Review

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Ti3C2TX MXene for Sensing Applications:

Recent Progress, Design Principles, and Future
Perspectives
Yangyang Pei, Xiaoli Zhang, Zengyu Hui, Jinyuan Zhou, Xiao Huang, Gengzhi Sun,* and Wei Huang*

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ABSTRACT: Sensors are becoming increasingly significant in our daily life

because of the rapid development in electronic and information technologies,
including Internet of Things, wearable electronics, home automation,
intelligent industry, etc. There is no doubt that their performances are
primarily determined by the sensing materials. Among all potential candidates,
layered nanomaterials with two-dimensional (2D) planar structure have
numerous superior properties to their bulk counterparts which are suitable for
building various high-performance sensors. As an emerging 2D material,
MXenes possess several advantageous features of adjustable surface properties,
tunable bandgap, and excellent mechanical strength, making them attractive in
various applications. Herein, we particularly focus on the recent research
progress in MXene-based sensors, discuss the merits of MXenes and their
derivatives as sensing materials for collecting various signals, and try to
elucidate the design principles and working mechanisms of the corresponding
MXene-based sensors, including strain/stress sensors, gas sensors, electrochemical sensors, optical sensors, and humidity
sensors. In the end, we analyze the main challenges and future outlook of MXene-based materials in sensor applications.
KEYWORDS: Ti3C2TX MXene, strain/stress sensors, gas sensors, electrochemical sensors, optical sensors, humidity sensors,
design principles, sensing mechanisms

T he widespread applications of wearable electronics and

Internet of Things drive the noteworthy expansion in
the global sensor market, which is poised to reach
$323.3 billion by 2024 with a compound annual growth rate of
13.3% according to BCC Research reports.1 Generally
illustrated in Figure 1, MXenes have a general formula of
Mn+1XnTX, where n = 1, 2, or 3, representing three common
structures. M stands for an early transition metal, such as Ti,
Mo, and V, X refers to carbon/nitrogen, while TX represents
various surface terminations, for example, fluorine (−F),
speaking, sensors are the devices that enable the acquisition hydroxyl (−OH), and/or oxygen (O).3 In case of double
of the changes in environment and output readable signals to transition-metal MXenes, the M atoms can exist either in
other electronics for postprocessing. As the essential integral random (solid solution) or ordered arrangement, where the
part, sensing material takes the responsibility to interact with ordered phase is energetically more stable. Typically, MXenes
the stimulus of either physical perturbation or chemical possess excellent mechanical strength, good thermal con-
reactions. To date, numerous nanomaterials have been ductivity, tunable bandgap from semiconducting to metallic,
synthesized and used as sensing component for various
and hydrophilic surfaces with abundant functional groups that
applications, including strain/stress sensors, humidity sensors,
can be postmodified and solution processed.4−7 These
gas sensors, photodetectors, biosensors, etc. Among all
candidates, two-dimensional (2D) layered materials have
their advantages of large surface-to-volume ratio, tunable Received: January 10, 2021
electronic structure, excellent flexibility, as well as outstanding Accepted: March 5, 2021
mechanical robustness. Published: March 11, 2021
Comparably, ever since their discovery in 2011, 2D
transition-metal carbides/nitrides (collectively denoted as
MXenes) are attracting enormous research interests.2 As

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Figure 1. Compositions of MXenes predicted theoretically and obtained experimentally. Reproduced with permission from ref 6. Copyright
2019 American Chemical Society.

characteristics render MXenes an ideal platform as sensing Ti3C2 + 2H 2O = Ti3C2(OH)2 + H 2 (2)

materials for a number of applications.
Herein, we comprehensively review the synthetic methods,
Ti3C2 + 2HF = Ti3C2F2 + H 2 (3)
physicochemical properties, and sensing applications of
MXenes. Particularly, we aim to cover the latest research The ab initio molecular dynamics (MD) simulations showed
achievements of using MXenes and their derivatives in strain/ that the H and F radicals decomposed from HF adsorbed on
stress sensors, gas sensors, electrochemical sensors, optical Ti atoms, weakening Al−Ti bonds, generating surface
sensors, and humidity sensors, highlight the principles of terminals, and ultimately forming Ti3C2TX.18−20 Subsequently,
device design, underscore the underlying sensing mechanisms, by using HF as etchant, numerous MAX phases, including
and provide insightful prospects for future endeavors. Ti2AlC, Ti3AlCN, Nb2AlC, Ti3SiC2, Mo2Ga2C, Zr3Al3C5, and
(Ti0.5Nb0.5)2AlC, were transformed into the corresponding
SYNTHESIS MXene nanosheets successfully.8,21 Since chemical etching is a
At present, the commonly used strategy for preparing MXene kinetically controlled process, several important reaction
nanosheets is the top-down etching from MAX phases parameters, such as duration, temperature, and HF concen-
(Mn+1AXn), where A represents an A-group element (e.g., Al tration, need to be considered. It was reported that a large n
and Si). Generally, the M−A bond is considered to be metallic, number in Mn+1AXn requires a prolonged etching time,
whereas the M−X bond features multiple characters of ionic, relatively high etching temperature, and low pH value.8 As
metallic, and covalent.8,9 Therefore, in contrast to the the main byproduct during etching is AlF3 (eq 1) which is not
exfoliation of graphene, the metallic M−A bond is difficult dissolvable in water, it is critically important to select an
to break by mechanical shearing. Nevertheless, it is feasible to appropriate temperature and time to avoid the precipitation of
be selectively etched rather than M−X bonds.10,11 The AlF3. On the other hand, Alhabeb and co-workers confirmed
preparation of MXenes typically includes two steps, namely that effective etching is preferentially achieved by HF with a
the selective etching of A and the delamination of high concentration (e.g., 30%), forming an accordion-like
MXenes.12−17 morphology, which was not observed when using 5% HF as
Etching. In 2011, it was reported that the MAX phase of the etchant (Figure 2a).22 The successful etching of Al in
Ti3AlC2 can be chemically etched by HF aqueous solution Ti3AlC2 was further evidenced by XRD analysis with an
following eqs 1−3, and Al was selectively removed forming obvious downshift of (002) peak (Figure 2b). Moreover, the
Ti3C2TX-based MXene.3 experimental results showed that vacancy defects derived from
the removal of surface Ti atoms can be adjusted by HF
2Ti3AlC2 + 6HF = 2AlF3 + 3H 2 + 2Ti3C2 (1) concentration. As shown in Figure 2c,d, vacancy clusters were
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Figure 2. (a) SEM images of (i) Ti3AlC2 (MAX) powder and multilayered Ti3C2TX etched by HF with the concentration of (ii) 5 wt %, (iii)
10 wt %, and (iv) 30 wt %. (b) XRD profiles of the pristine Ti3AlC2 powder and the obtained Ti3C2TX. Reproduced with permission from ref
22. Copyright 2017 American Chemical Society. (c) Scanning transmission electron microscopy images of Ti3C2TX flakes obtained by HF
etching with different concentrations of: (i) 2.7 wt %, (ii) 5.3 wt %, and (iii) 7 wt %. (d) Defect concentration calculated from the samples
shown in panel (c). Reproduced with permission from ref 21. Copyright 2016 American Chemical Society.

Figure 3. (a) The exfoliation of Ti3AlC2 via HF etching and TBAOH-assisted delamination. (b) Transmission electron microscopy (TEM),
selected area electron diffraction, and high-resolution TEM (HRTEM) images of (i) bulk Ti3AlC2, (ii) exfoliated Ti3C2-HF, and (iii)
delaminated Ti3C2-HF/TBA. Reproduced with permission from ref 30. Copyright 2020 American Chemical Society.

rarely observed at 2.7 wt % HF, but increased significantly at 7 for 45 h, and the experimental results indicated that the
wt % HF.21 copresence of fluorine ions and protons is the key for
To avoid direct utilization of toxic HF, in 2014, Halim and successful etching.24 Lipatov and co-workers further developed
co-workers utilized NH4HF2 as the etchant, which is much this approach by adjusting the feeding ratios between MAX
safer and milder.23 Alternatively, Ghidiu and co-workers and LiF (MAX: LiF = 1:5 or 1:7.5).25 It was found that excess
prepared Ti3C2TX by adding Ti3AlC2 powder in the mixture LiF promoted the etching of Al and the intercalation of Li+,
of LiF and HCl (6 M). The reaction was carried out at 40 °C leading to Ti3C2TX MXene nanosheets with larger size,
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Figure 4. (a) Stress−strain curves of Tin+1Cn samples. Reproduced with permission from ref 42. Copyright 2015 IOP Publishing. (b) TEM
images of a Ti3C2TX scroll with an inner diameter of <20 nm. Reproduced with permission from ref 9. Copyright 2014 John Wiley and Sons.
(c) An air plane model folded by Ti3C2TX film. (d) Tensile tests of Ti3C2TX/PVA films containing different amount of Ti3C2TX. (e) Photo
images of Ti3C2TX and Ti3C2TX/PVA scrolls loaded by weight. Reproduced with permission under a Creative Commons Attribution 4.0
International License (CC BY 4.0) from ref 44. Copyright 2014 National Academy of Sciences.

uniform thickness, and fewer defects. Typically, the etching Ti3C2 + a NH4HF2 + 2H 2O = (NH3)c (NH4)d Ti3C2(OH)x Fy
process transforms solid dense MAX into loosely accumulated (5)
accordion-like structure, which are also known as multilayer
MXenes (ML-MXenes). Therefore, an exfoliation step is For example, during the reaction between NH4HF2 and
necessary to separate ML-MXenes into monolayer. Ti3AlC2, (NH4)3AlF6 was generated instead of AlF3 (eq 4),
It is noteworthy that wet-chemical methods are not and in the meantime, NH3 and NH4+ were intercalated there
appropriate for etching nitride-based MAXs due to their between Ti3C2TX layers (eq 5). Lately, Li+, Na+, and Sn4+ were
higher formation energy.5 Urbankowski and co-workers also adopted as the intercalants.32,33 The obtained Ti3C2TX
developed a molten salt method (e.g., potassium fluoride, nanosheets had similar size to that of the original Ti3AlC2
lithium fluoride, and sodium fluoride) for preparing Ti4N3- crystals.22
based MXene by selectively etching aluminum from Ti4AlN3 at In addition to the above-mentioned top-down strategies,
550 °C in Ar.26 The residue fluoride in resultant powder was chemical vapor deposition (CVD) as a multifunctional
then removed using sulfuric acid (H2SO4) solution. bottom-up method was developed particularly suitable for
Exfoliation. In 2013, MXene nanosheets were exfoliated fabricating high-quality and large-area MXenes. For instance,
into single layer by inserting large organic molecules into the α-Mo2C crystals with a large lateral size of ∼10 μm and a
interlayers of the accordion-like structure followed by thickness of 3−20 nm were deposited on copper using
mechanical vibration or ultrasonication.4,12 The commonly molybdenum foil and methane (CH4) as the precursors at
used intercalants include tetrabutylammonium hydroxide 1085 °C in hydrogen.34 The molybdenum atoms diffused to
(TBAOH), dimethyl sulfoxide, hydrazine, urea, and the surface of liquid copper and reacted with carbon atoms
NH4+.12,27−29 For example, Chia and co-workers used generated from the decomposition of CH4 forming 2D Mo2C.
TBAOH as the intercalant to exfoliate Ti3C2TX MXene from Lately, TaN and ReC crystals were successfully prepared using
the products obtained via HF etching (Figure 3a).30 As shown the similar methods.35,36
in Figure 3b, MAX powder with micron-sized flakes was
expanded after the removal of Al, and the obtained Ti3C2-HF PROPERTIES
was delaminated into single-/fewer-layer MXenes by weaken-
ing the interlayer interaction using TBAOH. When NH4HF2 Typically, the properties of MXenes severely depend on their
was adopted as the etchant, the accordion-like multilayer composition, stacking order, and lateral size. When the Al
Ti3C2TX MXene was already intercalated with cations (e.g., atoms are removed from MAX phase (e.g., Ti3AlC2), Ti atoms
NH4+) in the aqueous solution.8,31 are exposed on both sides of Ti3C2 layer. These unstable Ti
atoms are prone to link with TX (e.g., −F, −OH, and O)
3 generated during the etching in aqueous solution to lower the
Ti3AlC2 + 3NH4HF2 = (NH4)3 AlF6 + Ti3C2 + H2
2 total surface energy.37,38 Therefore, it is necessary to
(4) fundamentally understand the influence of terminations on
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Figure 5. (a) Imaginary part of the in-plane (ε2,xx) and out-plane (ε2,zz) dielectric function, (b) in-plane (αxx) and out-plane (αzz) adsorption
coefficient, and (c) in-plane (Rxx) and out-plane (Rzz) reflectivity as a function of photon energy for functionalized Ti3C2T2 monolayer.
Reproduced with permission from ref 46. Copyright 2016 Royal Society of Chemistry.

Figure 6. (a) The electronic structures of Ti3C2 and Ti3C2TX monolayers with −F and −OH terminations. Reproduced with permission from
ref 2. Copyright 2011 John Wiley and Sons. (b) The electronic structures of I-Ti3C2F2, II-Ti3C2F2, III-Ti3C2F2, I-Ti3C2(OH)2, II-
Ti3C2(OH)2, and III-Ti3C2(OH)2. Reproduced with permission from ref 52. Copyright 2012 American Chemical Society. (c) The
temperature-dependent resistance measurements for Ti3C2TX, Ti3CNTX, and Mo2TiC2TX. (d) The electron transport mechanism of
Mo2TiC2TX before and after annealing. Reproduced with permission under a Creative Commons Attribution 4.0 International License (CC
BY 4.0) from ref 55. Copyright 2019 Springer Nature.

the physicochemical properties of MXenes so as to provide Naguib and co-workers directly converted Ti3C2TX in to
versatility in designing sensors.39 TiO2/carbon sheets simply by annealing at 1150 °C in air for
Thermal/Chemical Stability. The stability of MXene 30 s.41 Such transformation may induce some distinct
nanosheets is critically important for practical applications properties typically by sacrificing the merits of MXenes, such
because the materials may undergo a series of thermal/ as high conductivity, superior pseudocapacitance, and good
chemical treatments during device fabrication and face solution processability. Therefore, Ti3C2TX-based materials
specialized working environment. Typically, heat treatment in should be designed rationally depending on their applica-
inert atmosphere (e.g., Ar) at elevated temperature (e.g., 1200 tions.20
°C) results in the elimination of surface terminations and Mechanical Property. The Young’s moduli of Ti3C2 were
improves the crystallinity of MXene nanosheets without any theoretically calculated to be as high as 502 GPa (Figure 4a).42
damage of the layered morphology.40 Notably, Ti3C2TX The elasticity (E2D) of single Ti3C2TX was measured ranging
MXene is unstable in oxidative environment (e.g., hot air) from 278 to 393 N m−1 based on the force−deflection
and gradually transforms to oxide (TiO2).17 For instance, relationship in force−indentation experiments using the
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Poisson’s ratio of v = 0.227, while two-layer Ti3C2TX had a E2D 6b). Therefore, the electronic structures of monolayer MXenes
value falling in the range of 632−683 N m−1. The average E2D are possibly tuned by adjusting surface groups and their
of two-layer Ti3C2TX (655 ± 19 N m−1) was twice that of geometric conformation.53
monolayer sheet (326 ± 29 N m−1), suggesting the strong Regarding multilayer MXenes, the intercalating agents can
interlayer interaction between surface groups. The exper- enlarge the interlayer spacing, thereby increasing the resistance
imental results of nanoindentation showed that Ti3C2TX had a by an order of magnitude.39,54 A direct experimental
higher E2D than graphene oxide (GO), reduced GO (rGO), observation was reported by Hart and co-workers.55 They
and molybdenum sulfide (MoS2), yet lower than h-BN and found that the intercalation of H2O and TBA+ in MXenes
graphene.43 In addition, Ti3C2TX exhibited good flexibility and assemblies led to higher resistance and induced negative dR/
can be rolled into a conical shape with a radius of <20 nm dT (a negative temperature dependence of resistance) as
(Figure 4b).2 As a result, the free-standing paper assembled by shown in Figure 6c. Thermal annealing at 200 °C in vacuum
Ti3C2TX sheets can be folded into an airplane without any decreased Ti3C2TX and Ti3CNTX resistance by 18% and 36%
obvious damage (Figure 4c). The Ti3C2TX thin film (∼3.3 μm owing to the removal of H2O molecules. Since Mo2TiC2TX
thick) exhibited a mechanical strength of ∼22 MPa (Figure contained both H2O and TBA+, 24% and 69% reduction in
4d). The cylinder rolled up by Ti3C2TX paper (∼5 μm thick) resistance were obtained after annealing at 200 and 500 °C,
can support ∼4000 times its own weight. The incorporation of respectively, due to the removal of H2O and the decom-
10 wt % PVA further enhanced the mechanical strength of position of TBA+ accompanying with a transition of dR/dT
Ti3C2TX/PVA paper by 34%, bearing ∼15,000 times of its own from negative to positive (Figure 6d). Further increase in
weight (Figure 4e).44 annealing temperature accelerated the removal of surface
Optical Property. The optical properties of MXenes terminations, leading to an improved conductivity. A typical
intrinsically correlate to their electronic structures. The density example is the detachment of F-terminals from Ti3C2TX when
functional theory (DFT) calculation indicated that most the temperature rose from 300 to 775 °C.56 In comparison, the
Tin+1Xn exhibit metallic nature with overlap between the defunctionalization of Mo2TiC2TX occurred at a lower
conduction and valence bands at the Fermi level.45 Recent temperature of 500 °C, indicating the weaker interaction
studies showed the electronic structure of MXenes is largely between F and Mo.
affected by their surface terminations.9 The imaginary part (ε2)
of the dielectric function, adsorption coefficients (α), and APPLICATIONS
refractivity (R) were calculated for functionalized Ti3C2T2 Strain/Stress Sensors. Strain/stress sensors have been
monolayer (Figure 5). Within photon energy between 1.4 extensively studied and widely utilized in a broad range of
and 4.5 eV, F- and OH-terminated Ti3C2TX had lower in-plane applications, including scales, robotics, human-machine-inter-
αxx than pristine and O-terminated ones. Moreover, both αxx faces, healthcare, motion monitoring, electronic skins, artificial
and Rxx showed neglectable dependence on photon frequency eardrum, etc.57−59 The advantage features of MXenes,
in visible region.46 The above results were consistent with that including high electrical conductivity, excellent flexibility, and
reported by Berdiyorov and co-workers, which shows that the good hydrophilicity suitable for wet-processing, endow its
real and imaginary parts of the frequency-dependent dielectric potential applications in strain/stress sensors (Table 1).51,60,61
functions calculated for pristine Ti3C2, Ti3C2F2, Ti3C2O2, and For example, a tensile strain sensor based on the hybrid
Ti3C2(OH)2 greatly depending on the functional groups. The network of Ti3C2TX nanoparticles (NPs) and nanosheets was
peaks agreed well with the inter- and intraband transitions developed by Yang and co-workers (Figure 7a). The sensing
obtained from DFT predictions. Moreover, in visible range, F- mechanism was attributed to the resistance change originating
and OH-terminated Ti3C2TX showed lower absorption and from the migration of NPs and the bridging effect of Ti3C2TX
reflectivity than pristine Ti3C2, making them more suitable for nanosheets. The thus fabricated sensor exhibited a gauge factor
transparent electrode applications.47−49 In addition, depending (GF) of >178.4, a sensing range within 0−53%, a detection
on thickness, a strong absorption was observed between 700 limit of 0.025%, and stable response under a 20% strain
and 800 nm, implicating potential applications in photothermal without obvious degradation over 5000 cycles (Figure 7b).62
therapy.50 Cai and co-workers designed a sandwich-like thin film through
Electrical Property. According to DFT calculations, the alternatively spray-coating Ti3C2TX nanosheets and hydro-
electronic structure of Ti3C2TX severely depends on the philic single-walled carbon nanotubes (CNTs) (Figure 7c).63
surface terminations (Figure 6a). The presence of −F and Upon tensile loading and unloading, the interwoven thin film
−OH transforms metallic Ti3C2 to semiconductors with showed reversible resistance change due to the generation and
obvious bandgaps of 0.05 and 0.1 eV, respectively, reducing repair of cracks through the interconnection of one-dimen-
the carrier density and thus the conductivity.2,51 Moreover, it sional (1D) CNTs and 2D MXenes (Figure 7d). The resultant
was reported the electrical properties of the obtained sensor exhibited high sensitivity (GF = 772.6), a detection
Ti3C2(OH)2 and Ti3C2F2 monolayers showed dependence limit of 0.1% strain, tunable sensing range between 30% and
on the spatial arrangement of −OH and −F on Ti3C2TX 130%, and good reliability and stability over 5000 cycles. In
MXene surface, resulting in either narrow bandgap semi- addition to thin films, MXene-based hydrogels with self-healing
conductors or metallic characteristic.52 Three main possible ability were synthesized using poly(vinyl alcohol) (PVA) as
configurations were theoretically constructed: All −OH or −F polymeric matrix and applied as sensing materials for strain
directly linked to Ti atoms or located at the hollow sites above detection (Figure 7e).64,65 Ti3C2TX provided highly conductive
three adjacent C atoms (type I), all −OH or −F sat on the pathways as well as enhanced self-healing ability of the
topmost C atoms (type II), and the asymmetric arrangement hydrogel due to its hydrophilic properties (Figure 7f). The as-
of type I and type II on the two sides of Ti3C2 (type III). It was fabricated capacitive sensor showed a GF of 0.4 with a linear
found that I-Ti3C2F2 behaved as a semiconductor (∼0.04 eV response and low hysteresis within 200% strain (Figure 7g). In
bandgap), while II-Ti3C2F2 showed metallic features (Figure addition, the device exhibited only 5.8% relative capacitance
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 Table 1. MXene-Based Sensors
sensitivity (linear response/
type target MXene composition range) test range LOD recovery time ref
ACS Nano

force sensors tension Ti3C2TX Ti3C2TX-AgNW-PDA/Ni2+ 256.1 (0−15%) 0−83% − − 137

Ti3C2TX MXene/PU 12,900 0−152% − − 138
Ti3C2TX MXene/silver 309.1 (0−60%) 0−200% − − 139
Ti3C2TX Ti3C2/rubber 107.4 (0−10%) 0−75% 0.1% 50 ms 140
Ti3C2TX AgNW/WPU-MXene 128,800 (0−15%) 0−100% − 344 ms 141
Ti3C2TX MXene/polyurethane 22.9 (0−10%) 0−150% 0.1% − 142
Ti3C2TX MXene/PAAm/PVA 5.0 (0−200%) 0−350% − − 143
Ti3C2TX Ti3C2TX/graphene/PDMS 190.8 (0−52.6%) 0−74.1% ∼0.025% 130 ms 144
Ti3C2TX Ti3C2TX/PDMS 3.6 (0−75%) 0−75% − − 145
Ti3C2TX MXene/polystyrene 14,000 (120−240%) 130−900% − − 146
Ti3C2TX MXene/PDMS 7400 (0.6−0.7%) 0−0.7% − 88 ms 147
Pressure Ti3C2TX MXene/tissue paper 0.55 kPa−1 (23 Pa− 23 Pa−30 kPa 10.2 Pa 11 ms 148
982 Pa)
Ti3C2TX s-MXene/SWNTs 11.47 kPa−1 13 Pa−0.77 kPa − 50/20 ms 149
Ti3C2TX MXene/polyacrylate 148.26 kPa−1 (7 kPa− 0−16 kPa − 120 ms 150
16 kPa)
Ti2C Ti2C/PDMS 507 kPa−1 (0−5.75 0−40 kPa 8 Pa 60/40 ms 151
kPa)
Mo2TiC2O2 Mo2TiC2O2-based quantum 0.07 × 10−6 kPa−1 0−6 GPa − − 152
transport device
Ti3C2TX MXene/Au/PET 99.5 kPa−1(0.05 kPa− 0.05−3.5 kPa 9 Pa 4 ms 153

4002
1 kPa)
Ti3C2TX Ti3C2/natural microcapsules 24.63 kPa−1 10−200 Pa 8 Pa 14 ms 154
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Ti3C2TX CSx/MXene-C 80.4 kPa−1 0.1−5 kPa 1.0 Pa 109.6 ms 155

Ti3C2TX MXene/cotton textile 3.844 (0−29 kPa) 0−40 kPa − 26 ms 156
Ti3C2TX MXene/CNC 45.5 kPa−1 0−10 kPa 1.0 Pa 189 ms 157
Ti3C2TX MXene/PDMS − 10−600 mg 10 mg 20 ms 158
Ti3C2TX MXene/SWCNT 165.35 kPa−1 0.69 Pa−100.4 Pa 0.69 Pa 48 ms 159
Ti3C2TX MXene/bacterial cellulose 12.5 kPa−1 0−10 kPa 1.0 Pa 167 ms 160
Ti3C2TX MXene/ANFs 128 kPa−1 ∼623 kPa 100 Pa 320 ms 161
Ti3C2TX MXene/PVA/PVP 10.75 kPa−1 0−61.5 kPa 0.87 Pa 33.5 ms 162
gas sensors NH3 Ti3C2TX Ti3C2TX/polyacrylamide 4.7% (200 ppm) 0−200 ppm − 12.7/14.6 s 163
VOCs Ti3C2TX Ti3C2TX/fluoroalkylsilane − 5−120 ppm − 39/139 s 164
Ti3C2TX Ti3C2TX/W18O49 − 11.6−20 ppm 170 ppb 5.6/6 s 165
Ti3C2TX Ti3C2TX/WSe2 0.24 0−40 ppm − 9.7/6.6 s 166
Ti3C2TX MXene/Fe2(MoO4)3 43.1 (100 ppm) 5−1000 ppm 5 ppm 18/24 s 167
H2 Ti3C2TX MXene/Pd colloidal (23.0 ± 4.0)% (4%) 0.5−40% 0.5% (32 ± 7) s 168
nanoclusters
NO2 Ti3C2TX Ti3C2TX/ZnO spheres − 5−100 ppm 5 ppm 34 s 169
electrochemical Ag+/ Mn2+ Ti3C2TX Ti3C2TX nanosheets − the range of 0.1−40 μM and 0.5−60 μM for 9.7 nM for Ag+ 102 nM − 170
sensors Ag+ and Mn2+ ions. for Mn2+
organophosphorous Ti3C2TX AChE/CS-Ti3C2TX/GCE − 1 × 10−14−1 × 10−8 M 0.3 × 10−14 M − 171
pesticides
Review

synephrine Ti3C2TX MXene/MWCNTs − 0.5−70 μM 0.167 μM − 172

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decay after cyclic test for 10,000 times. Wang and co-workers

173
174
175
176
177
178
ref
designed an elastic core−sheath yarn using Ti3C2TX MXene as
recovery time conductive layer for strain sensing.66 The MXene-based core−
sheath yarn (MCSY) sensor had a GF of ∼0.67, a linear
response/

detection range to 120% strain, a LOD of 0.3% strain, and a

200 ms
∼1.8 s
∼10 s
6.3 s
response time of 0.12 s. The sensing mechanism was attributed
−
−

to the changes in contact points between conductive filaments.

Under compression, the distance between adjacent nano-
sheets in MXene-based assemblies decreases, leading to
resistance change, and this provides the basis for designing
piezoresistive sensors.67 For example, hybrid films composed
LOD

0.98 Fg mL−1
1.0 nmol L−1

of elastic P(VDF-TrFE) and Ti3C2TX nanosheets (mass ratio

of 1.6:1) were prepared by spin-coating and applied as pressure
0.7 nM

sensor (Figure 8a).68 The device showed a GF of 817.4 kPa−1

0.1 °C

at the low loading level of 0.072−0.74 kPa and a GF of

−
−

2213.68 kPa−1 under the high force level ranging from 0.74 to
3.083 kPa (Figure 8b), together with a response time of 16 ms
(Figure 8c). Alternatively, Cheng and co-workers fabricated a
piezoresistive sensor by spray coating a single layer of Ti3C2TX
nanosheets on PDMS surface patterned with spinous micro-
0.003 μmol L−1−20.0 μmol L−1

structures (Figure 8d).69 The sensing mechanism was

test range

essentially originated from the contact resistance change

between the microstructured PDMS and the interdigital
0.05−10,000 pg mL−1

electrodes (Figure 8e). The ΔI/Ioff raised rapidly with a

0−62% 25−40 °C

sensitivity of 151.4 kPa−1 below 4.7 kPa, then gradually

increased between 4.7 and 15 kPa with the corresponding
0−100 kPa

sensitivity of 33.8 kPa−1. Under 0.73 kPa, the response and

140 °C

recovery times of the sensor were 125 and 104 ms,

respectively. MXene-based aerogels and three-dimensional
(3D) foam also show sensitive responses to compression
596 mA cm−2 mM−1

deformation.70,71 For example, Ti3C2TX/rGO hybrid aerogels

sensitivity (linear

1.67 (0−100 kPa)

were prepared through a simple ice-templated freezing-drying

up to 986 °C1−
range)

220.8 (0−5%)

technology and applied as piezoresistive sensors (Figure 8f).

The robust 3D framework formed by Ti3C2TX and rGO
enabled the sensor a sensitivity of 22.56 kPa−1 (Figure 8g) with
a response time <200 ms.72
−
−

Gas Sensors. The identification and quantification of

pristine and oxidized Ti3C2TX

MXene-AgNW-PEDOT: PSS-

gaseous species, such as CO, NO, CO2, NO2, NH3, H2S, and
SOX, are of essential importance for human health, industry
safety, emission, and air quality monitoring.73−76 Because of its
composition

Ppy@Ti3C2TX/PMo12
MXene/NH2−CNTs

2D layered structure and adjustable surface terminations,

Ti3C2TX/PDMS

MXenes are considered an ideal platform for gas sensing.77,78

MXene/PAM

The suitability of Ti2CO2 MXene as sensing material for NH3

TeNW

was predicted using DFT calculations by Yu and co-workers.79

Ti2CO2 was the semiconductor and showed strong adsorption
to NH3 at Ti sites with a binding energy of −0.37 eV (Figure
9a). Comparably, due to the weak interaction, Ti2CO2 has no
MXene

response to H2, CO2, O2, CO, N2, NO2, and CH4 (Figure 9b).
Ti3C2TX
Ti3C2TX
Ti3C2TX
Ti3C2TX
Ti3C2TX
Ti3C2TX

The suitability of semiconducting M2CO2 (M = Sc, Ti, Zr, Hf)

for NH3 sensing was also theoretically evaluated, and the
results showed that the effective release/trapping of NH3 on
temperature and strain

M2CO2 can be controlled by the charge state of M.80 This

conclusion was supported by Khakbaz and co-workers who
target

analyzed the gas sensing performance of Ti3C2TX in the

temperature
osteopontin

presence of different surface terminations and water mole-

sensor

cules.81 The binding energy between NH3 and the Ti sites near
fisetin

H2O2
Table 1. continued

to O atoms is 60%−180% larger than that adjacent to F atoms,

indicating that the Ti3C2TX with a low content of F
terminations was preferred for NH3 sensing.
multifunctional

Lee and co-workers experimentally deposited Ti3C2TX thin

type

film on a polyimide substrate by a solution casting method.82

sensor

The Ti3C2TX film with a p-type semiconducting behavior

showed a resistance increase when exposed to ethanol,
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Figure 7. (a) Tensile behavior and (b) resistance change of the Ti3C2TX-based strain sensor. Reproduced with permission from ref 62.
Copyright 2019 John Wiley and Sons. (c) Fabrication of Ti3C2TX/CNT thin film with a laminar structure. (d) SEM images of the Ti3C2TX/
CNT sensing layer during the first stretching-releasing cycle from (i) 0%, (ii) 5%, (iii) 20%, (iv) 40%, to (v) 80%, then back to (vi) 0%.
Reproduced with permission from ref 63. Copyright 2018 American Chemical Society. (e) Photo images of the Ti3C2TX/PVA hydrogel. (f)
Self-healable and stretchable demonstrations of the Ti3C2TX/PVA hydrogel. (g) Capacitance response of the Ti3C2TX/PVA hydrogel
between 0 to 200% strain. Reproduced with permission from ref 65. Copyright 2019 John Wiley and Sons.

methanol, acetone, and ammonia, respectively. The sensing connected porous network via electrostatic attraction with
mechanism was attributable to the charge transfer between electrospun polymer scaffold (Figure 10d).86 The as-prepared
MXenes and the target gas molecules which were supposed to sensor presented response signals to a few different volatile
be adsorbed on the defect sites and/or surface terminations organic compounds (VOCs) with a sensitivity falling in the
(e.g., O and −OH) of MXene nanosheets. For example, range of 0.1−0.17 ppm−1, a LOD of 50 ppb, and the response/
according to eqs 6 and 7, when NH3 molecules are adsorbed recovery times <2 min (Figure 10e). Distinct from other 2D
on Ti3C2TX via O− and OH−, the generated electrons combine materials such as rGO, MoS2, and phosphorene, MXenes
with the holes in Ti3C2TX MXene, leading to resistance showed decreased resistance when exposed to gas species
increases. regardless of their type (n- or p-type).83 Koh and co-workers
2NH3 + 3O− → N2 + 3H 2O + 3e− (6) used an in situ X-ray diffraction (XRD) method to investigate
the swelling behavior of Ti3C2TX membrane upon the
− −
NH3 + OH → NH 2 + H 2O + e (7) exposure to gas/vapor (Figure 10f).87 The experimental
Further experiments by Kim and co-workers confirmed the observation indicated that the Ti3C2TX membrane selectively
high sensitivity of Ti3C2TX to acetone, ethanol, and NH3, with responded to ethanol vapor rather than CO2 with an obvious
minimal interference of CO2, NO2, or SO2.83 At room expansion. In addition, the dissolution of target molecules was
temperature, the sensor showed a detectable range of 50 to determined by the intercalated metal ions. It was found that
1000 ppb for NH3 with a limit of detection (LOD) of 0.13 the inserted Na+ derived from NaOH treatment enabled the
ppb. By coating Ti3C2 on ceramic tubes, Wu and co-workers significant swelling of Ti3C2TX membrane in the presence of
constructed NH3 sensors which had linear response between ethanol, thus gaining a high response (Figure 10g).
10 and 700 ppm.84 The sensing performance of Ti3C2TX can In addition to Ti 3 C 2 T X , other MXene nanosheets,
be further improved by hybridizing with rGO via wet spinning particularly V2CTX and V4C3TX, have been utilized for gas
method (Figure 10a). The obtained Ti3C2TX/rGO fibers sensing applications.79,88 The detection limits of V2CTX to H2
exhibited obvious electrical response (6.77%) to 50 ppm of and CH4 were determined to be 1 and 9 ppm, respectively, by
NH3 (Figure 10b), which was, respectively, 4.7- and 7.9-fold Lee and co-workers.89 Recently, Zhao and co-workers
higher than that of bare rGO and Ti3C2TX electrode.85 Such an demonstrated the selective acetone detection by V4C3TX-
enhancement was assigned to the expanded bandgap of based sensor with a LOD of ∼1 ppm due to the difference in
Ti3C2TX from 1.05 to 1.57 eV due to the heterogeneous adsorption energy.90
hybridization with rGO (Figure 10c). In another work, Yuan Electrochemical Sensors. Electrochemical sensors are
and co-workers fabricated a Ti3C2TX MXene-based inter- considered powerful tools for a variety of practical applications
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Figure 8. (a) The preparation, (b) current response, and (c) response time of Ti3C2TX@P(VDF-TrFE) film. Reproduced with permission
from ref 68. Copyright 2020 American Chemical Society. (d) The preparation of piezoresistive sensors by coating Ti3C2TX nanosheets on
spinous microstructures. (e) The sensing mechanism of the device in panel (d) under the original, heavy loading, light loading, and recovery
state, respectively. Reproduced with permission from ref 69. Copyright 2020 American Chemical Society. (f) The assembly of Ti3C2TX/rGO
aerogel and the corresponding sensing mechanism under pressure. (g) Comparison of the current responses between Ti3C2TX/rGO aerogel
and rGO aerogel. Reproduced with permission from ref 72. Copyright 2018 American Chemical Society.

Figure 9. (a) The density of states of the single-layer Ti2CO2 upon the adsorption of NH3 and CO2. (b) The side and top views of the
adsorption of H2, CO2, O2, NH3, CO, N2, NO2, and CH4 on Ti2CO2. Reproduced with permission from ref 79. Copyright 2015 American
Chemical Society.

due to their relatively good selectivity, linear output, excellent Environmental Pollutants. Carbendazim (CBZ), a sort of
repeatability, and low cost. Generally, the interactions between benzimidazole fungicide, has been wildly applied in agriculture,
sensing materials and analytes are critically important in horticulture, forest, and gardening as well as in the preservative
determining the sensing performance.91 MXenes as a typical industry, yet is harmful to the environment and human health.
2D material have biocompatibility, large specific surface area, Therefore, the sensitive and accurate detection of CBZ is
rich surface chemistry, tunable lateral size, good electrical highly necessary.93 Wu and co-workers drop-casted Ti3C2TX
on glass carbon electrode (GCE) as sensing material for the
conductivity, and mechanical robustness, allowing efficient and
determination of CBZ (Figure 11a).94 The results showed that
selective interaction with target species.63,92 MXene-based
CBZ can be electrochemically reduced on Ti3C2TX/GCE with
materials have been utilized directly or indirectly as redox a cathodic peak at 0.02 V. The electrocatalytic activity of
transducer and electrocatalysts for detecting small molecules, Ti 3 C 2 T X toward CBZ was attributed to the surface
pharmaceutical drugs, environmental pollutants, and bio- terminations on Ti3C2TX MXene. The adsorption energies
markers. Herein, the design and applications of MXene- (Ea) of CBZ on Ti3C2F2 and Ti3C2O2 were −1.31 eV and
based materials for electrochemical detection of environmental −0.30 eV, respectively, indicating that the fluorine termination
pollutants and biomarkers are the focus of this section. is favorable for electrochemical sensing. As a result, a detection
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Figure 10. (a) Wet spinning of Ti3C2TX/GO hybrid fiber. (b) Sensing responses of Ti3C2TX/rGO hybrid fiber (mass ratio = 4:6), rGO fiber,
and Ti3C2TX film to NH3. (c) Energy-level of Ti3C2TX/rGO and Ti3C2TX. Reproduced with permission from ref 85. Copyright 2020
American Chemical Society. (d) Electrospinning 3D Ti3C2TX MXene network. (e) Resistance changes of 3D Ti3C2TX upon exposure to
different gases. Reproduced with permission from ref 86. Copyright 2018 Royal Society of Chemistry. (f) In situ XRD measurement and (g)
the corresponding (002) peak shift of Ti3C2TX film upon the exposure to CO2 and ethanol. Reproduced with permission from ref 87.
Copyright 2019 American Chemical Society.

limit of 10.3 nM was achieved (Figure 11b). The sensing with the respective LOD values of 0.098, 0.041, 0.032, and
performance was further improved by Xie and co-workers 0.130 μM. Normally, modifying the MXene surface with active
through hybridizing Ti3C2TX with electrochemically reduced nanomaterials can further improve its sensing performance.
graphene oxide (ERGO) (Figure 11c).95 The obtained Following this direction, Zhu and co-workers reported the
Ti3C2TX/ERGO sensor exhibited a detection limit of 0.67 synthesis and application of MXene-bismuth (Bi@d-Ti3C2)
nM (Figure 11d). By utilizing Ti3C2TX/Au-Pd as a sensing hybrid for determining Zn (II), Cd (II), and Pb (II).101 The
material, Zhao and co-workers designed an electrochemical measured sensitivities were 0.60, 0.84, and 0.98 μA L μg−1 with
sensor toward the detection of organophosphorus pesticides the LOD of 0.5, 0.4, and 0.2 μg L−1 for Zn (II), Cd (II), and
(Figure 11e), which was adopted in agriculture to increase Pb (II), respectively, which are much lower than the guidance
crop yields yet caused severe environmental pollution.96,97 value of the World Health Organization for drinking water.
Taking paraoxon as a model pesticide, the as-fabricated sensor PANI-Ti3C2 composite was also prepared and loaded on GCE.
showed a linear detection range between 0.1 μg L−1 and 1000 The modified electrode showed a linear response to Hg2+
μg L −1 with a LOD of 1.75 ng L −1 (Figure 11f). within the concentration of 0.1−20 μg L−1 and a LOD of 0.017
Methamidophos was also electrochemically detected by the μg L−1.102 In addition to heavy metal ions, Rasheed and co-
combination of Ti3C2TX/Au and MnO2/Mn3O4 derived from workers demonstrated the electrochemical determination of
Mn-MOF (Figure 11g).98 The Ti3C2TX/Au/MnO2/Mn3O4/ bromine ions (BrO3−) in water using Ti3C2TX as a sensing
GCE exhibited a broad linear detection range of 10−12−10−6 M platform.103 The obtained sensor exhibited a LOD of 41 nM
(Figure 11h). In addition, MXene-based sensors can also and a linear response between 50 nM and 5 μM. The sensing
detect a variety of substances including synephrine and mechanism was attributable to the electrocatalytic capability of
methamidophos, which are shown in Table 1. Ti3C2TX nanosheets toward the selective reduction of BrO3− as
Heavy metal ions are another type of pollution that can displayed in the following equation:
cause cancer and serious environmental contaminations.99 A BrO3− + 3Ti2 + + 6H+ → Br− + 3Ti4 + + 3H 2O (8)
kind of alkaline intercalated Ti3C2 (alk-Ti3C2) was synthesized
for the detection of Cd (II), Pb (II), Cu (II), and Hg (II) Biomarkers. A biomarker as a fingerprint molecule that
(Figure 12a,b).100 The results showed that Cd (II), Pb (II), Cu exists in drugs, blood, fluids, and tissues can reflect the toxicity
(II), and Hg (II) with a concentration range from 0.1 μM to and pathogenic diseases. Therefore, their accurate detection is
1.5 μM were simultaneously determined in 0.1 M acetic acid of essential importance for early clinical diagnosis, risk
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Figure 11. (a) The detection of CBZ on Ti3C2TX modified electrode and (b) the corresponding calibration curve. Reproduced with
permission from ref 94. Copyright 2019 Elsevier. (c) The detection of CBZ based on Ti3C2TX/ERGO/GCE and (d) the corresponding
differential pulse voltammetry (DPV) plots in PBS (0.1 M, pH 7.0). Reproduced with permission from ref 95. Copyright 2019 IOP
Publishing. (e) The application of Ti3C2TX/Au-Pd nanocomposites in enzyme-based pesticide biosensor and (f) the corresponding
amperometric response in PBS (0.01 M, pH 7.4). Reproduced with permission from ref 96. Copyright 2020 Elsevier. (g) Methamidophos
assay based on Ti3C2TX/Au/MnO2/Mn3O4/GCE biosensor and (h) the corresponding DPV responses after inhibition with different
concentrations of methamidophos from 0, 10−6, 10−8, 10−9, 10−10, 10−11 to 10−12 M. Reproduced with permission from ref 98. Copyright
2019 Elsevier.

assessment, and even successful treatment.106,107 Electro- 10 nM and a LOD of 5 pM. Surface modification was proven
chemical technique has been widely utilized for noninvasive as an effective approach to stabilize MXenes at the anodic
sensing of biomarkers. Isoniazid (INZ) and acetaminophen potential window. Metal nanoclusters (such as Ag, Pd, Au, etc.)
(ACOP) as two types of commonly used drugs that have the were loaded on MXene surfaces and used for electrochemical
possibility to induce liver damage were determined by Zhang sensors.105,110,111 For instance, Pd NPs were uniformly grown
and co-workers using a modified screen-printed electrode on Ti3C2TX surface via self-reduction forming Pd@Ti3C2TX
(SPE) based on Ti3C2TX nanosheets.108 The as-fabricated nanocomposites toward the electrochemical determination of
Ti3C2TX MXene/SPE enabled simultaneous determinations of L-Cys (Figure 12d).
105
The sensor gave a linear response to L-
ACOP and INZ with respective linear detection ranges of Cys between 0.5 μM and 10 μM, providing a LOD of 0.14 μM.
0.25−2000 μM (LOD = 0.048 μM) and 0.1−4.6 μM (LOD = Neampet and co-workers modified the screen-printed carbon
0.064 μM), superior to bare SPE. Shahzad and co-workers
electrode with Pt/PANI/Ti3C2TX MXene for hydrogen
reported a dopamine (DA) sensor by drop-casting Ti3C2TX
peroxide and lactate sensing with respective detection limits
nanosheets on a GCE followed by Nafion coating. A LOD of
∼3 nM and a detectable window of 0.015−10 mM were of 1.0 μM and 5.0 μM.112 Similarly, Ti3C2TX MXene/graphite
achieved because of the electrostatic interaction between the composite showed an improved sensitivity to adrenaline (AD)
negatively charged Ti3C2TX/Nafion and the positively charged with a LOD of 9.5 nM.113 In addition, hybridizing Ti3C2TX
DA aromatic molecules.109 The abundant surface terminations MXene with layered double hydroxides (LDHs), the non-
(e.g., −OH, −F and O) on MXenes make them an ideal enzymatic determination of glucose with a linear response
platform as carriers for immobilizing active substances. For ranging from 0.002 mM to 4.096 mM was achieved by Li and
example, tetrahedral DNA nanostructures (TDNs) were co-workers.114 The possible mechanism for glucose oxidation
coordinately fixed on the surface of Ti3C2TX nanosheets on NiCo-LDH in alkaline solution was accomplished by the
(Figure 12c).104 By employing gliotoxin aptamer, mycotoxin reduction of Ni (III) to Ni (II) and CO (III) to CO (II), as
was efficiently detected with an inspection range from 5 pM to illustrated in eqs 9 and 10.
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Figure 12. (a) The synthesis of alk-Ti3C2 and (b) the corresponding electrochemical determination of Hg (II), Cu (II), Pb (II), and Cd (II)
with the concentrations ranging from 0.1 μM to 1.5 μM. Reproduced with permission from ref 100. Copyright 2017 Elsevier. (c) The
modification of GCE with TDN/Ti3C2TX for gliotoxin detection. Reproduced with permission from ref 104. Copyright 2019 Elsevier. (d)
The modification of GCE with Pd@Ti3C2TX composite for the detection of L-Cys. Reproduced with permission from ref 105. Copyright
2019 Royal Society of Chemistry.

Figure 13. (a) Schematic diagram of the Ti3C2TX MXene-based PHOS. (b) Phase shifts at 980 and 1540 nm wavelengths versus pumping
power. (c) Response of the designed PHOS. Reproduced with permission under a Creative Commons Attribution 4.0 International License
(CC BY 4.0) from ref 118. Copyright 2019 De Gruyter. (d) Ti3C2TX MXene-based fiber SPR sensor and RI sensor. (e) The enhanced
performance of fiber RI sensor induced by Ti3C2TX MXene coating. Reproduced with permission from ref 119. Copyright 2020 American
Chemical Society.

NiOOH + C6H12O6 (glucose) → Ni(OH)2 + C6H10O6 (glucolactone) functional groups, correspondingly they exhibit interesting
(9) nonlinear optical characteristics and can withstand a much
higher laser radiation power than graphene.116,117 It has been
CoOOH + 2C6H12O6 (glucose) → 2Co(OH)2 + C6H10O6 (glucolactone)
reported that Ti3C2TX has a wide optical absorption region
(10) covering from visible to short-wave infrared with a high
Ti3C2TX MXene/NiCo LDH provided a 2.5-fold higher photothermal conversion efficiency. Based on this character-
current than NiCo-LDH owing to prompt electron transfer istic, Zuo and co-workers built a photothermal optical sensor
accelerated by Ti3C2TX. Nonenzymatic sugar detection was (PHOS) by adding Ti3C2TX to the Mach−Zehnder interfer-
lately realized by the combination of NiFe-LDH and Ti3C2TX ometer (Figure 13a).118 As shown in Figure 13b,c, the control
(Ti3C2TX/NiFe-LDH) (Table 1).115 efficiency was determined to be 0.19 π mW−1 mm−1 under 980
Optical Sensors. Since MXenes have tunable electronic nm pumping, while the estimated rise and decay times were
structure depending on the number of layers and surface 23.4 and 5 μs, respectively. By depositing Ti3C2TX on optical
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Figure 14. (a) Schematic design of Ti3C2TX-TiO2-based photodetector. (b) UV response of Ti3C2TX film with a thickness of 16 nm in Ar at a
bias of 1 V. (c) The influence of air exposure on the photoresponse of Ti3C2TX film with a thickness of 38 nm. Reproduced with permission
from ref 120. Copyright 2018 American Chemical Society. (d) The charge-transfer mechanism of the photodetector based on Ti3C2TX and
CsPbBr3 in dark and under illumination. (e) I−V curves and (f) response/recovery times of the photodetector based on Ti3C2TX and
CsPbBr3. Reproduced with permission from ref 121. Copyright 2019 John Wiley and Sons.

Figure 15. (a) The device configuration and (b) the response of the Ti3C2-based humidity sensor. Reproduced with permission under a
Creative Commons Attribution 3.0 Unported License (CC BY 3.0) from ref 126. Copyright 2017 Royal Society of Chemistry. (c) The
adsorption of water molecules on Ti3C2/TiO2 composite. (d) Electrical response of the Ti3C2/TiO2 in the presence of different RHs. (e) The
interpretation of sensing mechanism based on the energy-band diagram of Ti3C2/TiO2 composite. Reproduced with permission from ref
130. Copyright 2019 American Chemical Society.

fiber surfaces, the sensitivities of the surface plasmon resonance 14a).120 The light response of Ti3C2TX-TiO2 was attributed to
(SPR) sensor and refractive index (RI) sensor were, the electron transitions in TiO2 induced by UV irradiation.
respectively, improved by 30% and 8 times (Figure 13d).119 The response behavior was reversible in Ar (Figure 14b), yet
The enhanced sensitivity was attributed to the wide optical changed dramatically in ambient air with a rapid current drop
absorption and the large surface area, resulting in enhanced owing to the adsorption/desorption of oxygen on TiO2
interaction between incident light, Ti3C2TX nanosheets, and (Figure 14c); interestingly, when the gas was switched from
target trace biochemical molecules (Figure 13e). air back to Ar, the light response behavior was fully restored
MXene nanosheets are chemically unstable in colloidal state (Figure 14c). Deng and co-workers used Ti3C2TX MXene and
and gradually oxidized to TiO2 starting from the defect sites. 2D CsPbBr3 as electrodes and active materials, respectively, to
According to this principle, Chertopalov and co-workers prepare paper-based flexible photodetectors (PDS) arrays. A
prepared Ti3C2TX-TiO2 composites for UV detection (Figure Schottky barrier at the contact between CsPbBr3 and Ti3C2TX
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Figure 16. (a) The adsorption of H2O on Ti3C2/Ag. Reproduced with permission from ref 134. Copyright 2019 Royal Society of Chemistry.
(b) The adsorption of water molecules on Ti3C2TX/polyelectrolyte multilayers. (c) The sensing mechanism and (d) the humidity response
of Ti3C2TX/polyelectrolyte-based sensor. Reproduced with permission from ref 136. Copyright 2019 American Chemical Society.

was formed due to different work functions (Figure 14d).121 by neutron scattering upon the exposure to water
When the incident light had a higher energy than the bandgap vapor.12,127,128 The average d-spacings of Ti3C2-Mg and
of CsPbBr3, electron−hole pairs were photogenerated and Ti3C2-K were 15 and 11 Å, respectively, and the Mg(H2O)62+
separated rapidly by the local electric field, leading to an cluster was considered the best pillar due to its rigid structure.
improved conductivity. The experimental results showed that The experimental results showed that the sensors had an
upon illumination (7.07 mW mm−2), the photocurrent sharply optimum LOD of ∼0.8% RH and a detectable range of 0−85%
rose to 5.7 μA at the bias of 10 V (Figure 14e). Once the light RH with ∼3% resolution. Alternatively, Yang and co-workers
was turned off, the current immediately dropped back to 1 nA synthesized alkalized Ti3C2TX for humidity sensing.129 The
with the response/recovery time of 48/18 ms (Figure 14f). alkalized Ti3C2TX presented good repeatability at 98% RH
This sensing behavior was mainly attributed to the high quality with the response time of 1 s and the recovery time of 201 s. Li
of the CsPbBr3 crystal, the excellent conductivity of Ti3C2TX, and co-workers prepared the sensing material of Ti3C2/TiO2
and the Schottky junction between Ti3C2TX and CsPbBr3, via an in situ oxidation reaction in KOH solution forming
leading to rapid separation of photogenerated carriers. numerous TiO2 nanowires (thickness of 10−100 nm thick and
Humidity Sensors. Humidity sensors are generally applied length of 500 nm−1 μm) on Ti3C2 surfaces (Figure 15c).130
in a number of traditional fields including meteorology, process The humidity sensor had a detection range of 7%−97% and a
control, automation, agriculture, and food storage as well as the high sensitivity of 1614 pF/% RH (Figure 15d) because of the
emerging fields such as smart home and health care.122 To increased charge density in Ti3C2/TiO2 heterostructures
date, numerous nanomaterials have been adopted as humidity (Figure 15e).131 The sensor was further demonstrated with
sensing materials, among which MXenes have the advantage of the capability of monitoring the fingertip approaching, proving
high conductivity, good hydrophilicity, and abundant surface its potential applications for human-machine interactions and
terminations (e.g., −F and −OH).123,124 As previously robotics. Wang and co-workers synthesized semiconductor/
reported, Ti3C2TX showed hydration over a wide range of metal heterostructure via hydrothermally growing TiOF2
relative humidity (RH).125 Water molecules (H2O) were nanospheres on Ti3C2 TX substrates.132 Owing to the
preferentially adsorbed on vacancies and hydrophilic groups protection of hydrophobic TiOF2 nanospheres, the hetero-
via double and/or single hydrogen bonds. The subsequent structure (TiOF2@Ti3C2TX) showed excellent stability for
water layers were mobilized in a way similar to those in bulk moisture detection. The TiOF2@Ti3C2TX composite exhibited
liquid with hydronium ions (H3O+) partially generated due to the response time and recovery time of 16 and 20 s,
the electric-field-induced ionization. Both H3O+ and the respectively.
hydrolyzed oxygen-containing functional groups on Ti3C2 Since AgNPs have been demonstrated to possess the ability
contributed to ionic conductivity. The resistivity of Ti3C2 to reduce the activation energy required for water adsorption,
film was examined versus humidity (Figure 15a).126 The initial Ti3C2/Ag composites were prepared as humidity sensors
resistance of Ti3C2-based sensor was 243 Ω in dry nitrogen (Figure 16a).133,134 Liu and co-workers assembled 1D AgNWs
(N2); it dramatically changed to 6341 Ω when exposed to a and 2D Ti3C2 MXene via a vacuum-assisted process, producing
RH of 80 ± 5%. Moreover, the device showed reversible a leaf-like structure.135 A sensing range of 0−80% and a
responses in the range of 0.1%−95% RH with a LOD of 0.1% response time of 5 s comparable to that of commercial sensors
RH (Figure 15b).124 As the insertion of cations between were achieved. However, the recovery time reached 80 s. The
MXene interlayers can enhance H2O diffusion, Muckley and humidity response can be further modulated by incorporating
co-workers intercalated Mg2+ and K+ between MXene water-sensitive polymers. An and co-workers layer-by-layer
nanosheets, then measured their resistance and mass changes hybridized poly(diallyldimethylammonium chloride) (PDAC)
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with Ti3C2TX MXene nanosheets and found the conductivity AUTHOR INFORMATION
of Ti3C2TX/PDAC showed strong dependence on the number Corresponding Authors
of Ti3C2TX MXene layers and the content of PDAC.136 In this
Gengzhi Sun − Frontiers Science Center for Flexible
work, the conductivity of three-layer and five-layer films was, Electronics, Xi’an Institute of Flexible Electronics (IFE), and
respectively, 21 S cm−1 and 27 ± 2 S cm−1. As the adsorption Xi’an Institute of Biomedical Materials and Engineering,
time was prolonged from 5 to 15 min, the content of PDAC Northwestern Polytechnical University (NPU), Xi’an
increased from 6.1 wt % to 9.3 wt %, leading to a 46% 710072, P.R. China; Institute of Advanced Materials (IAM),
improvement in humidity sensitivity. In addition, it was found Nanjing Tech University (NanjingTech), Nanjing 211816,
that with the increase of humidity, the distance between P.R. China; School of Materials Science and Engineering,
Ti3C2TX layers was enlarged, thereby increasing the interlayer Henan Polytechnic University, Jiaozuo 454003, P.R. China;
tunnel resistance (Figure 16b−d). orcid.org/0000-0002-8000-8912; Email: iamgzsun@
nwpu.edu.cn
CONCLUSIONS AND OUTLOOK Wei Huang − Frontiers Science Center for Flexible Electronics,
Xi’an Institute of Flexible Electronics (IFE), and Xi’an
To date, single-layer MXenes have been successfully top-down Institute of Biomedical Materials and Engineering,
synthesized via chemical etching and delamination. Benefiting Northwestern Polytechnical University (NPU), Xi’an
from their features of tunable conductivity, rich surface groups, 710072, P.R. China; Institute of Advanced Materials (IAM),
hydrophilicity, mechanical robustness, and optical properties, Nanjing Tech University (NanjingTech), Nanjing 211816,
numerous MXene-based sensors were developed, including P.R. China; Email: [email protected]
mechanical sensors, gas sensors, electrochemical sensors,
optical sensors, humidity sensors, and multifunctional sensors. Authors
In this review, we started with the preparation of MXene Yangyang Pei − Frontiers Science Center for Flexible
nanosheets, and then we introduced the latest development of Electronics, Xi’an Institute of Flexible Electronics (IFE), and
MXene-based sensors and highlighted the underlying sensing Xi’an Institute of Biomedical Materials and Engineering,
Northwestern Polytechnical University (NPU), Xi’an
mechanisms in order to provide the guideline for future
710072, P.R. China
endeavor in designing high performance sensing devices.
Xiaoli Zhang − Frontiers Science Center for Flexible
Although MXenes are considered a versatile 2D material and Electronics, Xi’an Institute of Flexible Electronics (IFE), and
impressive achievements have been accomplished, there are Xi’an Institute of Biomedical Materials and Engineering,
still challenges in utilizing MXenes for sensor applications. Northwestern Polytechnical University (NPU), Xi’an
The synthesis of MXene-based sensing materials in a 710072, P.R. China
controllable manner is still unachievable. For example, it Zengyu Hui − Frontiers Science Center for Flexible Electronics,
remains difficult to prepare MXene nanosheets with particular Xi’an Institute of Flexible Electronics (IFE), and Xi’an
size, defects, surface terminations (e.g., hydroxyl, fluorine, Institute of Biomedical Materials and Engineering,
oxygen, or hydrogen), and their arbitrary spatial distribution. Northwestern Polytechnical University (NPU), Xi’an
The etching of MAX phases unavoidably involves toxic 710072, P.R. China
chemicals and complicated procedures. In addition, due to Jinyuan Zhou − School of Physical Science and Technology,
the low yield, the scalable preparation of MXene nanosheets is Lanzhou University, Lanzhou 730000, P.R. China;
difficult. orcid.org/0000-0003-0284-105X
The interpretation of the interface properties between Xiao Huang − Frontiers Science Center for Flexible Electronics,
MXene nanosheets and other substances, such as surface Xi’an Institute of Flexible Electronics (IFE), and Xi’an
Institute of Biomedical Materials and Engineering,
functional groups, gas molecule, water molecule, and the
Northwestern Polytechnical University (NPU), Xi’an
hybrid phase, needs further investigations. The combination of 710072, P.R. China; orcid.org/0000-0002-0106-7763
experimental investigation (both in situ and ex situ observa-
tion) and theoretical analysis (or prediction) would be a Complete contact information is available at:
promising direction and deserves great endeavors in the future. https://pubs.acs.org/10.1021/acsnano.1c00248
The interferences from different signals (e.g., humidity, gas,
temperature, and strain) lead to inaccurate measurements, Notes
which may be partially resolved by a post-data process. The authors declare no competing financial interest.
Moreover, it is anticipated that the selectivity and sensitivity of
MXene-based sensors could be further improved by surface ACKNOWLEDGMENTS
engineering so as to provide specific adsorption and catalytic This work was supported by the National Natural Science
activity toward a particular molecule.
Last but not least, particular attention should be paid to the Foundation of China (nos. 21975123 and 61704076), the
chemical and thermal stability of MXene nanosheets especially Natural Science Basic Research Program of Shaanxi (no.
in humid environments with the presence of oxygen and high 2020JM-092), Six Talent Peaks Project in Jiangsu Province
temperature. The irreversible oxidation leads to the permanent (no. XCL-024), Postgraduate Research and Practice Innova-
degradation of MXenes, which would be a major obstacle
tion Program of Jiangsu Province (nos. SJCX20_0401 and
hindering MXene-based sensors from practical applications.
More efforts should be paid toward this, except for antioxidant KYCX20_0997), and the Fundamental Research Funds for the
modification and stabilizer hybridization of MXene nanosheets. Central Universities.
4011 https://dx.doi.org/10.1021/acsnano.1c00248
ACS Nano 2021, 15, 3996−4017
ACS Nano www.acsnano.org Review

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