtain pure MXene. Tetrabutyl
ammonium halide was added as a stabilizer salt in order to separate by-products. Halo-
Chemosensors
Chemosensors 2021, 9, 225 2021, 9, 225 8 of 40 8 of 4
Halogen Halogen
etching etching canused
also bean used as anmethod etching method for MXene.etJawaid et al. [98
Halogen
used etchingcan
halogens can (Br
also
also be
be usedas as anetching
etching methodfor forMXene.
MXene.Jawaid
2, I2, ICl, IBr) to synthesize Ti3C2Tx MXene successfully. Choosing dif
Jawaid etal. al.[98]
[98]
used
usedhalogens
halogens (Br
(Br22,, II22,, ICl,
ICl, IBr) to tosynthesize TiTi3 C 2 Tx MXene successfully. Choosing dif-
ferent halogens
ferent halogens for etching for IBr)
etching
led
synthesize
led to different
to different terminals
3C2Tx MXene successfully. Choosing dif-
terminals
on MXene. on MXene.
The processThe process
is shown is shown in
ferent halogens
Figure for
7. Foretching
reaction ledby-products,
to different terminals
the inert on MXene.
gas was The process
continuously is shownininthe puri
circulated
in Figure 7. For reaction by-products, the inert gas was continuously circulated in the pu-
Figure 7. For reaction by-products, the inert gas was continuously circulatedpurein the puri-
rification fication
system to system
remove to remove volatile
volatile by-products by-products
in order in to order
obtainto obtain
pure MXene. MXene.
Tetrabutyl Tetrabuty
fication system
ammonium to remove
halide volatile
was by-products
added as a in
stabilizer order to
salt obtain
in order pure
to MXene.
separate Tetrabutyl
by-products. Halo
ammonium halide was added as a stabilizer salt in order to separate by-products. Halogen
ammonium gen halide
etching waswas added
used as expand
to a stabilizerthe salt
MXene in order
layer to separate
spacing and by-products.
it could alsoHalo-
be etched in
etching was used to expand the MXene layer spacing and it could also be etched in other
gen etching
otherwasMAX used to expand
phases except theforMXene
Ti AlC layer
. spacing
Halogen and itcan
etching could also be
become a etched
new in F-free
green,
MAX phases except for Ti3 AlC2 . Halogen etching can become a new green, F-free etching
3 2
other MAX phases exceptShi foretTi
al.3AlC
[99]2.used
Halogen etching
etchingcan become a new green, F-free
method. etching
Shi et al.method.
[99] used iodine etching iodine
(IE) in anhydrous (IE) in anhydrous
acetonitrile (CH3acetonitrile
CN) to syn-(CH3CN
etching method. Shi etfluorine-free
to synthesize al. [99] used iodine etching (IE) inaverage
anhydrous sizeacetonitrile (CH3CN)
thesize fluorine-free Ti3 C2 Tx MXene.TiThe 3C2Taverage
x MXene. The
size of the obtained of the obtained
MXene was about MXene wa
to synthesize
about fluorine-free
1.8productivity
µm, with high Ti 3C2Tx MXene. The average size of the obtained MXene was
productivity (71%), high oxygen
1.8 µm, with high (71%), high oxygen content (18.7 wt %)content
and high (18.7 wt %) and high
conductiv-
about 1.8 µm, with high productivity (71%), high oxygen content
MAX (18.7 wt %) and high in the
cm−1 ). This(1250
ity (1250 Sconductivity method S cm
was -1). This
that themethod
MAX powder was thatwas
the immersed powderin thewas immersed
I2 –CH 3 CN
conductivity
2–CH3the
mixture. ISince (1250 S
CN Ti-Al cm
mixture.
-1). This method was that the MAX powder was immersed in the
bond Since
was the Ti-Althan
weaker bond thewas
Ti–Cweaker
bond,thaniodinethecould
Ti–C selectively
bond, iodine could
I2–CH3CN mixture. Since the Ti-Al bond was weaker than the Ti–C bond, iodine could
eliminate Al from the MAX phase. HCl solution was used to wash away excess to
selectively eliminate Al from the MAX phase. HCl solution was used AlIwash
3 andaway ex
selectively eliminate
cess AlI
MXene layers 3 and
in the Al from the
MXeneproducts.
obtained MAX
layers inThe phase.
the process
obtainedHCl solution
products.
is shown was used
The process
in Figure to wash away
is shown in
8. The performance ex-Figure 8
cess AlI3 and MXene layers in the obtained products. The process is shown in Figure 8.
The performance
of the supercapacitor prepared of thebysupercapacitor
this method was prepared
far superiorby this method
to the was far
previously superior to the
reported
The performance
MXene previouslyofreported
material. the supercapacitor
MXene material. prepared by this method was far superior to the
previously reported MXene material.
Figure 7. (A) Schematic

Figureillustration of theillustration
7. (A) Schematic preparation ofof
theTipreparation
2C2Tx by halogen
of Ti2 Cetching; (B) Experimental photos of reagent
2 Tx by halogen etching; (B) Experimen-
Figure 7. mixture;
(A) Schematic illustration ofphotos
(C) Experimental the preparation
of mixture ofwith
Ti2C2etchant;
Tx by halogen
(D) etching; (B) Experimental
Experimental photos the photos
of etchant;
crude of reagent
tal photos of reagent mixture; (C) Experimental photos of mixture with (D)MXene; (E) Experi-
Experimental
mixture; mental
(C) Experimental photos
photos of the of layer
single mixture with(Reproduced
MXene etchant; (D) with
Experimental
permissionphotos
from of theCopyright
[98]. crude MXene;
2021, (E) Experi-Chemical
American
photos of the crude MXene; (E) Experimental photos of the single layer MXene (Reproduced with
mental photos of the single layer MXene (Reproduced with permission from [98]. Copyright 2021, American Chemical
Society).
Society). permission from [98]. Copyright 2021, American Chemical Society).
Figure 8. The bond schematic diagram (a) and the model schematic diagram (b) of the preparation
Figure8.8. The
Figure The
of bond
Tibond schematic
3C2Txschematic diagram(a)
by iodinediagram
etching (a)and
andthe
the
(Reproduced model
model schematic
withschematic diagram
diagram
permission from (b)(b) of the
ofCopyright
[99]. the preparation
preparation
2021,of
John Wiley
of Ti 3C2Txand
by iodine
etching (Reproduced with permission from [99]. Copyright 2021, John WileyJohn
Sons).
Ti3 C2 Tx by iodine etching (Reproduced with permission from [99]. Copyright 2021, Wiley
and Sons).
and Sons).
Chemosensors 2021, 9,
Chemosensors 2021, 9, 225
225 9 9of
of 41
40
Lewis acid etching is a new fluorine–free etching method. Li et al. [74] immersed
Ti3SiCLewis acid etching is a new fluorine–free etching method. Li et al. [74] immersed
2 in the CuCl2 Lewis salt. Redox reaction occurred between Ti3SiC2 and CuCl2 to
Ti3 SiC2 in the CuCl2 Lewis salt. Redox reaction occurred between Ti3 SiC2 and CuCl2
etch the Si in order to form Ti3C2Tx MXene. Then, the obtained MXene was washed in
to etch the Si in order to form Ti3 C2 Tx MXene. Then, the obtained MXene was washed
ammonium persulfate solution (Figure 9). SiCl4, born during the reaction, could be used
in ammonium persulfate solution (Figure 9). SiCl4 , born during the reaction, could be used
as an expansion agent to be embedded in the MXene layer. MXene embedded by water
as an expansion agent to be embedded in the MXene layer. MXene embedded by water
did not release any –OH, which meant that the hydrophilicity of the MXene surface was
did not release any –OH, which meant that the hydrophilicity of the MXene surface was
reduced. The Lewis acid etching method proposed here provides a new idea for prepar-
reduced. The Lewis acid etching method proposed here provides a new idea for preparing
ing MXene without F. However, this method needs to be carried out at◦ 750 °C. Exces-
MXene without F. However, this method needs to be carried out at 750 C. Excessively
sively high temperature is detrimental to cost and product, so it still needs to develop the
high temperature is detrimental to cost and product, so it still needs to develop the other
other F-free methods.
F-free methods.
Figure
Figure 9.
9. Schematic
Schematic illustration
illustration of the preparation
of the preparation of
of Ti
Ti33C
C22T
Txx by
by Lewis
Lewis acidic
acidic etching
etching (Reproduced
(Reproduced
with permission from [74]. Copyright 2020, Springer Nature).
with permission from [74]. Copyright 2020, Springer Nature).
It
It is reported that
that the
the volume
volumeexpansion
expansionofofAl AlandandLiLiwill
willexceed
exceed 100%100% when
when form-
forming
ing Al–Li alloy. Using this expansion, the interlayer binding force
Al–Li alloy. Using this expansion, the interlayer binding force can be reduced, making can be reduced, mak-
ing
the the Al layer
Al layer to beto separated
be separated from from
the the
MAX MAX possible.
possible. Sun Sun et al.
et al. [89][89] prepared
prepared sin-
single-
gle-layer and few-layer
layer and few-layer fluorine-free fluorine-free
Ti3 C2 Tx basedTion 3Cthe2Tx intercalation-alloying-expansion-
based on the intercala-
tion-alloying-expansion-microexplosion
microexplosion mechanism. The electric mechanism.
field forcedThe electric field
to promote the forced of Li+
to promote
embedding
the embedding
in electrolyte in of
theLiAl
+ in electrolyte
layer of MAXinandthe an
Al Al–Li
layer of MAX
alloy wasand an Al–Li
formed. Then,alloy was
there formed.
happened
to be the
Then, expansion
there happened oftothebeAl–Al layer. When
the expansion placing
of the Al–Althe lithiated
layer. When MAX placing into
thethe water,
lithiated
the Al–Li layer would react
MAX into the water, the Al–Li layer with H O and bring H
2 would react with 2 . A micro explosion occurred
H2O and bring H2. A micro explo- between
layers,
sion which caused
occurred between MAX to peel
layers, whichoff caused
into Ti3 C 2 Tx nanosheets
MAX to peel off (Figure
into Ti310).
C2TxThe Ti3 C2 Tx
nanosheets
prepared
(Figure byThe
10). thisTi
method had an ultra-thin
3C2Tx prepared translucent
by this method had structure,
an ultra-thin andtranslucent
had a high structure,
yield and
a fasthad
and speed, which
a high yieldwasand advantageous
a fast speed,for realizing
which the actual production
was advantageous of MXene.
for realizing the actual
production of MXene.
Figure 10. Schematic illustration of the preparation of Ti3C2Tx by lithia-

Figure10. Schematic
Figure 10. Schematic
illustrationillustration
tion-expansion-microexplosion (Reproduced
of ofwithof
the preparation theTi3 Cpreparation
permission
T
2 x by from of
[89]. Ti3C2Tx 2019,
Copyright by Ameri-
lithia-
lithiation-expansion-microexplosion
tion-expansion-microexplosion
can Chemical Society). (Reproduced with permission from [89].
(Reproduced with permission from [89]. Copyright 2019, American Chemical Society). Copyright 2019, Ameri-
can Chemical Society).
In MXene,
MXene, Mo Mo22Ga22C C is an ultraviolet absorbing material, with with excellent
excellent ultraviolet
ultraviolet
responseIn MXene, Mo2Ga2C
characteristics is an
[60]. ultraviolet
According absorbing
to the
the UV material,
UV response
response with excellent
characteristics
characteristics of
ofMoultraviolet
Mo 22Ga
Ga22C,
response
Mei et al. characteristics
[60] successfully [60]. According
synthesized
et al. [60] successfully synthesized Mo Mo to
C the
MXene UV response
with high characteristics
yield, high
2 2C MXene with high yield, high quality, of
quality, Mo
and Ga 2C,
2meso-
and
Mei
porous et
mesoporous al. [60]
structure successfully
usingusing
structure synthesized
UV-induced Mo
etching
UV-induced C MXene
within
etching
2 with high
a fewahours.
within yield, high quality,
The experimental
few hours. The experimental and
pro-
mesoporous
cedure
procedure structure using
of UV–induced
of UV–induced etching UV-induced
was:
etching was:(1)1)Theetching
The Mo
Mo 2within
2 GaGa2 C a few hours.
2Cprecursor
precursor was The
was etchedexperimental
etched by UV ir-
procedure(2)
radiation; 2)ofThe
UV–induced
The MXene was
MXene etching
was peeled
peeledwas:off 1)
off Theultrasonic
with Mo2Ga2C in precursor
order totowas etched
obtain
obtain by UV ir-
independent
independent
radiation;
MXene 2) The
nanosheets. MXene
The was
procedure peeled
is off
shown with
in ultrasonic
Figure 11. in
This
MXene nanosheets. The procedure is shown in Figure 11. This method was fast and order
method to obtain
was fast independent
and did not
did
MXene
involve nanosheets.
HF acid. It The
was of procedure
great is shown
significance toin Figure
MXene 11.
with This
UV method
response
not involve HF acid. It was of great significance to MXene with UV response characteris- was fast and did
characteristics,
notitbut
but
tics, involve
limited HF acid.
its use
it limited itstoItthe
use was of great
togeneral
the significance
MXene,
general which
MXene, to
is MXene
which notwith
notissensitive UV response
to UV.
sensitive to UV. characteris-
tics, but it limited its use to the general MXene, which is not sensitive to UV.
the synthesis
Figure 11. Schematic illustration of the synthesis of
of Mo
Mo22Ga22C by UV-induced etching
etching (Reproduced
(Reproduced
Figure
with
with 11. Schematic
permission
permission from illustration
from [60]. of the
[60]. Copyright
Copyright synthesis
2020,
2020, of Mo2Ga2C by UV-induced etching (Reproduced
Elsevier).
Elsevier).
with permission from [60]. Copyright 2020, Elsevier).
One of the methodsmethods to to be
be mentioned
mentioned in in particular
particular isis electrochemical
electrochemical etching.
etching. Elec-
One ofetching
trochemical the methods
etching wouldtonot
would beonly
not mentioned
onlyetch
etch inAparticular
thethe A layer,
layer, is
butbut electrochemical
alsoalso over-etch
over-etch the Metching.
thelayer. Elec-
M layer.
Sun
trochemical
Sun
et al.et[95]
al. [95] etching would
successfully
successfully not only
synthesized
synthesized etch
Ti2CT the
Ti2x CT A layer,
x MXene
MXene but also over-etch
by electrochemical
by electrochemical the M
etching
etching layer. Sun
in HCl
in HCl so-
et al. [95]
solution
lution forforsuccessfully
thethe first
first time. synthesized
time.
TheThe process
process Ti CT
of2of
this x MXene
this method
method by electrochemical
was:
was: 1) (1) Al was
Al was etchinggetting
selectively
selectively in getting
HClridso-
lution
rid of for
from the
the first
MAX time. The
phase; process
(2) The of this
cathode method
potential was:
of from the MAX phase; 2) The cathode potential increased and both Al and 1)
increasedAl was
and selectively
both Al andgetting
Ti haverid
have
of from
etched the
away, MAX
leaving phase; 2) The
carbide-derived cathode
carbon potential
(CDC). increased
The procedure
away, leaving carbide-derived carbon (CDC). The procedure is shown in Figureand both
is shownAl and
in Ti
Figure have
12.
etched
The
12. etched
The away,sample
etched leaving
hadcarbide-derived
sample three
hadstructures: carbon (CDC).
carbide–derived
three structures: Thecarbon,
procedure
carbide–derived MXene,is shown
carbon, and in Figure
unetched
MXene, and
12.
MAX. The
unetched MXeneetched
MAX. sample
wasMXene
separatedhad
wasfrom three structures:
these structures
separated carbide–derived
from thesebystructures
ultrasound. carbon,
by Since MXene,
no fluoride
ultrasound. and
Sinceions
no
unetched
were involved
fluoride MAX.
ions were MXene
in the was
etching
involved inseparated
process, from
there were
the etching these–Cl,
only
process, structures
–O,were
there by
and –OH
onlyultrasound.
terminals
–Cl, –O, in Since
andMXene.
–OH no
fluoride ions
terminals in MXene. were involved in the etching process, there were only –Cl, –O, and –OH
terminals in MXene.
Figure12.
12.Schematic
illustration of
ofthe
thepreparation
preparationofofTiTiCT
2CTx by HCl solution (Reproduced with
Figure 2 x by HCl solution (Reproduced with
permission from [95]. Copyright 2017, the Royal Society of Chemistry).
permission from [95]. Copyright 2017, the Royal Society of Chemistry).
Until now,
Until now, the
the F-free
F-free etching
etching method
methodhas
hasnot
notbeen
beenstudied enough
studied andand
enough a lot
a of
lotthe-
of
oretical and practical work is still needed. The F-containing etching methods using
theoretical and practical work is still needed. The F-containing etching methods using HFHF
andLiF
and LiF++HCl
HClare
arestill
stillthe
themost
mostused.
used.
2.2.
2.2.Intercalator
Intercalator
Due
Dueto tothethein-plane
in-planecovalent
covalent bond bond andand the
the van
van derder Waals
Waalsforce
forcebetween
betweenthe thelayers,
layers,
the
theMXene
MXenehas hasa asmall
small interlayer
interlayer spacing.
spacing.TheThe
increase
increase in interlayer spacing
in interlayer makes
spacing the spe-
makes the
cific surface
specific area area
surface larger, makesmakes
larger, activeactive
sites greater, and makes
sites greater, ion transport
and makes channels
ion transport wider.
channels
Additionally, it is crucial
wider. Additionally, it istocrucial
the performance of MXeneof[102].
to the performance MXene When theWhen
[102]. intercalators
the intercala-were
added in MXene,
tors were addedthe intercalation
in MXene, makes the layers
the intercalation makesswell,theso the distance
layers swell, so between
the distance the layerbe-
increases. The intercalator mainly includes organic molecules
tween the layer increases. The intercalator mainly includes organic molecules and metal and metal cations. In 2013,
Mashtalir
cations. Inet2013,
al. [103] inserted
Mashtalir et hydrazine hydratehydrazine
al. [103] inserted (HM, N2 H 4 •H2 O)(HM,
hydrate and DMFin
N2H4•HTi2O) 3 C2and
Tx
in dimethyl sulfoxide (DMSO) for the first time. After ultrasonic
DMFin Ti3C2Tx in dimethyl sulfoxide (DMSO) for the first time. After ultrasonic treat- treatment, the embedding
of HM and
ment, DMF causedofthe
the embedding HM layerandspacing of MXene
DMF caused thetolayer
increase (Figure
spacing 13a,b). Since
of MXene then,
to increase
the research
(Figure on intercalators
13a,b). Since then, the used for layering
research has gradually
on intercalators usedincreased.
for layering Qian hasetgradually
al. [104]
used DMSOQian
increased. to layer Ti3 C
et al. 2 Tx in
[104] order
used to obtain
DMSO dispersed
to layer Ti3C2MXene flakes.toAs
Tx in order for the
obtain MXene
dispersed
treated by DMSO, there were the replacement of –F by
MXene flakes. As for the MXene treated by DMSO, there were the replacement of –F by –OH, the increase of interlayer
spacing,
–OH, the and the enhancement
increase of interlayer of hydrophilicity
spacing, and the during the delamination
enhancement process. The
of hydrophilicity the-
during
oretical model of DMSO that was embedded
the delamination process. The theoretical model of 3DMSO in Ti C O and
2 2 that wasTi C (OH)
3 2embedded 2 was studied.
in Ti3C2O2
Itand
wasTifound that the interlayer spacing of Ti3 C2the
3C2(OH)2 was studied. It was found that
(OH) 2 was larger
interlayer spacingthanofthat
Ti3Cof Ti3 C22was
2(OH)
O2
after
largerDMSO embedding.
than that of Ti3C2OIt2 aftermightDMSObe because of the hydrogen
embedding. It might be atoms
becauseof Tiof3 Cthe
2 (OH) 2 and
hydrogen
the methyl group of DMSO. Hydrogen atoms and the
atoms of Ti3C2(OH)2 and the methyl group of DMSO. Hydrogen atoms and the methylmethyl group were mutually exclu-
sive.
group In were
addition, Ti3 C2 (OH)
mutually 2 and DMSO
exclusive. interacted
In addition, Ti3C2electrostatically
(OH)2 and DMSO to promote
interacted interlayer
electro-
dispersion. Overbury et al. [105] embedded urea in Ti3 C2 Tx and found that urea was de-
statically to promote interlayer dispersion. Overbury et al. [105] embedded urea in
composed under the promotion of MXene, causing the C–N bond of the molecule to break.
Ti3C2Tx and found that urea was decomposed under the promotion of MXene, causing
The reason for the increasing interlayer spacing of MXene was that the decomposition of
the C–N bond of the molecule to break. The reason for the increasing interlayer spacing
urea produced the ammonium intercalation, so that the interlayer swelled. Xu et al. [106]
of MXene was that the decomposition of urea produced the ammonium intercalation, so
inserted ethylenediamine (EDA) into Ti3 C2 Tx MXene nanosheets, where EDA was an-
that the interlayer swelled. Xu et al. [106] inserted ethylenediamine (EDA) into Ti3C2Tx
chored to Ti3 C2 Tx through N-Ti coordination bonds, as shown in Figure 14. The insertion
MXene nanosheets, where EDA was anchored to Ti3C2Tx through N-Ti coordination
of organic molecules EDA made the interlayer spacing of MXene larger and there were
bonds, as shown in Figure 14. The insertion of organic molecules EDA made the inter-
abundant mesopores. Due to the expansion of the layer spacing, the specific surface area
layer spacing of MXene larger and there were abundant mesopores. Due 2to −the expan-
of EDA–Ti3 C2 Tx (59.2 m2 g−1 ) was much higher than pure Ti3 C2 Tx (13.6 m g 1 ). Large
sion of the layer spacing, the specific surface area of EDA–Ti3C2Tx (59.2 m2 g−1) was much
interlayer spacing, abundant mesopores and large specific surface areas were beneficial to
higher than pure Ti3C2Tx (13.6 m2 g−1). Large interlayer spacing, abundant mesopores and
the better performance of MXene. Wang et al. [107] inserted dipicolinic acid (DC) molecules
large specific
between MXene surface
layersareasunder werethe beneficial
ultrasound toand
the better performance
successfully realizedofthe MXene.
expansion Wangofet
al. MXene
the [107] inserted
nanosheet dipicolinic
spacing.acid MXene (DC)without
molecules DC hadbetween MXene
a typical layers under
accordion-like the ul-
structure
trasound and successfully realized the expansion of
(Figure 15a) with small inter-layer spacing. On the other hand, DC particles appeared the MXene nanosheet spacing.
MXene without DC had a typical accordion-like structure (Figure 15a) with small in-
ter-layer spacing. On the other hand, DC particles appeared on the surface or between
Chemosensors
Chemosensors
Chemosensors 2021,
2021,
2021, 9,9,225
9, 225 225 1212
12of
of of4141
41
on the
layers
layers
layers surface
ofofofMXeneor
MXene
MXene between
with
with
with DCDC
DClayers of15b,c),
(Figure
(Figure
(Figure MXene
15b,c),
15b,c),with
and
andand
theDC
the
the (Figure
layer
layer
layer 15b,c),
spacing
spacing
spacing wasand
was
wasthe layer spacing
significantlyin-in-
significantly
significantly in-
was significantly
creased.
creased. increased.
creased.
Figure
Figure 13.13.
Figure (a)(a)
13. (a)SEM
SEM
(a) SEM
SEM images
images
images
images before
before
before intercalation
intercalation
before of of
intercalation
intercalation off–Ti
f–Ti
of 3CC
f–Ti
3C23 3C
f–Ti 2 2with
with with
HMHM
HM and
andandDMF;(b)(b)
DMF;
DMF; SEM
(b)
SEM SEM images
images
images after
after
after
Figure 13. 2 with HM and DMF; (b) SEM images after
intercalation
intercalation
intercalation of
of of f–Ti
of
f–Ti 3C
f–Ti 2 2with
C
3C2Cwith
3 withHMHM and
andDMF
DMF (Reproduced
(Reproduced with
withpermission
permissionfrom
HM and DMF (Reproduced with permission from [103]. Copyrightfrom [103].
[103].Copyright
Copyright
intercalation f–Ti 3 2 with HM and DMF (Reproduced with permission from [103]. Copyright 2013,
2013,
2013,
2013, Springer
Springer
Springer Nature).
Nature).
Nature).
Springer Nature).
Figure
Figure
Figure 14.14.
Figure 14.
14. Schematic
Schematic
Schematic
illustration
illustration
illustration of
ofof
the the
ofthe
thepreparation
preparation
preparation ofof
preparation
of of3Ti
Ti
Ti C32C
Ti 2T
C
3T Tx xby
by
byEDAEDA
EDA
EDA (Reproduced
(Reproduced
(Reproduced with
with
with permis-
permis-
permission
3C 2T x x2by (Reproduced permis-
sion
sionsionfrom
from
from from [106].
[106].
[106]. Copyright
[106]. Copyright
Copyright
Copyright 2021,
2021,
2021,
2021, Elsevier).
Elsevier).
Elsevier).
Elsevier).
Figure15.15.
Figure
Figure
Figure (a)(a)
15.
15. (a)SEM
(a)
SEM SEM
SEM images
images
images
images without
without
without
without interacted
interacted
interacted
interacted DC;
DC;DC;
DC;(b,c)
(b,c)
(b,c)
(b,c) SEMSEM
SEM
SEM images
images
images
images interactedbyby
interacted
interacted
interacted by
by
DCDC
DC
DC (Reproduced
(Reproduced
(Reproduced
(Reproduced with
with
with
with permission
permission
permission
permission
from
fromfrom[107].
[107].
[107].
from Copyright
Copyright
Copyright
[107]. Copyright 2020,
2020, Elsevier).
2020, Elsevier).
Elsevier).
2020, Elsevier).
Since
SinceSince
Since metal
metalmetal
metal cations
cations
cations
cations can
can can
canbebe be
be spontaneously
spontaneously
spontaneously
spontaneously inserted
inserted
inserted
inserted into
into into
into the
the the
the MXene
MXene
MXene
MXene layer,
layer,
layer,
layer, they
they
they
they are
are are
are
widely
widely
widely
widely used
used used
used as
as as intercalators
as intercalators
intercalators
intercalators to
to to increase
toincrease
increase
increase the
thethethe interlayer
interlayer
interlayer
interlayer spacing
spacing
spacing
spacing of
of of MXene
ofMXene
MXeneMXene [108].
[108].
[108].
[108]. The
The The
The metal
metal
metal
metal
+ + +,+ Mg
ions
ions
ionsionsused
used used
usedasas asintercalators
intercalators
intercalators are:
are: are:
Na Na , K,++,K
Na
+Na K,+Mg
,,KMg ,2+Mg2+2+
, Li
2+
, ,Li +,+ Sn
, Li
+,Li
Sn
+4+ ,Sn
, ,Mn
, 4+Sn 4+,Mn 4+ 2+ [109–112].
2+2+[109–112].
2+ ,[109–112].
Mn Mn [109–112]. ForFor
For example, Kaji-
For example,
example,
example, Kaji-
Kaji-
yama
Kajiyama et al.et[109]
al. embedded
[109] embedded Na + +in Ti
Na + 3in
C T
2Ti (T
x3xC =
xT -OH,
(T = -O,
–OH, and -F)
–O, and
and found
–F) and that
foundthe in-
that
yama et al. [109] embedded Na in Ti C T (T
yama et al. [109] embedded Na in Ti3C2Tx (Tx = -OH, -O, and -F) and found that the in-
+ 3 2 2 x =
x -OH, x -O, and -F) and found that the in-
crease
crease of
of distance
distance between
between layers
layers waswas more
more than
crease of distance between layers was more than 4.0 Å owing to the embedding of Na . of
the increase of distance between layers was more
than 4.0
than
4.0 Å Å owing
4.0
owingÅ to
owing
tothe
the embedding
to the embedding
embedding ofofNa
Na
+
+.+
.
Na +
Additionally,
. Na
Additionally, + +could
Na + be regarded
could be as
regarded a pillar
as a that
pillar kept that distance
kept between
distance layers.
between There
layers.
Additionally,
Additionally, NaNa + couldcould be regarded
be regarded as aaspillar
a pillar thatthat kept kept distance
distance between
between layers.
layers. ThereThere
There
were
werewere
twotwowere
two twofor
reasons
reasons
reasons reasons
for
forthe
the the for the of
increase
increase
increase increase
ofofthe
the the of the interlayer
interlayer
interlayer
interlayer spacing
spacing spacing spacing
after
after after
NaNa after
+Na Na+ intercalation.
+ +intercalation.
intercalation.
intercalation. On On
On the
the the
one
one one hand,
hand,hand,Na NaNa
and and
andHHatoms
Hatoms
atoms repelled
repelled
repelled each
each each other
other otherand andand the the
the existence
existence
existence ofof–OH
of–OH–OH terminal
terminal
terminal ex-ex-
ex-
On the one hand, Na and H atoms repelled each other and the existence of –OH terminal
panded the interlayer distance. On the other hand, Na+ +intercalation allowed solvent
expanded the interlayer distance. On the other hand, Na intercalation allowed solvent
molecules to penetrate into the interlayer, resulting in a swelling effect and increasing
molecules to penetrate into the interlayer, resulting in a swelling effect and increasing
the spacing between layers.
the spacing between layers.
Zhang
Zhang et al. [113]
et al. [113]used
usedthethe hydrothermal
hydrothermal method
method and self-assembly
and self-assembly to prepare
to prepare Co3 O4 –
Co 3O4–MXene (Co–MXene) composite materials. This paper found that the introduction
MXene (Co–MXene) composite materials. This paper found that the introduction of
ofCo
CoO3O4nanoparticles
nanoparticlesinto
into MXene
MXene could
could effectively
effectively prevent
prevent self-weight
self-weight accumulation.
accumulation. First,
3 4
First, the cobalt ions were intercalated between the layers of MXene. Then,
the cobalt ions were intercalated between the layers of MXene. Then, in the hydrothermal in the hy-
drothermal
process, theprocess, the in
cobalt ions cobalt ions ininterlayer
the MXene the MXene interlayer
were were into
transformed transformed into vol-
volume-expanded
ume-expanded Co 3O4 nanoparticles. Co3O4 nanoparticles acted as a support for opening
Co3 O4 nanoparticles. Co3 O4 nanoparticles acted as a support for opening the laminated
the laminated
structure, structure,
resulting resulting
in the in theofproduction
production Co–MXene ofwith
Co–MXene
a large with a large
specific specific
surface area
surface
(Figurearea (Figure 16a,b).
16a,b).
Figure
Figure16. 16.(a)
(a)Schematic
Schematicillustration
illustrationof
ofthe
thesynthesis
synthesis of
of the
the Co-Ti
Co-Ti33C
C22TTxxcomposite;
composite;(b)FESEM
(b) FESEMimages
images
ofofTiTi
3AlC2, multilayer Ti3C2Tx and Co–MXene composite (Reproduced with permission from [113].
3 AlC2 , multilayer Ti3 C2 Tx and Co–MXene composite (Reproduced with permission from [113].
Copyright 2021, Elsevier).
Generally,
Generally,the theintercalators
intercalatorsare areadded
addedafterafterthetheend
endof ofetching.
etching.However,
However,there therewill
will
happen
happenthatthatthe
theinterlayer
interlayerspacing
spacingmay maydecrease
decreaseafterafterthe
theadjunction
adjunctionofofthe themetal
metalcation.
cation.
HuHuetetal.
al.[110]
[110]proposed
proposedaaone-step
one-stepmethod
methodtotoembed embedmetalmetalcations
cationsininMXene,
MXene,regarding
regarding
the
the metal cations as a part of the etchant instead of as an intercalatorafter
metal cations as a part of the etchant instead of as an intercalator afterthetheetching.
etching.
This
Thismethod
methodwas was used
used to to
solve
solvethethe
problem
problem of reducing
of reducing spacing
spacingbetween
between layers afterafter
layers the
intercalation of a cation.
the intercalation The two-step
of a cation. processprocess
The two-step was as follows: The etched
was as follows: TheMXeneetchedpowder
MXene
was dispersed
powder in Li, Na,inorLi,Sn
was dispersed salt
Na, orand stirred,
Sn salt and then
and stirred, and the
thenproduct was collected.
the product The
was collected.
one-step process
The one-step was as
process was follows: The Ti
as follows: The3AlC powder
Ti23 AlC 2 was
powder added
was to
addedthe tomixture
the of
mixture HFof
and
HF Li,
and Na,
Li,and
Na,Sn andsalt
Sntosalt
collect the product.
to collect The procedure
the product. The procedure is shown in Figure
is shown 17. The
in Figure 17.
study found that: (1) When using the one-step method, the interlayer
The study found that: (1) When using the one-step method, the interlayer spacing of MXene spacing of MXene
increased
increasedfromfrom18.5
18.5toto 24.84
24.84 Å;Å; (2) When the the embedding
embeddingprocess processoccurred
occurredafter afterthe
theetching
etch-
ing process,
process, thethe inter-layer
inter-layer spacingbecame
spacing becamesmaller.
smaller.Because
Because the interlayer of of MXene
MXenewas was
occupied
occupiedbybywaterwaterafter
afterthetheetching,
etching,thethemetal
metal cations
cationswerewereunevenly
unevenlydistributed
distributed duedueto
static electricity
to static afterafter
electricity embedding.
embedding. The distance
The distancebetween the layers
between wherewhere
the layers the metal ions
the metal
ions embedded
were were embedded increased.increased.
It broke Itthebroke the of
stability stability
the water of the
causedwater
thecaused the loss
loss of water andof
water and collapsed between the layers. So the inter-layer spacing
collapsed between the layers. So the inter-layer spacing became smaller when the em- became smaller when
the embedding
bedding process occurred
process occurred after the
after the etching etchingFor
process. process. For the
the one-step one-step
method, the method,
cations
the cations
were evenly were evenly
dispersed dispersed
between thebetween
layers due the to
layers due and
etching to etching
embeddingand embedding
at the sameat
the same
time, time,
so there wasso no
there was no collapse.
collapse.
Figure 17. Schematic illustration of the preparation of Ti3C2 by one-step method (a) and traditional
Figure17.
method
(b)Schematic illustration
(Reproduced ofthe
thepreparation
with permission
illustration of preparationofofCopyright
from [110]. TiTi 3C2 by one-step method (a) and traditional
2020, Elsevier).
3 C2 by one-step method (a) and traditional
method (b) (Reproduced with permission from [110]. Copyright 2020,
method (b) (Reproduced with permission from [110]. Copyright 2020, Elsevier).Elsevier).
In addition to the intercalation of organic molecules and metal cations, polymers,
InIn addition
hydroxides, addition
anions,
toto the
the intercalation
and intercalation
water can also ofof organic
organic
be molecules
intercalated
molecules and metal
to increase
and metal cations, polymers,
thecations,
interlayer polymers,
spacing
hydroxides,
hydroxides,
of MXene. For anions,
anions,
example, and water
and water
Boota can can
et al. also
also be intercalated
be intercalated
[114] has synthesized to increase
to increase the interlayer
the interlayer
polar charged, spacing
polar spacing
neutral,
ofMXene.
of
and MXene.
non-polar For example,
For example, Boota
polyfluorene Boota et al.
et al. [114]
derivatives [114] hassynthesized
has
(PFD) synthesized
(Figure 18),polar polar charged,
charged,
and made polar
thepolar neutral,
neutral,
adjusted ter-
andnon-polar
and
minal non-polar
PFD to interactpolyfluorene
polyfluorenewith Ti 3derivatives
derivatives
C2Tx. This(PFD) (PFD)
study (Figure
(Figure
found that18),
18), PFDand
and made
couldmade
the the adjusted
beadjusted
embedded terminal ter-
in the
minal
PFD toPFD
interlayerinteractto interact
with with Tiwith
increasingC
3 2 xT Ti
. C
This T
interlayer
3 2 x . This
study study
found
spacing. found
that PFDthat PFD
could
Additionally, could
bethe be
embedded
polar embedded
in
chargedthe in the
inter-
PFD
interlayer
layer with with
increasing increasing
interlayer interlayer
spacing. spacing.
Additionally, Additionally,
maximized the increase in interlayer spacing. Li et al. [115] used a positively chargedthe polar the
charged polarPFD charged
maximized PFD
maximized
the increase
Fe(OH) the
in
3 solution increase
interlayer in interlayer
as an spacing.
intercalator Li etto spacing.
al. [115] used
insert Li et al. [115]
a positively
negatively chargedused
charged a positively
MXene Fe(OH) charged
and3 solution
then re-
as an intercalator
Fe(OH)
moved the Fe(OH)to
3 solution as insert
3 solution negatively
an intercalator
with HCl. tocharged
insert
The MXene is
negatively
procedure and then in
charged
shown removed
MXene19.
Figure the
and Fe(OH)
then4~5
Then, re-
3
solution
moved
nm Fe(OH) with
the HCl. The
3Fe(OH)
formed procedure
3 solution
nanochannels withisHCl. shown
and Thein
the Figure 19.isThen,
procedure
nanochannels shown 4~5
increased innm Fe(OH)
Figure formed
19. Then,
interlayer 3 spacing.4~5
nanochannels
nm Fe(OH)
Srimuk and the
formed
et al.3 [116] used anion (Cl−) increased
nanochannels andanthe
as interlayertospacing.
nanochannels
intercalator Srimuk
increased
insert MXene et al.
the[116]
interlayer
for used
spacing.
first time
anion (Cl − ) as an intercalator to +insert MXene for the first time and at the same time
Srimuk et al. [116] used anion (Cl −) as an intercalator
and at the same time inserted Na to study its effect on seawater desalination. Fredrick- to insert MXene for the first time
inserted Na + to study its effect on +seawater desalination. Fredrickson et al. [117] studied
andet
son at al.
the[117]
samestudied
time inserted
the change Na toofstudy its effect
the surface on seawater
chemistry of Tidesalination.
2C and Mo2CFredrick- MXene
the
sonchange
when etHal. of
2O[117]
was thestudied
surface the
embedded. chemistry
changeofofTithe
However, 2 C and
the Mo2 C
surface
research ofMXene
chemistry when
of Ti2H
these intercalators C2 Oandwas
isMoembedded.
2C MXene
insufficient
However,
when
and the
theHapplications
2O wasresearch areofnot
embedded. these intercalators
However,
extensive is More
the research
enough. insufficient
of
time these and
should the
beapplications
intercalators
devoted is to are not
insufficient
research
extensive
and develop
and enough.
the applications More aretime
the intercalators should
furtherbe
not extensive devoted
inenough.
order toMore to research
improve timethe and
should develop the intercalators
be devoted
interlayer spacing toand
research
spe-
further
and in
developorder theto
cial properties of MXene. improve
intercalators the interlayer
further in spacing
order to and
improvespecialthe properties
interlayer of MXene.
spacing and spe-
cial properties of MXene.
Figure 18.
illustration of
of synthesis
synthesisof
ofthe
thepolymer
polymerand
andpolymer@
polymer@TiTi 3C2Tx (Reproduced
3 C2 Tx (Reproduced
Figure
with
with 18. Schematic
permission
permission from illustration
from [114].
[114]. of synthesis
Copyright
Copyright of the polymer
2017, American
2017, American and
Chemical
Chemical polymer@ Ti3C2Tx (Reproduced
Society).
Society).
with permission from [114]. Copyright 2017, American Chemical Society).
Figure 19. Schematic illustration of preparation of Ti3C2Tx interacted by Fe(OH)3 (Reproduced with
permission
Figure19. from [115].
19.Schematic
Schematic Copyrightof2017,
illustration John Wiley
preparation and Sons).
Figure illustration of preparation ofofTiTi3C2T x interacted by Fe(OH)3 (Reproduced with
3 C2 Tx interacted by Fe(OH)3 (Reproduced with
permission from [115]. Copyright 2017, John Wiley and
permission from [115]. Copyright 2017, John Wiley and Sons). Sons).
2.3. Dispersion
2.3.
2.3.Dispersion
Dispersion
Because the van der Waals force between MXene layers can stack MXene under its
weight, it leads
Because
Because theto
the vanthe
van derextension
der Waals
Waalsforce of ion
force transport
between
between MXene
MXenepathways
layers
layerscanand the
canstack
stacklack
MXene
MXeneof contact
under
underitsbe-
its
tween
weight,active
weight, ititleads
leads surface
toto
thethesites andofelectrolytic
extension
extension ion transport
of ion ions. Therefore,
pathways
transport pathwaysand wethe must
andlack
the of find ofa contact
contact
lack way to be-
between let
MXene
active remain
tweensurface
active dispersed
sites
surface sites[113,118].
and electrolytic ions.There
and electrolytic are
Therefore,two
ions. we main
mustaspects
Therefore, findwe to
a way
mustenhance
to let
find athe
MXene way dispersi-
remain
to let
dispersed
bility of [113,118].
MXene: There
changing are
the two main
dispersant aspects
and to enhance
surface the dispersibility
modification
MXene remain dispersed [113,118]. There are two main aspects to enhance the dispersi- of MXene. of MXene:
Usually,
changing
these
bility two the dispersant
aspects
of MXene: and the
are applied
changing surface modification
simultaneously,
dispersant of MXene.
not
and surface only Usually, different
choosing
modification these twodispersants,
of MXene. aspects are
Usually,
applied
but
thesealsosimultaneously,
two modifying
aspects are not only simultaneously,
MXene.
applied choosing differentnot dispersants,
only choosingbut also modifying
different MXene.
dispersants,
As
As for
but also for dispersants,
dispersants,
modifying MXene.organic
organic solvents
solvents are are the
themost
moststudied.
studied. Maleski
Maleski et et al.
al. [119]
[119] dis-
dis-
persed
persedAsMXene
MXene ininwater,
for dispersants, ethanol
water, (EtOH),
ethanol
organic methanol
(EtOH),
solvents the (MeOH),
methanol
are most(MeOH), acetone
studied. (ACE),
acetone
Maleski etetc.,
(ACE), research-
etc.,dis-
al. [119] re-
ing the
searchingstate the of dispersion
state of and
dispersion aggregation
and of
aggregation MXene of in
MXene
persed MXene in water, ethanol (EtOH), methanol (MeOH), acetone (ACE), etc., re- 12 different
in 12 types
different of
typessolvents
of sol-
(Figure
vents
searching20).the
(Figure Thestate
experiment
20). The foundand
experiment
of dispersion that MXene
found thathad
aggregation MXenepoor
of dispersibility
had
MXene poor in HEX,
in 12 dispersibility
different TOL
types and
inofHEX,
sol-
DCB,
TOL and
ventsand MXene
DCB,20).
(Figure ultimately
andTheMXene precipitated
ultimately
experiment after being
precipitated
found that MXeneplaced
afterhadfor
being 96 h. The
placed
poor higher the
for 96 h. The
dispersibility surface
high-
in HEX,
tension
er
TOLtheandof DCB,
surfacethe solvent,
tension the
of
and MXene theeasier the the
solvent,
ultimately 2D material
easier thewas
precipitated 2D tobeing
disperse.
material
after was The
placed tofor surface
disperse.
96 h. The tension
The sur-
high-
of
erother
face organic
thetension
surface solvents
oftension
other except
organic
of the ethanol
solvents
solvent, the was
except very
easier thehigh.
ethanol2D was Although
verywas
material the
high.tosurface
Although
disperse. tension of
the sur-
The
ethanol was very
face tension of low,
ethanol ethanol
was strongly
very low, interacted
ethanol with
strongly the surface
interacted terminals
with
of other organic solvents except ethanol was very high. Although the sur- the of
surface MXene.
termi-
Therefore,
nals
face tension theofdispersibility
of MXene. Therefore,
ethanol was
wasthe also
low,excellent.
dispersibility
very ethanol was also excellent.
strongly interacted with the surface termi-
nals of MXene. Therefore, the dispersibility was also excellent.
Figure 20.
Figure 20. Dispersions
Dispersions of
of Ti
Ti33C
C22TTxx in
in the 12 solvents
the 12 solvents (Reproduced
(Reproduced with
with permission
permission from
from [119].
[119].
Copyright
Figure 20. 2017, American
Dispersions of Chemical
Ti C T Society).
in
Copyright 2017, American Chemical Society).
3 2 x the 12 solvents (Reproduced with permission from [119].
Copyright 2017, American Chemical Society).
Chemosensors 2021,
Chemosensors 9, 225
2021, 9, 225 1616ofof 41
40
Zhang
Zhang et et al.
al.[118]
[118] developed
developed a high-concentration
a high-concentration organicorganic
solventsolvent
solutionsolution
of Ti3 C2 of
Tx
Ti
by3Cadjusting
2Tx by adjusting the microenvironment
the microenvironment of2 TTi
of Ti3 C x ,3C 2Tx, namely
namely the tuned
the tuned microenviron-
microenvironment
ment
method method
(TMM).(TMM). The steps
The steps of theofTMMthe TMM
method method were:were: (1) Etching
(1) Etching the MAX
the MAX phase phase
into
into
Ti3 CTi
2 T C
3x 2Tx MXene
MXene with with
HF; HF;
(2) (2)
Ti C
3 2 Ti
T 3xC2Tx was
was modified
modified by by
the the intercalation
intercalation and and
surfacesurface
modi-
modification of tetrabutylammonium
fication of tetrabutylammonium hydroxide
hydroxide (TBAOH); (TBAOH); (3) Stirring
(3) Stirring the modified
the modified Ti3 C2 Tx
Ti C T powder gently or shaking it by hand to easily disperse it into
powder gently or shaking it by hand to easily disperse it into the organic solvent. The pro-
3 2 x the organic solvent.
The
cedureprocedure
is shown is in
shown
Figurein21.
Figure 21. Thesolvents
The organic organic were solvents were propylene
propylene carbonate
carbonate (PC), N,N-
(PC), N,N–dimethylacetamide
dimethylacetamide (DMAc), and (DMAc), and N,N-dimethylformamide
N,N-dimethylformamide (DMF), which (DMF), which
had high had
surface
high
tensionsurface tension
and high andpoints.
boiling high boiling
The yield points.
of theThe yield of MXene
single-layer the single-layer
obtained byMXene
the TMMob-
methodbywas
tained the63.9%
TMMand the material
method prepared
was 63.9% by TMM
and the materialhadprepared
a larger sheet size, fewer
by TMM had adefects,
larger
and better
sheet dispersion.
size, fewer defects,Special attention
and better was thatSpecial
dispersion. the high dispersibility
attention was thatof the
the high
modified
dis-
Ti C T
persibility
3 2 x was because of the hydrophobic surface. The hydrophobicity
of the modified Ti3C2Tx was because of the hydrophobic surface. The hydro- was caused by
the insertion +
phobicity wasofcaused
TBA by between the MXene
the insertion layers
of TBA + and thethe
between adjustment of surface
MXene layers groups
and the ad-
in the TMM
justment method.
of surface groups in the TMM method.
Figure
Figure 21.
21.Schematic
Schematicdiagram
diagramof of
thethe
synthesis of Ti
synthesis of3C
Ti23TCx 2organic solvent
Tx organic dispersion
solvent via TMM
dispersion (Re-
via TMM
produced with permission from [118]. Copyright 2021, American Chemical Society).
(Reproduced with permission from [118]. Copyright 2021, American Chemical Society).
The
The dispersion
dispersion of of MXene
MXene in in non-polar
non-polar solvents
solvents hashas also
also been
been partially
partially reported.
reported.
However,
However, the the hydrophilicity
hydrophilicity and and negative
negative surface charge of the the original
original Ti Ti33C
C22Txx MXene
MXene
limit
limit its
itsdispersion
dispersionininnon-polar
non-polar solutions
solutions [120].
[120].Scholars
Scholarshavehave
researched
researchedthis issue. For
this issue.
example,
For example, Lim Lim et al.
et[121] used
al. [121] strong
used strongacid
acidpolyelectrolyte
polyelectrolyte (PAMPS)
(PAMPS)asasan anemulsifier
emulsifier to to
graft octyltriethoxysilane
graft octyltriethoxysilane(OTS) (OTS)onto ontothethe
surface
surfaceof MXene,
of MXene,making the hydrophilic
making MXene
the hydrophilic
becomebecome
MXene hydrophobic. The stable
hydrophobic. Theperiod
stableofperiod
hydrophobic MXene that
of hydrophobic MXenedispersed in non-polar
that dispersed in
hexane was more than one month. Carey et al. Carey
[122] found that when + exchanged +with
non-polar hexane was more than one month. et al. [122] foundLithat when Li ex-
di(hydrogenated
changed tallow) benzyl methyl
with di(hydrogenated tallow) ammonium
benzyl methyl chloride (DHT), the
ammonium surface
chloride of MXene
(DHT), the
changed from hydrophilic to organophilic, which could be
surface of MXene changed from hydrophilic to organophilic, which could be stably dis-stably dispersed in non-polar
solvents.
persed McDaniel solvents.
in non-polar et al. [123]McDaniel
used isocyanate
et al. [123]to covalently
used isocyanatemodify to Ti3 C2 Tx MXene
covalently modify for
the
Ti 3C2first time and
Tx MXene forsuccessfully
the first time obtained a large number
and successfully of MXene
obtained a largewith alkyl carbamate
number of MXene
groups
with alkylon carbamate
the surface. The modified
groups MXeneThe
on the surface. could be usedMXene
modified in hydrophobic
could be used thio amino
in hy-
groups andthio
drophobic be stable
aminodispersion
groups andinbe the formate
stable matrix. in the formate matrix.
dispersion
Surfacemodification
Surface modificationisis aa common
common method method to to change
change thethe hydrophilicity
hydrophilicity of of material
material
surface and many methods have been developed based on surface modification.exam-
surface and many methods have been developed based on surface modification. For For
ple, Zhang
example, et al. [124]
Zhang et al. used
[124]theusedsolution-phase flocculation
the solution-phase methodmethod
flocculation to successfully prepare
to successfully
a large amount
prepare of low-layer
a large amount Ti3 C2 Tx MXene
of low-layer Ti3C2Tx forMXenethe first time.
for the The
first solution-phase
time. floccula-
The solution-phase
tion method mainly used ammonium ions to solve the
flocculation method mainly used ammonium ions to solve the re-stacking of MXenere-stacking of MXene nanosheets.
The solution-phase flocculationflocculation
method wasmethod dividedwas intodivided
the NHinto +
nanosheets. The solution-phase 4 method
the NH and the im-
4+ method
proved NH + method. The NH + method was to quickly synthesize a few-layer Ti
4 4
and the improved NH4 method. The NH4 method was to quickly synthesize a few-layer
+ + 3 C2 Tx
powder by freeze-drying
Ti3C2Tx powder by freeze-drying the the electrostatic flocs which was formed by MXene
electrostatic flocs which was formed by MXene colloids and
adding subsequent removable NH + (Figure 22). In addition, all the methods discussed
colloids and adding subsequent 4removable NH4+ (Figure 22). In addition, all the
above are for the preparation of MXene suspension, but the solution-phase flocculation
methods discussed above are for the preparation of MXene suspension, but the
method could directly prepare MXene powder. The NH4 + method improved the dis-
solution-phase flocculation method could directly prepare MXene powder. The NH4+
persibility of MXene,the
method improved because the negative
dispersibility charge on
of MXene, the surface
because of MXenecharge
the negative was reduced
on the
after adding NH + . The MXene sheets were mutually repelled by static electricity and
4
surface of MXene was reduced after adding NH4 . The MXene sheets were mutually
+
were evenly
repelled dispersed
by static in water.
electricity Afterevenly
and were freeze-drying
dispersed and
in annealing,
water. AfterMXene nanosheets
freeze-drying and
could be gathered. The improved NH + method is adding step-by-step layering and auxil-
annealing, MXene nanosheets could 4be gathered. The improved NH4+ method is adding
iary centrifugation
step-by-step layeringin the
andelectrostatic flocculation process,
auxiliary centrifugation which wasflocculation
in+ the electrostatic mainly to shorten
process,
the freeze-drying
which was mainlytime further.the
to shorten The improved NH
freeze-drying methodThe
4 further.
time shortened
improvedtheNH
preparation
4+ method
cycle and obtained a yield as high as 70%.
shortened the preparation cycle and obtained a yield as high as 70%.
Figure 22.
Figure 22.Schematic
Schematicdiagram
diagramof
ofthe
thesynthesis
synthesisofofTiTi 3C2Tx powders by solution-phase flocculation
3 C2 Tx powders by solution-phase flocculation
strategy (Reproduced with permission from [124]. Copyright
strategy (Reproduced with permission from [124]. Copyright 2020,2020,American
AmericanChemical
ChemicalSociety).
Society).
2.4.
2.4. Large-Scale
Large-Scale Synthesis
Synthesis
In
In most experiments of
most experiments of preparing
preparing MXene,
MXene, thethe yield
yield of of MXene
MXene isisdeficient,
deficient,which
whichisis
unfavorable
unfavorable for for putting
putting MXene
MXene intointo production
production and and widely
widelyused. used. However,
However, except
except for
for
the
the yield
yield ofof less
less than
than20%
20%mentioned
mentioned in insome
someestimates,
estimates, itithas hashardly
hardlybeen
beenreported
reportedthat
that
the
theexact
exactyield
yieldofofMXene
MXene can be be
can obtained.
obtained. Therefore, it is ita pity
Therefore, that we
is a pity thatcannot give the
we cannot yield
give the
here. It is significant to develop a method that can prepare
yield here. It is significant to develop a method that can prepare a large amount of a large amount of powder.
In order toInachieve
powder. order totheachieve
mass production
the mass of MXene, the
production ofcritical
MXene, technology
the criticalis technology
to swell MXene,is to
and
swell MXene, and then use physical methods (stirring or ultrasound) to For
then use physical methods (stirring or ultrasound) to layer MXene. layerexample,
MXene.
in
For2015, Naguib
example, in et al. [54]
2015, Naguibusedetmacromolecular organic bases organic
al. [54] used macromolecular (tetrabutylammonium
bases (tetrabu-
hydroxide
tylammonium (TBAOH), choline
hydroxide hydroxide,
(TBAOH), or n-butylamine)
choline hydroxide, orton-butylamine)
react with MXene in order
to react with
to cause the swelling of the MXene. They then used simple stirring
MXene in order to cause the swelling of the MXene. They then used simple stirring or or sonication to cause
large-scale
sonication delamination of the MXene
to cause large-scale layer. In 2016,
delamination of theWang
MXene et al.layer.
[125] In
used arylWang
2016, diazonium
et al.
salts to modify the surface of Ti3 C 2 MXene in order to cause
[125] used aryl diazonium salts to modify the surface of Ti3C2 MXene in order to cause swelling and large-scale
delamination
swelling and occurred
large-scale through gentle ultrasonic
delamination treatment.
occurred through In 2020,
gentle Huang
ultrasonic et al. [126]
treatment. In
used the different densities of water and ice to develop a new
2020, Huang et al. [126] used the different densities of water and ice to develop a new method freeze-and-thaw
(FAT)
method auxiliary method. After
freeze-and-thaw (FAT)etching,
auxiliary H2method.
O entered the etching,
After interlayers H2Oofentered
MXene,the froze to
inter-
become ice, and expanded. Then, the ice thawed in order to re-embed more H2 O. Through
layers of MXene, froze to become ice, and expanded. Then, the ice thawed in order to
multiple cycles of FAT without ultrasonic treatment, the yield of MXene could reach
re-embed more H2O. Through multiple cycles of FAT without ultrasonic treatment, the
39.0%. After 1 h of ultrasonic treatment, the yield of MXene reached 81.4%. In addition,
yield of MXene could reach 39.0%. After 1 h of ultrasonic treatment, the yield of MXene
large-scale MXene can be prepared through various methods developed. However, when
reached 81.4%. In addition, large-scale MXene can be prepared through various methods
the production volume is expanded, it must be considered whether the product obtained
developed. However, when the production volume is expanded, it must be considered
after expanding the dosage is the same as the small batch production. Shuck et al. [68]
whether the product obtained after expanding the dosage is the same as the small batch
compared Ti3 C2 Tx prepared in large batches with Ti3 C2 Tx prepared in small batches and
production. Shuck et al. [68] compared Ti3C2Tx prepared in large batches with Ti3C2Tx
found that mass production was feasible. It is necessary to research the mass production of
prepared in small batches and found that mass production was feasible. It is necessary
MXene, which is important to the actual application of MXene.
to research the mass production of MXene, which is important to the actual application
ofMXene-Based
3. MXene. Gas Sensors
Because of rich surface functional groups, large specific surface area, large porosity,
high conductivity, and other properties, MXene is considered as a promising sensor mate-
rial with abundant gas adsorption active sites [127]. MXene can get fast charge transfer
under low temperature conditions because of its good metal conductivity and high carrier
mobility, leading the gas response to improve at room temperature [128]. For example,
NH3 can interact with some oxygen terminals such as –OH and –O. MXene with a large
number of oxygen–containing terminals can strongly interact with NH3 , which helps to
obtain excellent gas response [129]. Here, we will describe the performance of pristine
MXene and MXene composite in gas sensors in detail. MXene composite includes metal
oxide composite, polymers composite and Pd-MXene.
Table 1 shows gas-sensitivity performances of MXene-based gas sensors.
Table 1. Gas sensing performances of MXene-based gas sensors.
Conc. Operating Response Response/Recovery

Material Gas References
(ppm) Temp (◦ C) % Time (s/s)
Acetone 5 RT 3.6 90/102 [130]
Ti3 C2 Tx
Ethanol 100 RT 22.47 -/- [131]
Mo2 CTx Toluene 100 RT 2.65 -/- [132]
Ti3 C2 Tx /CuO Toluene 50 250 11.4 270/10 [49]
Ti3 C2 Tx /ZnO NO2 100 RT 41.93 34/105 [133]
Ti3 C2 Tx /SnO2 NH3 50 RT 40 36/44 [129]
Ti3 C2 Tx /SnO-SnO2 Acetone 100 RT 12.1 18/9 [134]
Ti3 C2 Tx /Co3 O4 HCHO 10 RT 9.2 83/5 [135]
Ti3 C2 Tx /WO3 NH3 1 RT 22.3 119/228 [128]
Ti3 C2 Tx /W18 O49 Acetone 0.17 300 1.4 5.6/6 [136]
Ti3 C2 Tx /In2 O3 Methane 5 RT 29.6 6.5/3.5 [137]
Ethanol 200 RT 41.1 0.4/0.5 [138]
Ti3 C2 Tx /PANI
NH3 50 RT 400 -/- [139]
Nb2 CTx /PANI NH3 100 RT 301.31 105/143 [140]
Ti3 C2 Tx /PEDOT:PSS NH3 100 RT 36.6 116/40 [141]
H2 2 RT - 120/420
V2 CTx [85]
Methane 25 RT - 480/330
4000 RT 23 37/161 [142]
Pd-Ti3 C2 Tx H2
100 RT 56 -/- [143]
SnS2 /Ti3 C2 Tx NO2 1000 RT 115 64/10 [144]
Ti3 C2 Tx /WSe2 Ethanol 40 RT 24 9.7/6.6 [145]
S-Ti3 C2 Tx Toluene 10 RT 59.1 -/- [146]
Ti3 C2 Tx Ethanol 120 RT 14 39/139 [147]
Ti3 C2 Tx /Fe2 (MoO4 )3 N-butane 100 RT 43.1 18/24 [148]
Ti3 C2 Tx NH3 100 RT 28.87 1/201 [149]
Ti3 C2 Tx /GO NH3 100 RT 7.21 -/- [150]
rGO/N-Ti3 C2 Tx /TiO2 HCHO 20 RT 132 -/- [151]
Co3 O4 @PEI/Ti3 C2 Tx NOx 100 RT 27.9 1.6/73.1 [152]
Ti3 C2 Tx /rGO/CuO Acetone 100 RT 52.09 6.5/7.5 [127]
3.1. Pristine MXene

Among various MXene materials, Ti3 C2 Tx is the most widely used and mature mate-
rial, which is also the first MXene material used in gas sensors in 2017. Lee et al. [153] used
a solution casting method to integrate Ti3 C2 Tx MXene (prepared by HCl + LiF etching) on
a flexible polyimide platform in order to make a gas sensor. The gas response to ethanol,
methanol, acetone, and NH3 at room temperature was studied. The study showed that
the resistance of the MXene film increased after the introduction of ethanol, methanol,
acetone, and NH3 . At this time, MXene possessed a p-type semiconductor gas sensing
behavior. Generally speaking, MXene with high conductivity is theoretically metallic,
but the abundant terminals on the surface of MXene will transform it from metallic to
semiconductor. Figure 23 is the gas response of the MXene sensor exposed to 4 different
gases. It could be seen from the figure that the sensor was the most sensitive to ammonia
and the least sensitive to acetone. The high gas response to NH3 was mentioned above.
methanol, acetone, and NH3. At this time, MXene possessed a p-type semiconductor gas
sensing behavior. Generally speaking, MXene with high conductivity is theoretically
metallic, but the abundant terminals on the surface of MXene will transform it from me-
tallic to semiconductor. Figure 23 is the gas response of the MXene sensor exposed to 4
Chemosensors 2021, 9, 225 different gases. It could be seen from the figure that the sensor was the most sensitive 19 of 40
to
ammonia and the least sensitive to acetone. The high gas response to NH3 was men-
tioned above. NH3 gas molecules can react vigorously with –O and –OH to make a sig-
nificant change in resistance. The solution casting method or vacuum-filtration (vacu-
NH3 gas molecules can react vigorously with –O and –OH to make a significant change
um-filtration)
in resistance. Theis usually
solutionused to prepare
casting method MXene into gas sensors.
or vacuum-filtration The film obtained
(vacuum-filtration) by
is usu-
this method is relatively thick and covers the active sites greatly,
ally used to prepare MXene into gas sensors. The film obtained by this method is relatively which is unfavorable
for the
thick gas
and response.
covers In 2018,
the active sites Yuan et which
greatly, al. [130] used MXeneforself-assembly
is unfavorable the gas response. to prepare
In 2018,a
structurally interconnected, porous 3D MXene framework and studied
Yuan et al. [130] used MXene self-assembly to prepare a structurally interconnected, porous its gas response
to acetone.
3D First, an electrospinning
MXene framework and studied its method was used
gas response to to prepareFirst,
acetone. a positively charged 3D
an electrospinning
method was used to prepare a positively charged 3D frame. The 3D frame was aithighly
frame. The 3D frame was a highly interconnected porous structure that made easier
for gas molecules to enter or spread. The positive charge on the
interconnected porous structure that made it easier for gas molecules to enter or spread. surface could combine
the subsequent
The positive chargeMXene with
on the the 3D
surface frame.
could Then,the
combine a negatively
subsequentchargedMXene MXenewith thewas added
3D frame.
and the 3D MXene was self-assembled through the electrostatic
Then, a negatively charged MXene was added and the 3D MXene was self-assembled interaction between the
3D framethe
through and MXene (Figure
electrostatic 24a–c).between
interaction Owing to thethe3Delectrostatically
frame and MXene attracted,
(Figure the24a–c).
polar
gas molecules
Owing could form hydrogen
to the electrostatically bonds
attracted, thewith
polar thegas
terminal part could
molecules of the form
MXene surface.
hydrogen
It induced
bonds with charge transfer
the terminal partbetween MXenesurface.
of the MXene and theIt tested
induced molecule. This ledbetween
charge transfer the 3D
MXene sensor to generate excellent gas response of VOCs
MXene and the tested molecule. This led the 3D MXene sensor to generate excellent which can generate strong
gas
hydrogen bonds. The 3D MXene sensor was placed in 50
response of VOCs which can generate strong hydrogen bonds. The 3D MXene sensor ppb–30 ppm acetone and it
was placed
was found inthat
50the sensor
ppb–30 ppmalsoacetone
had a andgoodit response
was found to that
50 ppb acetonealso
the sensor (Figure
had a25a–d).
good
This was to
response the50first
ppbreport
acetonethat could 25a–d).
(Figure detect ppb-level
This wasacetone.
the first Thereportsensitivity
that could of the 3D
detect
MXene sensor
ppb-level in an
acetone. environment
The sensitivity of the5 ppm acetone sensor
3D MXene at room in temperature
an environment was of3.6%
5 ppmand
the response
acetone at room and recovery time
temperature was and
was 3.6% 1.5/1.7
themin (Figure
response and25e,f).
recoveryIt hadtimeexcellent
was 1.5/1.7 repeata-
min
bility and
(Figure flexibility.
25e,f). After 1000
It had excellent bending/extension
repeatability cycles,
and flexibility. the 1000
After sensor response did not
bending/extension
show noticeable
cycles, deviationdid
the sensor response (Figure 25g).noticeable
not show This research laid the
deviation (Figurefoundation
25g). This forresearch
flexible
laid the foundation
wearable VOC sensors for flexible wearable VOC sensors in the future.
in the future.
Figure 23.
23. Gas
Gasresponse
responseofofTiTi
3C2Tx sensor to four different gas (Reproduced with permission from
Figure 3 C2 Tx sensor to four different gas (Reproduced with permission
Chemosensors 2021, 9, 225 [153]. Copyright 2017, American Chemical Society). 20 of 41
from [153]. Copyright 2017, American Chemical Society).
Figure 24. (a)

Figure 24. (a)Schematic
Schematicdiagram
diagramofofthe
thefabrication process
fabrication of of
process a 3D MXene;
a 3D (b) (b)
MXene; SEM image
SEM of the
image of 3D
the
3D polymer scaffold; (c) SEM image of a 3D MXene (Reproduced with permission
polymer scaffold; (c) SEM image of a 3D MXene (Reproduced with permission from [130]. Copyrightfrom [130].
Copyright
2018, 2018,Society
the Royal the Royal Society of Chemistry).
of Chemistry).
Chemosensors 2021, 9, 225 20the
Figure 24. (a) Schematic diagram of the fabrication process of a 3D MXene; (b) SEM image of of 40
3D polymer scaffold; (c) SEM image of a 3D MXene (Reproduced with permission from [130].
Copyright 2018, the Royal Society of Chemistry).
Figure
Figure 25. (a) Dynamic response 25. (a)
curve Dynamic
of 3D MXeneresponse curve
gas sensor; (b)of 3DofMXene
Plot gas sensor;
responses versus (b)
timePlot
for of responses
a 3D-M versus
sensor upontime
for a 3D-M sensor
exposure 50 ppm acetone concentration; (c) Theupon exposure
relationship 50 ppmresponse
between acetone and
concentration; (c) The relationship
acetone concentration; between re-
(d) Relationship
sponse and acetone concentration; (d) Relationship between response and acetone concentration in
between response and acetone concentration in a wide range up to saturated vapor; (e,f) The curve of the response and
a wide range up to saturated vapor; (e,f) The curve of the response and recovery time under 5
recovery time under 5 ppm acetone; (g) Response of the 3D-M sensor under 20 ppm acetone after different bending cycles
ppm acetone; (g) Response of the 3D-M sensor under 20 ppm acetone after different bending cy-
(Reproduced with permission from
cles ref. [130]. Copyright
(Reproduced 2018, the
with permission Royal
from Ref.Society of Chemistry).
[130]. Copyright 2018, the Royal Society of Chemis-
try).
Using metallic materials to prepare gas sensors, it is necessary to consider that these
low-noise
Usingmetallic
metallicmaterials
materialslack highly active
to prepare gas adsorption
gas sensors, sites. to
it is necessary Inconsider
2018, Kimthatet these
al. [81]
transferred Ti 3 C 2 Tx to a SiO wafer printed with gold sensing electrodes
low-noise metallic materials lack highly active gas adsorption sites. In 2018, Kim et al.
2 and fabricated
a[81]
Ti3 Ctransferred
2 Tx MXene Ti sensor with low noise, high conductivity and rich hydrophilicity on the sur-
3C2Tx to a SiO2 wafer printed with gold sensing electrodes and fabri-
face. They have studied
cated a Ti3C2Tx MXene sensor the gaswith
response of acetone,
low noise, ethanol, ammonia,
high conductivity and richpropanal at room
hydrophilicity
temperature.
on the surface. They have studied the gas response of acetone, ethanol, ammonia, apro-
The study found that the sensor was susceptible to VOC gas and had high
response, however, it was not sensitive to other inorganic gases.
panal at room temperature. The study found that the sensor was susceptible to VOC gas The gas sensor had
an
and had a high response, however, it was not sensitive to other inorganic gases. The gasto
excellent response to VOC gas. This was the first time that a sensor has been made
detect
sensora had
variety of VOCs at
an excellent room temperature.
response to VOC gas.InThis 2019,
was Koh theetfirst
al. [154]
timestudied the effect
that a sensor hasof
the
beeninterlayer
made toexpansion of Ti3 Cof
detect a variety 2 TVOCs
x film on the gas
at room sensitivity performance.
temperature. In 2019, Koh et Inal.addition,
[154]
Na + was embedded in order to improve the swelling behavior. MXene was relatively insen-
studied the effect of the interlayer expansion of Ti3C2Tx film on the gas sensitivity per-
sitive
formance. Inadsorption
to gas addition, Na due to itsembedded
+ was high conductivity.
in order However,
to improvesince gas readily
the swelling diffused
behavior.
between layers, interlayer expansion might dominate in terms of
MXene was relatively insensitive to gas adsorption due to its high conductivity. How-gas sensitivity. The study
found
ever, since gas readily diffused between layers, interlayer expansion might dominatefrom
that when ethanol was introduced, the interlayer spacing of MXene increased in
13.24
termsÅoftogas14.06 Å and the
sensitivity. Thegas response
study foundincreased
that whenrapidly;
ethanolwhen ethanol wasthe
was introduced, removed,
inter-
the interlayer
layer spacing spacing
of MXene of increased
MXene decreasedfrom 13.24to 13.55 Å andÅthe
Å to 14.06 andgastheresponse decreased.
gas response in-
This showed
creased thatwhen
rapidly; the swelling
ethanol behavior
was removed,inducedthe by gas wasspacing
interlayer reversible and thedecreased
of MXene interlayer
expansion increased the gas response. The intercalation of metal ions into the interlayer of
MXene would change the diffusion coefficient of H2 O, which lead to the change of swelling
behavior. It was found that proper Na+ intercalation could promote ethanol intercalation,
which led to larger interlayer spacing. Because the dehydration caused by Na+ intercalation
provided a location for ethanol intercalation, it would lead to swelling behavior. In 2021,
Hou et al. [131] used oxygen plasma activated by microwave energy to treat Ti3 C2 Tx MX-
ene and studied the gas sensitivity of activated Ti3 C2 Tx to different VOC gases. Figure
26a shows the gas response of pristine Ti3 C2 Tx and activated Ti3 C2 Tx to different ethanol
concentrations at room temperature. It could be seen that the gas sensitivity performance
of activated Ti3 C2 Tx was more excellent than that of pristine Ti3 C2 Tx . The response of
activated Ti3 C2 Tx increased with the concentration of ethanol gas. The sensor had good
stability and selectivity. After activation, the gas-sensing performance became better, be-
cause plasma could open the interlayer of MXene and increased the interlayer spacing
the gas sensitivity of activated Ti3C2Tx to different VOC gases. Figure 26a shows the gas
response of pristine Ti3C2Tx and activated Ti3C2Tx to different ethanol concentrations at
room temperature. It could be seen that the gas sensitivity performance of activated
Ti3C2Tx was more excellent than that of pristine Ti3C2Tx. The response of activated
Ti3C2Tx increased with the concentration of ethanol gas. The sensor had good stability
and selectivity. After activation, the gas-sensing performance became better, because
plasma could open the interlayer of MXene and increased the interlayer spacing and
specific surface area. Plasma could also remove the fluorine terminal and increase the
oxygen-containing
and specific surface terminal,
area. Plasmathereby
could providing
also removemore theadsorption sites to and
fluorine terminal improve gas
increase
sensitivity.
the In an environment
oxygen-containing terminal, of 100 ppm
thereby ethanol,
providing the adsorption
more response ofsites
Ti3Cto2Timprove
x activated
gasat
500 °C wasIn22.47
sensitivity. at room temperature
an environment of 100 ppm (Figure 26c).the
ethanol, Theresponse
sensor prepared
of Ti3 C2 Tby MXene had
x activated at
500 ◦ C was
a strong 22.47 attoroom
response temperature
various VOC gases. (Figure 26c). The sensor
It is undoubtedly preparedfor
unfavorable bytheMXene had
selectivity
aofstrong response
the VOC to various
gas-sensing VOC gases.
response. It is undoubtedly
If a specific VOC gas isunfavorable for the
to be detected, selectivity
a highly selec-
of theVOC
tive VOCgasgas-sensing
sensor mustresponse. If a specific
be developed. VOCsensor
Virtual gas is array
to be detected,
(VSA) is a highly selec-
single sensor
tive
thatVOC gas sensor
can generate must be developed.
multi-dimensional signalsVirtual sensor different
and identify array (VSA)
VOCisgases
a single sensor
accurately.
that can generate
Combining withmulti-dimensional
measuring impedance signals and identify different
spectroscopy, VSAVOC cangases accurately.
provide mul-
Combining
ti-dimensionalwithinformation
measuring impedance spectroscopy,
for distinguishing VSAtypes
different can provide
of VOC.multi-dimensional
Li et al. [155] used
information for distinguishing
Ti3C2Tx to prepare a VSA, which different
could types
detectofand
VOC. Li et al.
identify [155] used
different Ti3of
types C2VOC
Tx to pre-
with
pare a VSA, which could detect and identify different types of VOC with
high accuracy and estimate the concentration of a single VOC in a VOC mixture. Based high accuracy and
estimate the concentration
on the proposed VSA, theofaccuracy
a single VOC in a VOC
of ethanol mixture. Based
concentration on thewas
estimation proposed
93.4%.VSA,
This
the accuracyhigh-precision
high-level, of ethanol concentration estimation
identification was 93.4%.
technology couldThis high-level,
be used high-precision
in various industries
identification
in order to solvetechnology could which
the obstacle be usedwas in various
caused industries
by the lowinsensor
order to solve theinobstacle
selectivity gas de-
which
tecting.was caused by the low sensor selectivity in gas detecting.
Figure 26.(a)(a)
Figure26. Gas sensitivity
Gas of the
sensitivity of pristine Ti3 C2 Ti
the pristine Tx3C
and
2Tx activated Ti3 C2 TTi
and activated x to
3C2ethanol; (b) Response–
Tx to ethanol; (b) Re-
sponse–recovery
recovery curve of Ti
curve of activated activated Ti3C2ethanol
3 C2 Tx under Txunderrange
ethanol rangeto10
10 ppm 800ppm
ppm; to(c)
800Dynamic
ppm; (c)response–
Dynamic
response–recovery
recovery curve of thecurve of the
activated Ti3activated Ti3C
C2 Tx under 2Txppm
100 under 100 ppm
ethanol; (d) ethanol;
Response(d) of Response ofTi
the pristine the pris-
3 C2 Tx
and activated Ti3 C2 Tx under 100 ppm different gases; (e) Dynamic response–recovery curve of
the activated Ti3 C2 Tx under 100 ppm different gases; (f) The stability of the activated Ti3 C2 Tx under
100 ppm ethanol (Reproduced with permission from [131]. Copyright 2021, Elsevier).
In addition to Ti3 C2 Tx , there are some other MXene materials used in gas sensors,
such as V2 CTx [156] and Mo2 CTx [132]. Lee et al. [156] coated a small layer of V2 CTx on
a polyimide film to make a gas sensor and studied the gas sensitivity to polar gas (H2 ) and
non-polar gas (methane), respectively. Compared with other 2D materials, this study found
that V2 CTx MXene had a highly oxygen-functionalized surface and its conductive carbide
core, which was conducive to its realization of trace detection and high signal-to-noise
ratio. The sensor prepared by V2 CTx had the most enormous response to H2 . It was
different from Ti3 C2 Tx that had the largest response to NH3 reported in the past. Based
on the previous vanadium-containing gas sensors, the selectivity to hydrogen was very
high. It was believed that the V atoms of V2 CTx mainly caused this difference. At the same
time, the detection limits of V2 CTx for H2 and methane at room temperature were 2 ppm
and 25 ppm, respectively. This paper showed that the sensitivity of the MXene sensor
to different gases could be different by changing the surface transition metal elements.
This paper provided a new method to develop accurate MXene gas sensors in the future.
Guo et al. [132] obtained Mo2 CTx MXene from Mo2 Ga2 C by etching. They used
photolithography to fabricate Mo2 CTx gas sensors on Si/SiO2 substrates and studied its
gas response to VOC gas. When the Mo2 CTx sensor was exposed to toluene and benzene
gas, the resistance changed positively. This was because the adsorption of VOC increased
the channel resistance. The Mo2 CTx sensor showed a high response to toluene. Because
the benzene ring with high activity had a strong interaction with Mo2 CTx , toluene could
be readily adsorbed to the sensor surface and was more sensitive to changes in resistance.
In addition, compared with benzene, the methyl group with electron-donating properties
in toluene increased the activity of the benzene ring, so the sensor’s response to toluene
was higher than that of benzene. The application of Mo2 CTx on the sensor provides another
way of thinking for future MXene gas sensors, which are significant for developing more
different MXene gas sensors in the future.
3.2. MXene/Metal Oxide Gas Sensors

Metal oxides are often prepared as gas sensors owing to their high sensitivity, good
selectivity, and mature technology. At the same time, they are often used to composite
with other gas-sensitive materials to enhance gas-sensing performance, such as carbon
nanotubes [157]. There have been many reports on the 2d MXene/metal oxide materi-
als, including CuO [49], ZnO [133], SnO [129,134], Co3 O4 [135], WO3 [128], W18 O49 [136],
and In2 O3 [137]. Using metal oxide and MXene to prepare gas sensors, most of the perfor-
mance of composites is better than the pristine MXene and pure metal oxide. The main rea-
son for the improved performance is combining two different materials to form a heterojunc-
tion or p-n junction. Therefore, when the sensor captures the measured gas molecules, a de-
pletion layer and a hole accumulation layer that can regulate electrons’ transfer are formed.
Hermawan et al. [49] used electrostatic interaction between CuO and Ti3 C2 Tx in an ul-
trasonic bath to self-assemble the two materials into a CuO/Ti3 C2 Tx MXene heterostructure
and studied the gas response of the sensor to detect toluene (see Figure 27a). After CuO
has compounded with Ti3 C2 Tx , CuO was not inserted between the layers of Ti3 C2 Tx but
inserted between the gaps of the layered plate composed of multiple layers. So the layer
spacing of Ti3 C2 Tx did not increase. The CuO/Ti3 C2 Tx MXene composite sensor had
an excellent gas response to toluene (The response value to 50 ppm toluene at 250 ◦ C was
11.4 and the response and recovery time was 270/10 s, shown in Figure 27b,c). The reason
for the improved gas response of the composite was that a Schottky barrier was formed
between CuO and MXene. When the sensor was placed in toluene gas, –O would be
removed from the CuO surface, leading the depletion area (HAL) to thin and the resis-
tance of sensors to increase. Therefore, the gas sensitive response increased. At the same
time, the conductive layer Ti3 C2 Tx allowed charge carriers to migrate faster in the CuO
nanoparticles. This fact helped to reduce response and recovery time.
There were three reasons that the gas sensitivity of this 3D MXene/ZnO composite was
enhanced. First, there formed more line defects with more adsorption sites because of
the breaking of the internal chemical bonds. Second, a great amount of O2- adsorbed on
the surface of ZnO nanoparticles at room temperature, and O2− played a crucial role in
Chemosensors 2021, 9, 225 the gas response. Third, the oxygen-containing terminals of MXene sphere/ZnO23 of 40 in-
creased and formed a p-n heterojunction with ZnO.
Figure
Figure 27. (a)27. (a) Schematic
Schematic diagram
diagram of theof the fabrication
fabrication process
process of CuOofNanoparticles/Ti
CuO Nanoparticles/Ti
3 C2 Tx3C2Tx gas
and andsensor
gas sensor
device device (Repro-
(Repro-
ducedduced with permission
with permission from from [49]. Copyright
[49]. Copyright 2020, 2020, American
American Chemical
Chemical Society);
Society); (b) Gas(b)response
Gas response of CuO,
of CuO, Tix3C
Ti3 C2 T 2Tx MXene,
MXene,
and CuO/Ti3 C2 Tx MXene at different operating temperatures (Reproduced with permission from [49]. Copyright 2020,
American Chemical Society); (c) Response and recovery times of CuO/Ti3 C2 Tx MXene under 50 ppm of toluene (Repro-
duced with permission from [49]. Copyright 2020, American Chemical Society); (d) Schematic diagram of the fabrication of
3D MXene sphere and the flexible gas sensing device (Reproduced with permission from [133]. Copyright 2021, Elsevier).
The common problem of 2D materials is the stacking of layers, leading to a smaller

specific surface area. The decrease of active sites is detrimental to gas-sensing performance.
A 2D material layer can be inserted on a spherical substrate to form a 3D ball with reference
to metal oxide nanoflowers. Yang et al. [133] prepared a three-dimensional corrugated MX-
ene sphere. Although this sphere was not formed by inserting it on the substrate, preparing
a 2D material into a 3D sphere was beneficial to increase its surface area. This report
described using ultrasonic spray pyrolysis technology to prepare three-dimensional corru-
gated MXene spheres and then composite the MXene spheres with ZnO to form a composite
material. The process of preparing 3D MXene spheres was as follows: (1) The Ti3 C2 Tx
precursor was dispersed with ultrasound, and the Ti3 C2 Tx , at this time, was a single micro–
mist particle. (2) The water of the dispersed aerogel evaporated and the internal stress
disappeared. So that all MXene sheets collapsed inward isotropically to self-assemble into
a 3D shrinking MXene. Figure 27d is a route map of the preparation process. The prepared
composite material showed excellent gas sensitivity to NO2 . In the environment of 100
ppm NO2 at room temperature, the response was 41.93%, and the response and recovery
time was 34/105 s (The response of the original material was 27.27% and the response
and recovery time was 53 s/5 min). There were three reasons that the gas sensitivity of
this 3D MXene/ZnO composite was enhanced. First, there formed more line defects with
more adsorption sites because of the breaking of the internal chemical bonds. Second,
a great amount of O2 − adsorbed on the surface of ZnO nanoparticles at room temperature,
and O2 − played a crucial role in the gas response. Third, the oxygen-containing terminals
of MXene sphere/ZnO increased and formed a p-n heterojunction with ZnO.
He et al. [129] used a hydrothermal method to synthesize a 2D MXene decorated with
SnO2 nanoparticles successfully and studied the gas response of SnO2 /MXene sensors to
NH3 . The study found that the introduction of SnO2 increased the content of adsorbed
oxygen, which tended to get more adsorption sites in order to enhance the sensing ability.
Since the C–F bond was easily affected by temperature, most fluorine terminals were
removed and made the surface hydrophilic better when the composite material was pre-
pared by hydrothermal. When a pristine MXene sensor detected NH3 , the resistance of
the sensor increased (Figure 28a). Because the author believed that MXene showed p-type
semiconductor characteristics in this paper. The oxygen-containing terminals of MXene and
NH3 interacted strongly. NH3 provided electrons to MXene due to its electron-donating
properties. The electrons and holes recombined to make the carrier in MXene decrease.
These electrons interfered with the metal conductivity of the Ti-C core channel, resulting
in a decrease in conductivity. However, the resistance of the sensor under NH3 decreased,
indicating that the SnO2 /MXene was a n-type semiconductor. When the SnO2 /MXene sen-
sor worked at different temperatures, the gas sensor response decreased and the response
time increased as the operating temperature increased (Figure 28b,c). It was the opposite of
the gas sensor made of metal oxide. The reason was that the –OH terminal amount of MX-
ene decreased in the higher temperature, which led to the decrease of gas adsorption active
sites. Figure 28d is the influence of humidity on the gas sensor. It was seen that the gas
sensor response reached the highest when the humidity was 45%, which met the needs
of daily gas detection. Compared with the pristine MXene sensor, the gas performance
of the SnO2 /MXene sensor has been improved (The response to 50 ppm NH3 was 40%
and the response and recovery time was 36/44 s at room temperature). There were two
reasons for the enhancement of gas sensitivity. First, MXene had a strong interaction
with NH3 . Secondly, MXene and SnO2 formed a heterojunction and the charge transfer
in the heterojunction enriched the electrons in the surface area, thereby leading to the in-
crease of the sensitivity. In addition to the above-mentioned research on recombination
with n-type semiconductor SnO2 , a type of SnO2 partially oxidized by p-type SnO was used
to form a p–n junction in situ and then SnO–SnO2 combined with MXene. Wang et al. [134]
used a hydrothermal method to synthesize in-situ p–n junction SnO–SnO2 (Figure 28e
is a schematic diagram of SnO–SnO2 ). Then, SnO–SnO2 was composited with Ti3 C2 Tx
in order to form a SnO–SnO2 /Ti3 C2 Tx sensor and studied the effect of this composite
sensor on the acetone response. Figure 28f is the response curve of MXene, SnO–SnO2 ,
and SnO–SnO2 /Ti3 C2 Tx to 10~100 ppm acetone gas. The figure showed that the response
of the SnO–SnO2 /Ti3 C2 Tx composite sensor was more excellent than the other two materi-
als (The response of the composite sensor to 100 ppm acetone at room temperature was
12.1 and the response and recovery time was 18/9 s). The reason for the improved sensing
performance was the different work function, so that a Schottky barrier was formed be-
tween SnO and Ti3 C2 Tx , which acted as a hole accumulation layer (HAL) in the composite
sensor. At the same time, SnO–SnO2 was embedded in the interlayer of MXene. It increased
the interlayer spacing, so the surface area increased and the gas response enhanced.
As mentioned in Section 2.3, embedding Co3 O4 as an intercalant in MXene can in-
crease the interlayer spacing of MXene and obtain a larger specific surface area. This is
beneficial to more gas adsorption sites and excellent gas sensitivity. Zhang et al. [135]
successfully prepared MXene/Co3 O4 composite materials and studied the gas-sensitive
response of MXene/Co3 O4 sensors to formaldehyde. In the composite material, Co3 O4
existed on the surface and between layers of MXene. The MXene/Co3 O4 sensor had a high
gas response to formaldehyde and a short recovery time (At room temperature, the re-
sponse to 10 ppm formaldehyde was 9.2% and the response and recovery time was 83/5 s).
Furthermore, it showed an extremely low detection limit (10 ppb formaldehyde could be
detected). The MXene/Co3 O4 sensor could also be used as a flexible sensor. The bending
angle of the flexible electrode was proportional to the resistance change, that was, the re-
sponse increased with the increase of the bending angle. The response was speedy and
it could instantly return to the baseline resistance. The enhancement of gas response was
attributed to the cooperative interface interaction between MXene and Co3 O4 .
Chemosensors 2021,9,9,225
Chemosensors2021, 225 2543
26 of of 40
Figure
Figure 28. (a) The response of 28. (a) The response
the MXene/SnO of the MXene/SnO2 and MXene under 50 ppm ammonia; (b) The rela-
2 and MXene under 50 ppm ammonia; (b) The relationship of responses and
tionship of responses and operating temperatures of MXene/SnO2; (c) The relationship of response
operating temperatures of MXene/SnO2 ; (c) The relationship of response and recovery time and operating temperatures of
and recovery time and operating temperatures of MXene/SnO2; (d) The relationship of responses
MXene/SnO2 ; (d) The relationship of responses and humidity of MXene/SnO2 (Reproduced with permission from [129].
and humidity of MXene/SnO2 (Reproduced with permission from [129]. Copyright 2021, Elsevier);
Copyright 2021, Elsevier); (e)
(e) Schematic
Schematic of of the
the preparation
preparationofofSnO–SnO
SnO–SnO 2 /Ti
2/Ti
C Tx nanocomposites;
3C23Tx 2nanocomposites;
(f) response
(f) Gas Gas response of
of acetone
acetone of Ti3 C2 Tx , SnO–SnO NPs
of2 Ti 3C2and SnO-SnO22 /Ti
Tx, SnO–SnO NPs3 Cand
2 Tx SnO-SnO
nanocomposites)
2/Ti3C2Txat 10–100 ppm (Reproduced
nanocomposites) at 10–100 with
ppm permission
(Reproduced
from [134]. Copyright 2021, with
Elsevier).
permission from [134]. Copyright 2021, Elsevier).
Chemosensors
Chemosensors2021,
2021,9,9,225
225 2626ofof41
40
Guo et al. [128] used the ultrasonic method to composite Ti3C2Tx and WO3 into a
Guo et al. [128] used the ultrasonic method to composite Ti C2 Tx and WO3 into
sensor and studied the relationship of contents of WO3 with the gas 3sensitivity of NH3 at
a sensor and studied the relationship of contents of WO3 with the gas sensitivity of NH3 at
room temperature. Figure 29a shows the relationship between the gas sensitivity re-
room temperature. Figure 29a shows the relationship between the gas sensitivity response
sponse and the WO3 content. It could be seen that when the WO3 content was 50 wt%, the
and the WO content. It could be seen that when the WO3 content was 50 wt%, the response
response was3 the largest (22.3%), which was much higher than the original Ti3C2Tx sensor
was the largest (22.3%), which was much higher than the original Ti3 C2 Tx sensor (1.45%).
(1.45%). Figure 29b is the response time and recovery time of the original Ti3C2Tx and
Figure 29b is the response time and recovery time of the original Ti3 C2 Tx and Ti3 C2 Tx /WO3
Ti3C2Tx/WO3 to 1 ppm NH3. It could be seen that the response and recovery speed of the
to 1 ppm NH3 . It could be seen that the response and recovery speed of the Ti3 C2 Tx /WO3
Ti3C2Tx/WO3 sensor was faster than that of the original Ti3C2Tx, which meant that the
sensor was faster than that of the original Ti3 C2 Tx , which meant that the participation of
participation
WO3 improved of WO improved
the 3gas the gas
performance of performance
MXene. ThereofwereMXene.
threeThere were
reasons forthree reasons
improved gas
for improved gas sensitivity. First, WO 3 was distributed on Ti3C2Tx in order to obtain a
sensitivity. First, WO3 was distributed on Ti3 C2 Tx in order to obtain a porous structure
porous structure
that was conducivethat was conducive
to the entry and to the entry and
diffusion diffusion
of gas of gas Second,
molecules. molecules.theSecond,
defects
the defects of WO 3 became adsorption sites for the measured gas on the surface of the
of WO3 became adsorption sites for the measured gas on the surface of the composite
composite material.
material. Third, the Third, the metal
metal phase Ti3 C2phase 3C2Tx and the n-type semiconductor WO3
Tx andTithe n-type semiconductor WO3 combined to
combined to form a metal–semiconductor contact.
form a metal–semiconductor contact. Schottky barrier Schottky barrier and
and depletion depletion
layer layer
were formed
were formed in order to improve the gas sensitivity at the same time. Ti3C2Tx/WO3 had
in order to improve the gas sensitivity at the same time. Ti3 C2 Tx /WO3 had excellent
excellent gas response,
gas response, short and
short response response andtime
recovery recovery time selectivity
and great and great toselectivity to NH
NH3 (Figure 3
29c).
(Figure 29c). It was a potential
It was a potential NH3 sensor. NH 3 sensor.
Figure29.
Figure (a)The
29.(a) Therelationship
relationship of
of the
the gas
gas response
response and WO33 content; (b) Response and and recovery
recovery time
timeof
ofTi
Ti33CC22Txx/WO
/WO33and
and
Ti
Ti33CC2T
2T sensor
xx sensorunder
under11ppm
ppmNHNH3;3 (c)
; (c)Gas
Gasresponse
responseof
ofTi
Ti33CC2T
2Tx/WO 3 exposed
x /WO to to
3 exposed different gas
different (Reproduced
gas (Reproducedwith
withpermission
permission
from
from[128].
[128].Copyright
Copyright2021,
2021,Elsevier).
Elsevier).
InInaddition
addition to to single metal
metal oxides,
oxides,thethecomposite
compositeofof bimetallic
bimetallic oxides
oxides withwith MXene
MXene has
alsoalso
has beenbeen reported. Iron Iron
reported. molybdate (Fe2 (MoO
molybdate (Fe2(MoO 4 )3 ) is
4)3used as a sensing
) is used material
as a sensing because
material of
be-
its abundant
cause oxygen vacancies.
of its abundant Zou et al.Zou
oxygen vacancies. [148]etprepared
al. [148] aprepared
sensor composed
a sensor of Fe2 (MoOof
composed 4 )3
Feand Ti3 C4)23Tand
2(MoO x to detect
Ti3C2Tn-butanol.
x to detect The composite
n-butanol. Thestructure
composite was composed
structure wasof composed
MXene layersof
and loosely stacked Fe2 (MoO ) nano-layers, with a high surface area (47.0 m 2 /g). The large
MXene layers and loosely stacked
4 3 Fe 2(MoO 4 ) 3 nano-layers, with a high surface area (47.0
msurface
2/g). The area of the
large composite
surface area of increased
the composite the adsorption
increased the andadsorption
diffusion ofandgas molecules.
diffusion of
Therefore, the sensor had excellent gas sensing properties
gas molecules. Therefore, the sensor had excellent gas sensing properties (The response(The response to 100 ppm n-
tobutanol
100 ppm wasn-butanol
43.1% and wasthe43.1%
response
andand the recovery
response time and was 18/24time
recovery s). The
wasrecombination
18/24 s). The
of bimetallic oxides
recombination expandsoxides
of bimetallic the way to improve
expands the way the to
gasimprove
sensing the
performance
gas sensing of perfor-
MXene,
and it of
mance is expected
MXene, and to obtain gas sensors
it is expected with better
to obtain gas sensorsperformance.
with better performance.
3.3.MXene/Polymer
3.3. MXene/PolymerGasGasSensors
Sensors
The conductive polymer is considered one of the promising gas sensors materials due
The conductive polymer is considered one of the promising gas sensors materials
to its advantages–low resistance, low cost, and adjustable functions. The conductive poly-
due to its advantages–low resistance, low cost, and adjustable functions. The conductive
mers which was used in gas sensors include polyaniline (PANI) [29,158–160], polypyrrole
polymers which was used in gas sensors include polyaniline (PANI) [29,158–160],
(PPy) [6,161,162], and polythiophene (PTh) [163,164]. PPy and PTh have not been reported
polypyrrole (PPy) [6,161,162], and polythiophene (PTh) [163,164]. PPy and PTh have not
to be combined with MXene and applied in gas sensors, so there will not be details. Polyani-
been reported to be combined with MXene and applied in gas sensors, so there will not
line (PANI) is one of the most widely used polymers in gas sensors [159]. PANI has three
be details. Polyaniline (PANI) is one of the most widely used polymers in gas sensors
states: fully reduced state (leucoemeraldine), semi-oxidized state (emeraldine), and fully
[159]. PANI has three states: fully reduced state (leucoemeraldine), semi-oxidized state
oxidized state (pernigraniline) [158]. Due to the amine group of the polyaniline molecule,
(emeraldine), and fully oxidized state (pernigraniline) [158]. Due to the amine group of
PANI shows great gas sensitivity to nitrogen-containing substances, so PANI is often used
the polyaniline molecule, PANI shows great gas sensitivity to nitrogen-containing
as a NH3 sensor [29]. The protonation and deprotonation process of PANI is the root of NH3
substances, so PANI is often used as a NH3 sensor [29]. The protonation and
Chemosensors 2021, 9, 225 deprotonation process of PANI is the root of NH3 sensing behavior. When27 the of 40
protonated PANI is placed in the environment of NH3, the protons in the PANI are
transferred to the NH3 molecule, causing the state of PANI to change (The conductive
emerald salt (ES) state change to the emerald base (EB) state), thereby increasing
sensing behavior.
electrical resistance When the protonated
[139]. For example, PANIKulkarni
is placed in et the
al.environment of NH3 , the
[160] synthesized pro-
PANI
tons in the PANI are transferred to the NH molecule, causing
nanofibers using an in-situ chemical oxidation polymerization process and studied the
3 the state of PANI to change
(The conductive
gas-sensitive emerald
response of salt (ES) state
sensors madechange
of PANIto the emerald base
nanofibers to NH (EB) state),
3. The thereby
PANI increas-
nanofiber
ing electrical resistance [139]. For example, Kulkarni et al. [160]
sensor showed good selectivity for NH3 (The response of 62% under 100 ppm NH3) and synthesized PANI nanofibers
using detect
could an in-situ chemical
1 ppm NHoxidation polymerization process and studied the gas-sensitive
3 at room temperature. Aiming at further improving the
response ofperformance
gas-sensing sensors madeofofPANI, PANI it nanofibers
was oftentocompounded
NH3 . The PANI withnanofiber sensor
metal oxides showed
[165,166],
carbon nanotubes, etc. [167,168], to become a composite sensor. For example, Liu 1etppm
good selectivity for NH 3 (The response of 62% under 100 ppm NH 3 ) and could detect al.
NH3 used
[165] at room temperature. Aiming
electrospinning, at further
hydrothermal andimproving the gas-sensing performance
in-situ polymerization techniques to of
PANI, it was often compounded with metal oxides [165,166],
synthesis a gas sensor composed of polyaniline (PANI) and SnO2 nanotubes (PMS) carbon nanotubes, etc. [167,168],
to become
coated witha MoS
composite sensor. For example, Liu et al. [165] used electrospinning, hydrother-
2 nanosheets. The gas response to NH3 was studied. The sensitivity of
mal and in-situ polymerization
PANI/MoS2/SnO2 under 100 ppm techniques
NH3 at to synthesis
room a gas sensor
temperature was composed
10.9, which of had
polyaniline
a low
(PANI) and SnO2 nanotubes (PMS) coated with MoS2 nanosheets. The gas response to NH3
detection limit (200 ppb).
was studied. The sensitivity of PANI/MoS2 /SnO2 under 100 ppm NH3 at room temperature
The combination of MXene and PANI into composite sensors has been studied. For
was 10.9, which had a low detection limit (200 ppb).
example, Zhao et al. [138] used low-temperature in-situ polymerization to anchor the
The combination of MXene and PANI into composite sensors has been studied. For ex-
aniline monomer in situ on Ti3C2Tx MXene nanosheets, and then dropped the
ample, Zhao et al. [138] used low-temperature in-situ polymerization to anchor the aniline
PANI/Ti3C2Tx solution onto flexible polyethylene terephthalate (PET). The sensor was
monomer in situ on Ti C2 Tx MXene nanosheets, and then dropped the PANI/Ti3 C2 Tx
formed on the substrate3(Figure 30a) and its gas sensitivity to ethanol was studied. The
solution onto flexible polyethylene terephthalate (PET). The sensor was formed on the sub-
study found that PANI anchored on MXene nanosheets could prevent MXene from
strate (Figure 30a) and its gas sensitivity to ethanol was studied. The study found that
gathering in order to exert the maximum gas sensitivity. The gas sensitivity of the
PANI anchored on MXene nanosheets could prevent MXene from gathering in order to
PANI/Ti3C2Tx composite sensor to ethanol was better than that of the original Ti3C2Tx
exert the maximum gas sensitivity. The gas sensitivity of the PANI/Ti3 C2 Tx composite
(Figure 30b). The response of the PANI/Ti3C2Tx composite sensor to 200 ppm ethanol
sensor to ethanol was better than that of the original Ti3 C2 Tx (Figure 30b). The response of
was
the 41.1%
PANI/Ti andCthe response and recovery time was 0.4/0.5 s at room temperature. There
3 2 Tx composite sensor to 200 ppm ethanol was 41.1% and the response and
were three reasons
recovery time was 0.4/0.5 for the senhancement of gas sensitivity
at room temperature. There were ofthree
composite
reasonssensors. ➀ The
for the enhance-
unique structure and large specific surface area of composite
ment of gas sensitivity of composite sensors. ¬ The unique structure and large specific materials resulted in a
large number of target gas adsorption sites. ➁ Ti 3C2Tx had a large number of functional
surface area of composite materials resulted in a large number of target gas adsorption
groups
sites. on Tiits surface, which increased the number of active sites. ➂ The excellent metal
3 C2 Tx had a large number of functional groups on its surface, which increased
conductivity
the number ofofactive Ti3C2sites.
Tx ensured effectivemetal
® The excellent charge carrier transfer
conductivity of Ti3 C2 Tinx ensured
the composite
effective
material. The PANI/Ti 3C2Tx sensor was very flexible, so bending it to 120°still
charge carrier transfer in the composite material. The PANI/Ti3 C2 Tx sensor was very
maintained
flexible, so high
bendingsensitivity
it to 120very well
◦ still (Figure 30c).
maintained high sensitivity very well (Figure 30c).
Figure 30. (a) Schematic illustration of coating the PANI/Ti3 C2 Tx nanocomposites on the interdigital electrode; (b) Dynamic
transient Figure 3. C2 Tx and PANI/Ti3 C2 Tx -based flexible sensors under ethanol gas range from 50 ppm to 200 ppm; (c) The image
of PANI/Ti3 C2 Tx -based flexible sensors. (Reproduced with permission from [138]. Copyright 2019, John Wiley and Sons).
In addition to the commonly used Ti3 C2 Tx and PANI polymerization, some scholars
predict that niobium carbide MXene (Nb2 CTx ), which has fewer atomic layers, is a poten-
tial gas-sensitive material. Wang et al. [140] made the composite material Nb2 CTx /PANI
composed of polyaniline (PANI) and Nb2 CTx into a sensor–driven by a simple friction
nanogenerator (TENG) and studied its gas sensitivity to NH3 . This simple triboelectric nano-
generator (TENG) comprised two aluminum electrodes and two triboelectric films connected
to a PET substrate. It could be used as a power source to drive the NH3 sensor. Figure 31a–c is
the preparation process of the Nb2 CTx /PANI sensor. Nb2 CTx /PANI had better gas sensitivity
than the original PANI (Figure 31d). As the Nb2 CTx content in PANI increased, the gas
response increased first and then decreased. Because when the Nb2 CTx nanosheets were
densely coated, it would hinder NH3 molecules to adsorb on the PANI. When the sensor was
placed in 100 ppm NH3 at room temperature, the response was 301.31% and the response
and recovery time was 105/143 s. The Nb2 CTx /PANI sensor showed high selectivity to NH3 ,
and the sensor achieved the highest gas response when the ambient humidity reached 70%
Chemosensors 2021, 9, 225 (Figure 31e,f). This meant that the Nb2 CTx /PANI sensor could be used as an NH 29 3ofsensor
41
in a high humidity environment to achieve NH3 detection.
Figure31.
Figure 31.(a)
(a)Schematic
Schematicillustration
illustration of
of preparation
preparation of
of the
the ultrathin
ultrathin2D
2DNbNb2CT x nanosheets;
2 CT x nanosheets;(b)(b)
Schematic of of
illustration
preparationofofthe
preparation theNb
Nb2CT
CTx/PANI
/PANI sensor;
sensor;(c)
(c)Schematic
Schematicillustration ofof
illustration preparation
preparationof of
thethe
TENG-driven
TENG-drivengasgas
sensing system;
sensing system;
2 x
(d) The relationship of response and NH3 concentration fitting curves of the different sensors toward 10–100 ppm NH3;
(d) The relationship of response and NH3 concentration fitting curves of the different sensors toward 10–100 ppm NH3 ;
(e) Selectivity of the Nb2CTx/PANI-2 sensor; (f) The relationship of response and humidity of PANI and Nb2CTx/PANI-2
(e) Selectivity of the Nb2 CTx /PANI-2 sensor; (f) The relationship of response and humidity of PANI and Nb2 CTx /PANI-2
sensor for 100 ppm NH3. (Reproduced with permission from [140]. Copyright 2021, Elsevier).
sensor for 100 ppm NH3 . (Reproduced with permission from [140]. Copyright 2021, Elsevier).
3.4. Pd-MXene Gas Sensor
Noble metal particles are widely used as modified gas sensors, such as Pd, Pt, Au,
etc. [173–175]. Pd has an affinity for H2 and can absorb up to 900 times its own volume in
hydrogen, so scholars generally use Pd particles to compound with gas-sensitive mate-
PEDOT:PSS, which is a composite of poly(3,4–ethylene dioxythiophene) (short for

PEDOT) and poly(4–styrenesulfonic acid) (short for PSS), has been popular because of its
simple synthesis process and high conductivity. The PEDOT:PSS gas sensor could detect
nitrogen-containing gas at room temperature [169,170]. For instance, Lin et al. [171] made
a PEDOT:PSS gas sensor and studied its gas response to NO. The PEDOT:PSS sensor had
excellent gas-sensitivity performance (The response time was 527 s and the recovery time
was 1780 s), with a detection limit of 350 ppb for NO. The study also found that when
the sensor detected 10 ppm NO, it was significantly affected by O2 or CO. PEDOT:PSS
is often used to compound graphene to improve gas sensitivity. Some scholars thought
of compounding PEDOT:PSS with MXene, which is also a 2D material. For example,
the Ti3 C2 Tx /PEDOT:PSS prepared by Jin et al. [141] showed good gas sensitivity to NH3
(When the amount of MXene was 15 wt%, the response to 100 ppm NH3 was 36.3% and
the response and recovery time was 116/40 s). MXene itself was very sensitive to NH3
and there was a synergistic effect between PEDOT:PSS and Ti3 C2 Tx , which lead to further
enhance gas sensitivity.
In addition to detecting nitrogen gas, Ti3 C2 Tx combined with PEDOT:PSS can also
detect VOC gas. Wang et al. [172] combined Ti3 C2 Tx and PEDOT:PSS to prepare a compos-
ite sensor and studied the gas sensitivity of the sensor to VOC gas. The obtained sensors
showed the most sensitive to methanol. When the mass ratio between PEDOT:PSS and
Ti3 C2 Tx was 4:1, the gas response was the highest. Because the conductive path in the sen-
sor at this time was contributed by PEDOT:PSS instead of MXene. After combination,
it destroyed the conductive path of MXene and increased the distance between the PE-
DOT chains, which made the electronic jumping process difficult and made the resistance
increase, bringing about the increase of gas response. However, the study found that
the response and recovery time of Ti3 C2 Tx /PEDOT:PSS was slightly longer than that of
traditional sensors. This still needs to be solved, and it also pointed out a direction for
the future development of sensors.
3.4. Pd-MXene Gas Sensor

Noble metal particles are widely used as modified gas sensors, such as Pd, Pt, Au,
etc. [173–175]. Pd has an affinity for H2 and can absorb up to 900 times its own volume
in hydrogen, so scholars generally use Pd particles to compound with gas-sensitive materi-
als to improve its gas response to H2 [175,176]. For example, Wang et al. [177] obtained
Pd–SnO2 sensors by electrospinning and magnet sputtering in order to detect H2 at low
temperatures. Experiments showed that Pd enhanced the sensor’s response to H2 at low
temperatures. The Pd–SnO2 sensor showed a detection limit of ~0.25 ppm under 100 ppm
H2 and a short response time of 4 s. At present, it has been reported that gas sensors made
by introducing Pd particles into MXene materials are all detecting H2 .
Zhu et al. [142] combined Ti3 C2 Tx nanosheets and Pd colloidal nanoclusters to form
a paper membrane H2 sensor using a full solution vacuum filtration method. The study
found that the sensor could detect 0.5% of H2 and it still had high resolution when the H2
content reached 40% (Figure 32a). As the H2 content increased, the obtained gas response
and response and recovery time increased (Figure 32c). At the same time, the Pd–Ti3 C2 Tx
sensor had good stability and flexibility (Figure 32d–f). Loading Pd was the reason why
the gas-sensing performance of MXene was improved. When the Pd–Ti3 C2 Tx sensor was
placed in H2 , H2 was preferentially adsorbed on the surface of Pd and then dissociated into
H atoms, resulting in Pd to being converted to PdHx. Because the work function of PdHx
was lower than that of Pd, it caused electrons to move to Ti3 C2 Tx . The Ti3 C2 Tx in this
paper was metallic and the loading of electrons led to an increase in carrier concentration,
thereby reducing resistance. In addition, Doan et al. [143] used the polyol method to
grow Pd particles on the surface of Ti3 C2 Tx directly and successfully synthesized Pd–
Ti3 C2 Tx . At room temperature, the Pd–Ti3 C2 Tx sensor showed excellent gas response to
H2 (The response of H2 was 56% to 100 ppm).
grow Pd particles on the surface of Ti3C2Tx directly and successfully synthesized
Pd–Ti3C2Tx. At room temperature, the Pd–Ti3C2Tx sensor showed excellent gas response
to H2 (The response of H2 was 56% to 100 ppm).
So far, only Pd particles loaded with MXene as a gas sensor have been reported.
Chemosensors 2021, 9, 225 Loading metal ions on gas-sensitive materials have great prospects. In the future,30more
of 40
gas sensors loaded with MXene and other metal particles can be developed, further ex-
panding the family of gas sensor materials, and contributing to the gas sensor industry.
Figure32.
Figure 32.(a)
(a)Response/recovery
Response/recovery curves
curves of of MXene@Pd
MXene@Pd CNC CNC sensor
sensor to Hto H2 (0.5∼40 v/v %); (b) The
2 (0.5∼40 v/v %); (b) The rela-
relationship of sensitivities and H 2 concentration; (c) The relationship of the response and recovery
tionship of sensitivities and H2 concentration; (c) The relationship of the response and recovery times
times and H2 concentration; (d) Repeatability of the MXene@Pd CNC film sensor under 4% H2; (e)
and H2 concentration; (d) Repeatability of the MXene@Pd CNC film sensor under 4% H2 ; (e) Response
Response and response times of MXene@Pd CNC film sensor under 4% H2 under different bend-
and response times of MXene@Pd CNC film sensor under 4% H2 under different bending angles; (f) Re-
ing angles; (f) Response and response times of MXene@Pd CNC film sensor under 4% H2 after
sponse
n-timeand response
bending times
cycles fromof θ
MXene@Pd
= 0o to 180CNC
o and film
backsensor under 4% H2 with
to 0o (Reproduced after n-time bending
permission fromcycles
[142].
from θ = 0o to 180o and back to 0o (Reproduced with permission from [142]. Copyright 2020, Elsevier).
So far, only Pd particles loaded with MXene as a gas sensor have been reported.
Loading metal ions on gas-sensitive materials have great prospects. In the future, more gas
sensors loaded with MXene and other metal particles can be developed, further expanding
the family of gas sensor materials, and contributing to the gas sensor industry.
3.5. Miscellaneous Sensors

In addition to the MXene gas sensor described above, MXene is also modified by two-
dimensional transition metal dichalcogenides (TMD) [144,145], S doping [146], surface treat-
ment [147], alkali treatment [149], carbon-based materials [150], two compounds [127,151,152].
They are prepared into sensors for detecting various gases. Since these reports on the mod-
ification or compounding of MXene materials are too few, we focus on the discussion here
rather than specific classification.
TMD is considered as a candidate material for NO2 detection. Zhang et al. [144]
combined SnS2 with MXene and MXene’s derivative TiO2 to prepare NO2 sensors with
a large response and ultra-fast reaction in seconds. The recombination process in this work
was as follows: the negative charge on the surface of MXene reacted with Sn4+ , which led
to the derivation of TiO2 from MXene and the formation of SnS2 during the formation of
TiO2 . It could also be said that TiO2 derived from MXene provided a platform which SnS2
was recombined in order to form heterojunctions and increase its surface area. The sensor
showed a strong response to NO2 , but the low response to other interfering gases such
as H2 , NH3 , and HCHO. Therefore, this sensor could detect NO2 and had excellent gas-
sensing performance (The response to 1000 ppm NO2 gas at room temperature was 115%
and the response and recovery time was 64/10 s). There were two reasons for the en-
hancement of the performance of the composite sensor: (1) The heterojunction was formed
between SnS2 /TiO2 , which might improve the sensing performance; (2) The specific sur-
face area increased, which increased the total number of gas adsorption sites, leading to
the enhancement of gas sensitivity.
Doping ions are of great significance to improve the properties of materials, and it is
one of the most commonly used methods to improve the properties. Scholars also try
to adulterate MXene. Shuvo et al. [146] introduced S ion into MXene for the first time
and studied the gas sensing performance of the sensor for toluene. It was found that
the response of S-doped MXene was higher than that of pure MXene (The response was
214% to 1 ppm toluene and the response to 50 ppm toluene was 312%). The gas sensing
performance was greatly improved. The doped MXene sensor could also detect toluene
as low as 500 ppb with a very low detection limit. The reason for the improvement of
sensing performance was that sulfur had the affinity to obtain two electrons, resulting
in a greater change in resistance. Sulfur doping increased the binding ability of MXene to
toluene, which was why it had a better selectivity to toluene. Doping is a very effective
method to improve performance, and it is hoped that more reports about doping will
emerge in the future.
The water absorption of the MXene surface will affect the life of MXene. Surface mod-
ification can be used to prolong the life of MXene and ensure its stability. Chen et al. [147]
used fluoroalkylsilane (FOTS) to modify the surface of Ti3 C2 Tx and studied its gas sensing
properties for ethanol. The modified Ti3 C2 Tx MXene had a hydrophobic surface and excel-
lent gas sensing properties (The response to 120 ppm ethanol was 14% and the response and
recovery time was 39/139 s). The hydrophobicity was obtained because FOTS molecules
fixed –OH on the surface of MXene to avoid its reaction with H2 O, and reduced the surface
energy. Therefore, MXene had better stability. On the other hand, FOTS molecules could
also act as intercalators to increase the interlayer spacing of MXene and improve the gas
sensing properties.
Yang et al. [149] prepared NH3 sensors by alkaline treatment of MXene with NaOH
solution. The essence of NaOH alkali treatment was that the embedding of Na+ lead
to the increase of surface area. In addition, alkali treatment could effectively remove –F
terminal and increased –O, that was, increasing the ratio of oxygen to fluorine atoms
([O]/[F]). The increase of [O]/[F] led to the increase in gas response. The response of
alkalized Ti3 C2 Tx sensor to 100 ppm NH3 (28.87%) was twice that of pure Ti3 C2 Tx and
the response time was as low as 1s. The alkali-treated MXene sensor was expected to be
a sensor for overspeed response.
Lee et al. [150] prepared graphene-based fibers (GFs) and Ti3 C2 Tx composites by wet
spinning process, and studied the gas sensing properties of the sensor to NH3 . The response
of the composite to 50 ppm NH3 was 7.9 times higher than that of pure MXene. When
the detection concentration was as low as 10 ppm, the composite sensor still showed 4.26%
gas response. Owing to the excellent flexibility and the high bending of fibrous material,
GFs was very suitable to be made into a flexible sensor. Because the GFs/MXene flexible
sensor was more flexible and stable than the simple MXene sensor, the change of resistance
was only ±0.2% after being bent more than 2000 times. This laid the foundation for future
wearable sensors.
In addition to compounding MXene with a single other material, scholars also com-
posite the two materials with MXene simultaneously to improve the gas sensing properties.
Sun et al. [150] first functionalized Ti3 C2 Tx with polyethyleneimine (PEI), and then riveted
Co3 O4 to form Co3 O4 @PEI/Ti3 C2 Tx composites. The gas sensing properties of the sensor to
NOx gas were studied. In the composite, the active site Co3 O4 was uniformly dispersed on
Ti3 C2 Tx and formed a heterostructure. The electron transfer channel PEI connected Co3 O4
and Ti3 C2 Tx . Because of this unique structure, Co3 O4 @PEI/Ti3 C2 Tx had a mesoporous
structure and high selectivity, low detection limit, high response, and short response time
for NOx gas. At room temperature, the composite sensor had a response of 27.9 to 100
ppm NOx and a response and recovery time of 1.6/73.1 s. There were two reasons for en-
hancing sensing performance: (1) Heterojunction and synergism improved the diffusivity
and carrier velocity of NOx molecules; (2) There were oxygen vacancies on the surface of
the composites, which could improve the efficiency of electron transport.
4. Sensing Mechanism of MXene-Based Gas Sensors

Since MXene has high conductivity, MXene generally exhibits metallic properties.
The gas-sensing mechanism of other semiconductor materials is that the increase or de-
crease of resistance depends on the type of gas molecules (donor or acceptor) and the type of
channel material (p-type or n-type). Nevertheless, the resistance changes of MXene always
increase regardless of the MXene gas sensor detects both electron donor gas and the elec-
tron acceptor gas. It is indicated that the concentration of electrons in the MXene gas sensor
always decreases or the transportation of electrons is always hindered [81,130,147,154,178].
Chen et al. [147] used the MXene sensor to detect ethanol and acetone and found that
the changes of resistance were always positive. They interpreted this phenomenon as
that the carriers in MXene decreased when gas molecules adsorbed on the surface of
the metallic MXene. Therefore, the resistance of MXene increased. For two-dimensional
materials, the gap between layers is an essential channel for electronic transportation.
The gap between layers of 2D MXene is relatively large, which is the primary channel
for electron transportation. The expansion of the lamellae is one of the main reasons
why MXene consistently exhibits a positive resistance phenomenon. Junkaew et al. [178]
researched the effect of interlayer expansion on gas-sensing performance and found that
interlayer expansion would affect the conductivity of the channel. Because the expansion
of the two-dimensional material sheet layer reduced the interlayer spacing and electrons
were easily affected. Because of the obstacles of the surface, the transmission of electrons
became more difficult. Therefore, MXene appeared as an increase in resistance. The gas
sensing mechanism of other 2D materials is the same as that of semiconductor materi-
als. Because their interlayer spacing is too small, which hinders the embedding of gas
molecules in a non-pressurized environment. So interlayer expansion will not affect their
gas response.
In the etching process of Ti3 C2 Tx MXene, the adsorbed molecules (H2 O and O) are p-
type Ti3 C2 Tx doping, resulting in the transformation of metallic Ti3 C2 Tx into semiconductor
characteristics [153]. At this time, the gas-sensing mechanism of MXene is consistent with
that of semiconductor materials. When the Ti3 C2 Tx sensor is placed in the air, the surface
will be adsorbed by O2 molecules. O2 molecules can obtain electrons from semiconductors
and change them into chemically adsorbed molecular oxygen (O2 − , O− , O2− ). O2 − which
was generated on the surface leads the hole accumulation layer (HAL) to form, reducing
electrical resistance. When the sensor is placed in the tested gas, the gas reacts with
O2 − on the surface. The electrons captured by O2 are released back into Ti3 C2 Tx and
the electrons and holes recombine in order to reduce the carrier of the Ti3 C2 Tx sensor,
resulting in an increase in resistance [127,129,134,135].
O2 (gas)→O2 (ads)
O2 (ads) + e− →O2 −
The work function of MXene is different from that of other n-type semiconductors.
When p-type MXene and n-type semiconductors are recombined, in order to keep the Fermi
level at the same level, electron transfer occurs between them, thus forming a built-in
electric field and Schottky barrier. The heterogeneous p–n junction formed by this interface
O2(ads) + e−→O2−
The work function of MXene is different from that of other n-type semiconductors.
When p-type MXene and n-type semiconductors are recombined, in order to keep the
Fermi level at the same level, electron transfer occurs between them, thus forming a
built-in electric field and Schottky barrier. The heterogeneous p–n junction formed by
this interface greatly affects the gas sensing mechanism of the gas sensor
[127,133,139,140,152,179,180].
greatly affects the gas sensingAt this time, the
mechanism positive
of the change
gas sensor or negative change of the
[127,133,139,140,152,179,180].
sensor
At thisresistance
time, thedepends
positiveon the electron
change donorchange
or negative and acceptor
of the characteristics
sensor resistance of the target
depends
gas molecule.
on the electronFor example,
donor the work
and acceptor function of of
characteristics MXene (4.79gas
the target eV)molecule.
is lower Forthan Co3O4
example,
the work
(6.48 eV), sofunction of MXene
the electrons (4.79 eV)
of MXene is lower
migrate to Cothan Co3 O4an
3O4. Then, (6.48 eV), so
electron the electrons
depletion layer
of MXene migrate to Co
with a positive zone is formed O . Then, an electron depletion layer with
3 4 on the MXene side and the negative one is formed on the a positive zone is
formed
Co on the
3O4 side. MXene side
A built-in and field
electric the negative
was built. oneThe is formed
built-inonelectric
the Co3field
O4 side. A built-in
counters the
electric of
transfer field was built.
electrons untilThe
the built-in
Fermi levelelectric fieldthe
reaches counters the transfer
same level of electrons
and a Schottky barrieruntil
is
the Fermi
created level 33a,b).
(Figure reachesWhenthe same level and amaterial
the composite Schottkyisbarrier
placedisincreated
NO2, gas(Figure 33a,b).
molecules
When the
adsorb composite
on the surface material
and capture is placed in NO
electrons 2 , gas
from themolecules
sensor. The adsorb on the
built-in surface
electric fieldand
is
capture electrons from the sensor. The built-in electric field is
destroyed and more electrons are transferred from MXene to Co3O4. It will cause thedestroyed and more electrons
are transferred
conductivity from
of the MXene
sensor to Co3 O4(Figure
to increase . It will33c) cause the In
[152]. conductivity
addition to of the sensor
p–type Ti3C2Tto x
increase (Figure 33c) [152]. In addition
MXene, there is also n-type MXene. For example, the Nb to p-type Ti C T
3 22CT MXene, there is
x x studied by Wang et al. also n-type
[140]
MXene. as
behaved Foranexample, the Nb2 CTx studied
n-type semiconductor. When by Wang
it was et al. [140] behaved
compounded with p-type as an n-type
PANI, it
semiconductor.
resulted in forming When it was
a p–n compounded
heterojunction with p-type
(Figure PANI, it resulted
33d). Additionally, the in forming
hetero a p–n
interface
heterojunction
generated (Figure
a narrow 33d). Additionally,
depletion the heteroininterface
layer. The electrons the NHgenerated a narrow depletion
3 molecule were transferred
to PANI when the sensor was placed in NH3. It would reduce the hole the
layer. The electrons in the NH 3 molecule were transferred to PANI when sensor was
concentration,
which caused 3the depletion layer on the PANI side to widen, thereby narrowinglayer
placed in NH . It would reduce the hole concentration, which caused the depletion the
on the PANI
conductive sideoftoPANI
path widen, andthereby
changingnarrowing the conductive path of PANI and changing
the resistance.
the resistance.
Figure 33. (a) Band diagram of Ti3 C2 Tx and Co3 O4 before contact; (b) Band diagram of Ti3 C2 Tx and Co3 O4 after contact;
(c) Energy band structure of the composites in different atmosphere (Reproduced with permission from [152]. Copyright
2021, the Royal Society of Chemistry); (d) The change of depletion layer and conductivity pathway of the Nb2 CTx /PANI
film (Reproduced with permission from [140]. Copyright 2021, Elsevier).
5. Conclusions and Outlook

This paper reviews the effects of etching method (HF etching, in-situ HF etching,
fluorine-free etching), intercalator, dispersion, and oxidation resistance and large-scale
preparation of MXene on the morphology and performance of the new two-dimensional
material MXene. Fluorine-containing etching makes MXene have more fluorine terminals
that are unfavorable to performance. However, etching with HF and fluoride to obtain
MXene is still the most widely used method. We should continue to develop more mature
and feasible fluorine-free etching vigorously. Corrosion methods to avoid problems caused
by fluorine terminal should be researched. This paper describes the application of original
MXene and its composite materials in gas sensors and explains the gas sensing mechanism
of MXene as a gas sensor to detect gases. The formation of composite materials by MXene
can increase the surface area, the spacing between layers and the active sites for gas
adsorption. The gas-sensing mechanism of metallic MXene is affected by the expansion of
the lamellae. MXene will be doped with H2 O and O during the etching process to become
a p-type semiconductor. In order to regulate and control the gas sensitivity of composite
materials, the semiconductor MXene was combined with other type semiconductors to
form a p–n heterojunction and a Schottky barrier. Although there are still few reports
on the application of MXene materials to gas sensors, MXene and its composite materials
possessing sizeable specific surface area, large porosity and high conductivity are expected
to become materials that can effectively detect gases at room temperature, especially for
the detection of NH3 and VOC gas.
Author Contributions: Writing, Q.L.; Supervision, Y.L.; Review and editing, W.Z. All authors have
read and agreed to the published version of the manuscript.
Funding: This work was financially supported by the Graduate Scientific Research and Innovation
Foundation of Chongqing, China (No. CYS20001) and the Science and Technology Research Program
of Chongqing Municipal Education Commission (No. KJQN201801320).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: No new data were created or analyzed in this study. Data sharing is
not applicable to this article.
Conflicts of Interest: The authors declare no conflict of interest.
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Chemosensors 2021, 9, 225. https://doi.org/10.3390/chemosensors9080225 https://www.mdpi.com/journal/chemosensors

Ti3 AlC2 + 3HF = AlF3 + 3/2H2 + Ti3 C2 (1)

Ti3 C2 + 2H2 O = Ti3 C2 (OH)2 + H2 (2)

Figure 3. Schematic illustration of the synthesis of Ti3C2(OH)2 by water-assisted potassium hy-

Figure 7. (A) Schematic

Figure 10. Schematic illustration of the preparation of Ti3C2Tx by lithia-

Table 1. Gas sensing performances of MXene-based gas sensors.

Conc. Operating Response Response/Recovery

3.1. Pristine MXene

Figure 24. (a)

3.2. MXene/Metal Oxide Gas Sensors

creased and formed a p-n heterojunction with ZnO.

The common problem of 2D materials is the stacking of layers, leading to a smaller

PEDOT:PSS, which is a composite of poly(3,4–ethylene dioxythiophene) (short for

3.4. Pd-MXene Gas Sensor

3.5. Miscellaneous Sensors

4. Sensing Mechanism of MXene-Based Gas Sensors

5. Conclusions and Outlook

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