Accepted Manuscript

MXene: An emerging material for sensing and biosensing

Ankita Sinha, Dhanjai, Huimin Zhao, Yujin Huang, Xianbo Lu, Jiping Chen, Rajeev
Jain

PII: S0165-9936(18)30139-0
DOI: 10.1016/j.trac.2018.05.021
Reference: TRAC 15166

To appear in: Trends in Analytical Chemistry

Received Date: 3 April 2018

Revised Date: 29 May 2018
Accepted Date: 29 May 2018

Please cite this article as: A. Sinha, Dhanjai, H. Zhao, Y. Huang, X. Lu, J. Chen, R. Jain, MXene: An
emerging material for sensing and biosensing, Trends in Analytical Chemistry (2018), doi: 10.1016/
j.trac.2018.05.021.

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Graphical Abstract

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MXene: An Emerging Material for Sensing and Biosensing

Ankita Sinhaa, c, †, Dhanjaib, c, †, Huimin Zhaoa*, Yujin Huanga, Xianbo Lu b, Jiping Chenb*
and Rajeev Jainc

a: Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education,

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China), School of Environmental Science and Technology, Dalian University of Technology,
Dalian-116024, PR China

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b: CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of
Chemical Physics, Chinese Academy of Sciences, Dalian-116023, PR China

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c: School of Studies in Chemistry, Jiwaji University, Gwalior-474011, India
(ankita.mica2011@gmail.com)

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*Corresponding author e-mail: zhaohuim@dlut.edu.cn, chenjp@dicp.ac.cn
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†: Authors contributed equally

Outline
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1. Introduction

2. Electronic properties and surface functionalization

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3. MXenes as sensors
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3.1 Electrochemical sensors

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3.2 Soild state gas adsorptive sensors

3.3 Peizoresistive wearable sensors

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3.4 Photoluminescent sensors

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3.5 Other advanced sensors

4. Conclusion and future outlook

5. References

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Abstract

MXene has emerged as an amazing family of two dimensional (2D) layered materials

and drawn great attention from researchers of diverse scientific fields. MXenes are the recent

advancements of materials chemistry which include early transition metal carbides, nitrides

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and carbonitrides produced by exfoliation of selective MAX phases. MAX phase corresponds

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to the general formula Mn+1AXn (n=1, 2, 3) where M represents early d-block transition

metals, A stands for main group sp elements (specifically group 13 and 14) and X is either C

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or N atoms. MXenes have left a prodigious impact on scientific communities with new

technological advancements for a plethora of potential applications in the field of catalysis,

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clean energy, electronics, fuel cells, supercapacitors etc. With high metallic conductivity,
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hydrophilicity, low diffusion barrier, high ion transport properties, biocompatibility, large

surface area and ease of functionalization, the conductive clay MXenes act as fascinating
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interface for designing next generation detection systems exploiting their utilization in
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analytical chemistry. Recent progress in the field of MXenes emphasizing their significant role
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in analytical sensing has been well discussed in this review. Future perspectives with a

motivated research in the field of MXenes based sensors have been focused at the end. The
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underlying goal of this review is to acquaint the readers with the sensing applications of

MXenes and to document the latest advancements made in this area till date with possible
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future prospects of MXenes.

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Keywords: MXene; Sensors; Biosensors; Advanced Material; Titanium Carbide; Sensitivity.

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1. Introduction

Since the discovery of graphene, various two-dimensional (2D) layered materials have

gained attention and extensively studied for multiple scientific applications. These 2D layered

graphene analogues most commonly include layered double hydroxides (LDH), transition metal

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dichalcogenides (TMDs), boron nitride (BN), silicenes and germanene. These materials offer

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exceptional structural/physical/chemical properties which make them highly suitable for

catalysis, optoelectronics, supercapacitors, sensors, energy storage and biomedical applications

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[1-3].

Quiet recently, a new class of 2D layered materials has emerged as graphene analogue which

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are also known as MXenes and include transition metal carbides, nitrides and carbonitrides [4-7].
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These novel MXenes are produced by etching layers of sp elements from their corresponding

three-dimensional (3D) MAX phases which are layered ternary metal carbides, nitrides, or
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carbonitrides [8]. MAX phases correspond to the general formula Mn+1AXn (n=1, 2, 3) where M
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represents early d-block transition metals (Ti, Sc, V, Cr, Ta, Nb, Zr, Mo, Hf), A represents main
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group sp elements (specifically group 13 and 14) and X is either C or N atoms. In general, higher

number of n corresponds to a more stable MXene [4]. More than 60 members of MXene family
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have been discovered which constitute unique properties of ceramic and metals [4, 5].

All the known MAX phases are layered hexagonal with P63/mmc symmetry. Ideally, M
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layers are packed with X atoms between the octahedral sites and Mn+1Xn layers are interleaved
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with layers of A atoms as shown in figure 1a & b [4]. Strong bonding of covalent/metallic/ionic

character is observed in M-X bond whereas M-A layers are weakly bonded possessing pure

metallic nature [4]. Consequently, M-A bond tend to decompose at high temperatures into

Mn+1Xn form which leads to recrystallization and formation of 3D Mn+1Xn rocksalt like structure

[5]. Unlike weak Van der Walls interactions of graphite or TMDs, the MX layers in MAX phases
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are held together by partial ionic bond making the separation of MX layer difficult by other

methods like mechanical exfoliation, ultrasonication or dispersion [2]. However, reports suggest

selective etching of reactive A layers from their MAX phases by treatment with suitable

chemicals without destroying MX layers [7]. The process lead to formation of highly stable

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closely packed Mn+1XnTx layers where Tx represents the surface terminating functional groups

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such as oxygen (O), hydroxyl (–OH) or fluorine (–F) where the thickness of Mn+1XnTx is

dependent on the value of n [4, 7].

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In detail, synthesis of MXene is performed by selective etching of the A layers from the

MAX phases at room temperature. According to methodology, the MAX phase powder is stirred

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in aqueous hydrofluoric acid (HF) for a certain period of time followed by centrifugation and
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several times washing with distilled water till pH reaches between 4 to 6 [4, 5]. Consequently,

loosely packed exfoliated graphite like layered structures are formed and named as MXenes
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(Figure 1c). For example, successful preparation of 2D Ti3C2 was performed by exfoliation of
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Ti3AlC2 in 50% HF at room temperature for 2h. The process undergo as per the following
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reactions [4, 5];

Mn+1AlXn + 3HF = AlF3 + Mn+1Xn + 1:5 H2 ……………………………………….…………(i)

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Mn+1Xn + 2H2O = Mn+1Xn (OH)2 + H2 ………………………………………………………(ii)

Mn+1Xn + 2HF = Mn+1Xn F2+H2……………………………………………………………..(iii)

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Figure 1
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In the above process, the Al atoms are replaced by O, OH or F atoms and subsequently,

interactions between the Mn+1Xn layers become weak making their separation easy. Furthermore,

replacement of Al-M bond through hydrogen or van der Waals bonds allows the facile

delamination of MXene by the ultrasonication of HF treated MAX phases in solvents like

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isopropyl alcohol or methanol. Here, it is important to note that the delaminated MXene are more

stable than graphene sheets which has been observed under electron beam (200 eV) during TEM

experiment [7]. In certain cases, use of strong etchants (Cl2 gas) at elevated temperatures (above

200 ° C) results in the etching of A and M atoms to produce carbide derived carbons [4]. Overall,

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the experimental conditions such as etching times, temperature, particle size of MAX phases and

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HF concentrations need to be optimized for achieving high yield and high quality MXenes.

Layered MXenes offer unique chemical, physical, electrical and ion transport properties

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which promise for a wide range of potential applications in various fields [9-11]. Extensive

research has been carried out on MXenes exploring their utility in catalysis [9, 12-16], sensing

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[9], energy storage devices [17-19] and adsorption studies [9, 20-24] in past five years. Owing to
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their high metallic and narrow band gap semiconducting characteristics, MXenes exhibit intrinsic

advantages of good electrical conductivity which favors their potential application in Li-ion
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batteries and supercapacitor applications [25]. Recently, MXene based sensing and biosensing
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have emerged as a popular trend towards rapid and sensitive screening of different analytes
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exploiting their exciting sensing features [9]. The present review focuses on the unique analytical

features of MXenes and different state-of-the-art detection methodologies for multiple sensing
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applications. Overall, the review provides an overview of the recent efforts in utilizing MXene in

fabricating next generation detection devices.

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2. Electronic properties and surface functionalization

It is clear from the above discussion that in the aqueous environment of HF solutions, the

outer surfaces of the exfoliated MX layers are usually chemically terminated or functionalized

with O, F or OH functional groups [26-29]. This surface functionalization leave significant

impacts on the electronic and ion transport properties of MXenes which are directly correlated to

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their conductivity and heterogenous electron transfer processes occurring at their surfaces.

Therefore, MXenes show variable electronic activity depending upon their functionalization

[26]. For instance, all the pristine MXenes (M2X) are metallic in nature due to the presence of

Fermi energy at d orbitals of transition metal M. On functionalization, some MXenes show

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seminconducting properties [4, 26]. For example, Ti3C2 is a metal while Ti3C2F2 and Ti3C2OH2

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are semiconductors. In most MXenes, the p bands of C or N (X) are below the d bands of M

which are separated by a small band gap. On functionalization, new bands are generated below

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the Fermi energy due to the hybridization between p orbitals of terminating groups with d

orbitals of transition metal M. Furthermore, due to the lower electronegativity, M becomes

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positivity charged very easily by the donation of electrons to X and the terminating groups (F/O).
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This forms the basis of the semiconducting nature of various MXenes such as Sc2CF2, Sc2COH2,

Sc2CO2, Ti2CO2, Zr2CO2 and Hf2CO2 which is due to the shifting of Fermi energies towards
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centre of the gap between d bands of M and p bands of X. It is worth to be noted that metallic to
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semiconducting behavior is also dependant on the transition between T (centered honeycomb)

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and H (honeycomb) phases of MXenes where the difference exists between the atomic stacking

sequences of M atoms [30].

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3. MXenes as sensors

Owing to its multiple unique features, MXene materials have been proved as highly sensitive
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and selective detection platform for sensing applications in spite of their very short journey. This
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section includes MXene based relevant sensing interfaces for a plethora of potential applications

in various fields.

3.1 Electrochemical sensors

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After the extensive application of various carbon nanomaterials, metal oxide nanoparticles

and other layered materials in sensing and biosensing [31-37], MXene is the latest one to be

applied in this area. Besides unique morphology, extraordinary surface chemistry and excellent

conducting properties, biocompatibility is among one of the most prominent features of MXenes

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which make them highly suitable matrix for fabrication of advance biosensing platforms. MXene

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based electrodes have been utilized as effective transducers for immobilization of biological

receptors onto its surface and shown considerable sensing characteristics. Basically, realization

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of direct electron transfer (DET) of enzymes and protein seems difficult due to the deeply rooted

location of their redox active centers [38]. MXenes allow easy immobilization of

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enzymes/protein onto its surface thus acting as a promising support to achieve DET with
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accelerated electrode kinetics, lower detection limits, high sensitivity and selectivity. Moreover,

decoration of metal/metal oxides nanoparticles onto the surface of enzyme immobilized MXene
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interface lead to increase in overall working electrode surface area and decrease in overpotential
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during electroanalysis enhancing the overall catalytic activity of MXene sensors. Nanoparticle-
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MXene hybrid transducer systems help to incorporate the biological receptors (enzymes/protein)

onto the surface of working interface through physical adsorption (drop-casting) method to
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fabricate novel biosensors. Furthermore, MXene biosensors enhance the catalytic performances

of sensing matrix and help enzymes/protein to retain their bioactivity without altering the
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original native conformation. Specifically, enzyme/protein based MXene biosensors have been
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well explored for electrochemical determination of different biomolecules [38-44]. For example,

a typical glucose biosensor was developed by immobilizing glucose oxidase (GOx) onto nafion-

AuNP-MXene nanocomposite over glassy carbon electrode (GCE) [38]. The study suggested a

new way to quantify the irregularities in blood glucose level for point of care diagnostics at ultra

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advance MXene biosensors. As stated above, DET between the redox centers of GOx and

working electrode becomes difficult to be accomplished due to the complex GOx scaffold. The

redox active flavin adenine dinucleotide (FAD) of GOx is deeply protected from prosthetic

protein shells which makes it hard to realize DET of GOx at conventional bare electrodes. In the

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developed biosensing matrix, MXene (Ti3C2Tx) showed high conductivity and improved electron

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transfer between the active redox center (FAD) of GOx and electrode interface. Sensing

performance of the biosensor (GOx-Au-MXene-naf/GCE) was greatly improved in the presence

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of Au nanoparticles which reduced the effect of protective protein shell covering FAD. Further,

it decreased the overpotential towards detection of hydrogen peroxide (H2O2) which was formed

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as a byproduct during glucose oxidation. MXene biosensor reflected a characteristic glucose
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oxidation peak at −0.402 V due to conversion of FAD to FADH2 showing direct

electrochemistry between GOx and fabricated biosensor during glucose oxidation according to
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the following reaction;

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Glucose + GOx (FAD) → Gluconolactone + GOx (FADH2)…………………….……………(1)

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GOx (FADH2) + O2→ GOx (FAD) + H2O2 …………………………..………….……………(2)

Negatively charged nafion reduced the permeability of negatively charged interfering molecules
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and thus improved the selectivity of the MXene biosensor. The fabricated biosensor exhibited

excellent sensing performance for detection of glucose using amperometry with high sensitivity
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of 4.2 µA mM−1 cm−2 and excellent reproducibility. Further, the stability of GOx-Au-MXene-
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naf/GCE biosensor was investigated by monitoring the response current for 3.0 mM glucose

concentration which retained 93% of its initial response current even after two months of

storage. Similarly, hemoglobin (Hb) immobilized organ like Ti3C2-MXene was explored for its

mediator free biosensing activity towards H2O2 [39] and NaNO2 [40]. In both cases, proposed

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methodology followed the preparation of Hb-naf-MXene modified GCE sensor which was

successfully applied to study the direct electrochemistry between Hb and the working electrode.

For illustration, the biosensor (Hb-naf-MXene/GCE) showed well defined quasi reversible redox

peaks in 0.1M PBS (Figure 2a) which was ascribed to the electron transfer between Fe (III) and

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Fe (II) sites of Hb and the MXene modified underlying electrode interface. Specifically, for

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H2O2, MXene biosensor exhibited a typical electrochemical sensing strategy as per the following

mechanism [39];

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Hb (Fe III) + e- → Hb (Fe II)……………………………………………………………………(3)

Hb (Fe II) + H2O2 + 2H+ → Hb (Fe III) + 2H2O……………………………………….…….…(4)

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The long-term stability of the biosensor contributed to its high biocompatibility which provided a
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favorable microenvironment for Hb to retain its bioactivity. The catalytic performance of Hb-

naf-MXene/GCE was analyzed at -0.35 V using amperometry (Figure 2b).

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Figure 2
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Likewise, for reduction of NO2-, fabricated Mxene biosensor showed low detection limit of 0.12
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µM in the wide linear range from 0.5 µM- 11.8 mM and followed a multistep strategy which has

been demonstrated as follows [40];

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Hb (FeIII) + e- →Hb (FeII)…………………………………………………………………(5)

Hb (FeII) + HNO2 + H+ → [Hb (FeII) – NO] + + H2O……………………………………..(6)

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[Hb(FeII) – NO]+ + e- → [Hb(FeII) – NO] ͦ ………………………………….…………….(7)

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[Hb(FeII) – NO] ͦ + e- → [Hb(FeII) – NO]- …………………………………..….……….(8)

[Hb(FeII) – NO]- + H+ → Hb(FeII) + HNO…………………………………..….….…….(9)

2HNO → N2O + H2O………………………….……………………………..….….…….(10)

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The specialty of the sensor lied in the fact that Ti3C2-MXene provided a compatible

microenvironment to the bioreceptor molecule (here Hb) and enhanced the effective surface area

of the immobilized surface to increase the rate of collision between the substrate and Hb. Real

time application of naf-Hb-MXene/GCE for detection of spiked NO2- in environmental water

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samples showed high potential of MXene materials in routine analytical procedures for

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environmental safety and pollution affairs. Furthermore, decoration of TiO2 nanoparticles on

organ like Ti3C2-MXene biosensor was successfully performed and exploited for H2O2 detection

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with high sensitivity of 447.3 µAmM-1 cm-2 and detection limit of 14 nM [41]. Studies showing

the effect of Mxene exposure to redox potentials (anodic/cathodic) were highly appreciable for

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electrochemical sensing. In a recent study, Ti3C2Tx-PtNPs/GCE was fabricated to study different
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biomolecules such as ascorbic acid (AA), dopamine (DA), uric acid (UA), acetaminophen

(APAP) including H2O2 [43]. The electroactivity of Ti3C2Tx/GCE was greatly improved by
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PtNPs and biomolecules were detected with high sensitivities and low detection limits.
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Reduction of H2O2 was observed at more positive potential (0V) in comparison to Ti3C2Tx
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modified GCE (−160 mV). Moreover, AA, DA, UA, APAP were oxidized at a potential higher

than +250 mV. Furthermore, in another example, application of large anodic potential (+200
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mV) to Ti3C2Fx resulted in the oxidation of its outer surface and utilized for oxidation of NADH

[44]. Oxidation of Ti3C2Fx left behind the TiO2 layers which were subsequently dissolved by F-
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ions making MXene less electroactive than pristine form. Electrochemical assay suggested lower
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oxidation current for NADH at o-Ti3C2Fx as compared to pristine Ti3C2Fx. Furthermore, sensing

of H2O2 was performed by exposing large cathodic potential (-500 mV) to Ti3C2Fx using

chronoamperometry. The study showed great potential applicability of MXene based biosensors

which show dehydrogenase and oxidase like activity for efficient electrochemical sensing of

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NADH and H2O2 respectively. Further it drives great motivation for design and fabrication of

MXene biosensors for other small biomolecules and macromolecules.

Apart from their high sensing applicability for biomolecules, MXenes have shown

promising application for environmental and agricultural safety. For instance, Ti3C2 MXene was

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explored as a sensible matrix for immobilization of tyrosinase (Tyr) enzyme which was used for

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the detection of phenol [45]. The prepared MXene based enzymatic biosensor acted as highly

efficient interface for the oxidation of phenol to corresponding o-quinone which was studied

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using amperometry. The biosensor showed high sensitivity towards phenol which was attributed

to the highly compatible MXene surface which helped tyrosinase to retain its activity even after

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its immobilization. The biosensor retained 89 % of its initial response when measured for its
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stability after six weeks towards 1.5 µM phenol suggesting long term stability. Further, the real

time analysis of water samples suggested the fabrication of MXene biosensors for frequent
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environmental monitoring and biomedical applications. Moreover, an alkaline (KOH)

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intercalated Ti3C2-MXene was prepared and utilized for sensing of toxic heavy metals using
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square wave stripping voltammetry (SWASV) [46]. Electroactivity of alk-Ti3C2/GCE was

compared with pristine Ti3C2/GCE sensor towards detection of Cd2+, Pb2+, Cu2+ and Hg2+. Well
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defined redox peaks were obtained for the target heavy metals under optimized conditions with

detection limits of 98 nM, 41 nM, 32 nM 130 nM for Cd2+, Pb2+, Cu2+ and Hg2+ respectively.
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Presence of [Ti-O]-H+ and [Ti-O]-K+ moieties in alk-Ti3C2 promoted the cation exchange and
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accelerated the adsorption and reduction of heavy metal ions into metallic form during stripping

analysis. Substitution of stronger electronegative F- ions with hydroxyl groups after alkaline

treatment of Ti3C2 resulted into enhanced hydrophilicity with small surface dipole and thus

showed high conductivity for electron transfer processes of heavy metals. The alkTi3C2-

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MXene/GCE sensor was stored at 4 ͦC for three weeks to check its stability. The stripping peak

currents for Cd2+, Pb2+, Cu2+ and Hg2+ retained 90.5%, 94.3%, 96.3% and 93.8% of their initial

response respectively which demonstrated long term stability of the prepared sensor. Further, a

Ti3C2Tx/GCE sensor was prepared for the detection of bromate ions (BrO3−) which are

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considered as a mojor contamiant of drinking water. The sensor showed unique electrocatalytic

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properties towards BrO3− reduction with a detection limit of 41 nM. The formation of TiO2

crystals at the surface of MXene sensor confirmed the reduction of BrO3− ions which has been

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shown by the following equation [47];

BrO3− + 3Ti2+ + 6H+ → Br− + 3Ti4+ + 3H2O……………………………….……….…..(11)

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These studies [46, 47] revealed the promising applications of MXene sensors in environmental
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safety operations. Mxene biosensors have been successfully applied in agriculture for pesticide
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detection. For example, an amperometric biosensor based on acetocholinesterase (AChE)

enzyme immobilized Ti3C2Tx nanosheets was fabricated for sensitive and rapid screening of
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organophosphate pesticide malathion [48]. Low detection limit, high reproducibility, excellent
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stability and anti-interference ability were shown by the developed sensor towards malathion

oxidation suggesting novel platform for pesticide monitoring. After ten days of storage, no
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obvious change in the biosensor activity was observed however, after 38 days of storage period,

the sensor retained 85.39% of its initial current response towards malathion detection. With high
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biocompatibility and conducting surface of the MXene biosensor (AChE-chitosan-

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Ti3C2Tx/GCE), a highly suitable detection strategy was developed which could be extended to

other class of pesticides including herbicides, insecticides, fungicides etc. that cause potential

toxicity to human and other species. Detection of malathion in water samples with high

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recoveries (95.0%-105.0%) justified the analytical applicability of MXene materials for

agricultural analysis and environment safety.

In addition, potential applicability of MXene towards fabrication of field effect transistor

(FET) sensor was justified by its utilization as an efficient probe for monitoring dopamine (DA)

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in spiked hippocampal neurons [49]. The conductance of Ti3C2Tx-Mxene FET sensor was

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evaluated by ultrathin MXene micropatterns and different gating controls. The MXene sensor

acted as an n-type FET when gate voltage was above +0.3 V and as p-type FET when gate

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potential level was below +0.3 V. The apparent field effect response to front gate modulation and

the semiconductive characterizations enable the effective implication of MXene for biosensing

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applications. The π-π interactions between DA and functionalized surface of MXene led to the
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efficient sensing of DA. In detail, DA molecules interacted with the terminating groups of

MXene which increased the number of holes and enhanced the conductivity of the sensor.
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Further, the MXene micropatterns allowed the calcium imaging for evaluating neural activity
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which was simultaneously conducted and compared with results obtained by electrical
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measurements at MXene–FET.

3.2 Soild state gas adsorptive sensors

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Apart from electrochemical biosensors, MXene have driven an impressive research in gas

sensing applications. Determination of volatile organic compounds (VOCs) at ultratrace level

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(ppb) is highly crucial for pollution analysis, detection of toxic gases and therapeutic breath
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analysis for early identification of many diseases. For example, detection of ammonia is highly

essential to diagnose peptic ulcers caused by H. pylori and also to detect lung disorders.

Likewise, positive detection of acetone in the breath of a patient indicates the early symptoms of

diabetes. Mxene materials have been considered as solid state gas sensors with low electrical

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noise and well designed to detect these gaseous molecules with strong signal intensity, high

manufacturing substrate flexibility and portability. In a typical study, gas sensing performance of

Ti3C2OH2 MXene was studied over gases like acetone (CH3COCH3), ethanol (C2H5OH),

ammonia (NH3), propanal (C2H5CHO), nitrogen oxide (NO2) and sulfur dioxide (SO2) at room

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temperature. The Ti3C2OH2 MXene sensor displayed a positive change in the resistance of the

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sensing channel over absorption of gases. Mxene sensor outperform other semiconducting

sensors for detection of gases as in the later the sensing response varies depending on the

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electron-donating/accepting properties of gases and on the charge carrier (p or n type) of the

sensing channel [50]. In another study, monolayer Ti2CO2 MXene was prepared which acted as

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an efficient base for NH3 sensing (Figure 3a). Adsorption of various gases such as NH3, H2, CH4,
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CH3COCH3, CO2, N2, NO2 and O2 on Ti2CO2 surface was investigated to exploit its potential

application as gas sensor. However, adsorption energies of other gases except NH3 were slightly
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affected on application of biaxial strain (0-4%) on Ti2CO2 due to their weak interactions (Figure
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3b). A significant change in the adsorption energy of Mxene was observed with operating biaxial
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strain to capture NH3 molecules on its surface which formed the basis of high selectivity of

Ti2CO2 towards NH3. The electronic interactions of NH3 with Mxene resulted in the orbital
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overlap and large charge transfer of 0.174 electrons. Furthermore, conductivity of MXene

interface was considerably enhanced after adsorption of NH3 under strain suggesting strong
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interaction and high sensitivity towards NH3 which could further be increased with increasing
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strain. However, desorption was possible by removing strain from Ti2CO2 thus making the

Mxene as a strong platform for NH3 storage, capture and determination [51]. Justifying the

concept, Mxene materials were further proved as a strong detection platform towards NH3 with

high regenerating ability by reversible release and capture of the gas through control on the

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charge state of the system [52]. Introduction of two extra electrons to ZrCO2 resulted in the

release of NH3 from MXene film and conversion of the process of chemisorption to

physisorption. Interestingly, it is important to note that the adsorption induced charge transfer

often affect the resistivity of the sensing device (here MXene film) and considered as a marker

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for detection of gaseous molecules [53]. For example, strong adsorption of polarized gases

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(ethanol, methanol, acetone and NH3) with the functionalized active sites/defects of p type

semiconductor Ti3C2Tx resulted in the enhancement of resistance within Ti3C2Tx film. In the case

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of NH3, adsorption of the gas with functionalized groups of Ti3C2Tx such as O- or OH- led to

generation of electrons according to equations 12 and 13 which minimized the concentration of

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charge carrier on MXene film and thus increased the resistance of the device [53]. Possible
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mechanism of NH3 sensing mechanism at MXene surface has been illustrated in figure 3c.

2NH3 + 3O- → N2+ 3H2O + 3e-………………………………………………………………. (12)

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NH3 +OH- →NH2 + H2O + e- ……………………………………………………………….... (13)

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With large adsorption energy, NH3 was easily adsorbed on the defect sites of Ti3C2Tx MXene
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than other gaseous molecules suggesting MXene as a promising interface for gas sensing studies.

Figure 3
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3.3 Peizoresistive wearable sensors

In recent times, advance sensing approaches often include wearable nanoelectronics which
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have gained inexplicable attention for monitoring various health related activities such as
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physical stimuli, weak pressure and physiological signals. However, the system needs to possess

large stretchability, high gauge factors (GF) and should be able to access a broad range of strain

to meet with the prospects of highly sensitive design of device conformation. Interestingly,

recent reports suggest the fabrication of ultrathin MXene nanocomposite materials which have

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shown high sensitivity (GF~772.6) and tunable sensing range (30%-130% strain). These

properties enabled MXenes to be used as highly advanced platform for detection of phonations

and substantial movements like walking, jumping, running or other human activities like

coughing, joint bending etc. [54, 55]. For example, Ti3C2Tx MXene nanocomposite with single

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walled carbon nanotubes (SWCNTs) was prepared through layer by layer (LBL) spray coating

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technique and utilized as a strain sensor with detection limit as low as 0.1% [54]. The

nanocomposite strain sensor (Ti3C2Tx/CNTs) was utilized as skin attachable wearable devices for

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real time applications like capturing physiological signal and motion monitoring. For example,

Ti3C2Tx/CNTs sensor identified skin stretching over human throat while speaking carbon, sensor

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and MXene several times and generated considerable peaks as a function of time (figure 4a).
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Furthermore, sensor mounting to knee joints accessed the motion behavior of human in terms of

running, walking and jumping by significant change in its resistance with high signal-to-noise
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ratios repeatedly as shown in figure 4b.

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Figure 4
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The mechanism followed the tunneling distances between MXene layers and interconnected

CNTs which change their overlapping areas and distances when external pressure is applied. As
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the applied pressure can be monitored by the resistivity change originated from the changed

interlayer distance, the peizoresistance of the MXene nanocomposite sensor was studied under
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applied strain from 1%-80% suggesting an increase in resistance with substantial enhancement
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in applied strain. Basically, a peizoresistive sensor is a form of pressure sensor which converts

the external pressure into resistance signal. Recently, a peizoresistive sensor based on Ti3C2

MXene was developed in which the distance between two neighboring MXene interlayers was

decreased when external pressure was applied which reduced the resistance of the sensor [55].

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The fabricated sensor was applied to various locations of human body such as eye corner, cheek,

throat etc to monitor the physical stimuli such as eye blinking, cheek bulging and throat

swallowing. Furthermore, the knee bending release movement was also monitored through

change in current over the function of time. For increased portability, the sensor was connected

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to bluetooth device which converted the current signals into wireless electromagnetic radiations

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with high conductivity. Thus, MXene sensor displayed high stability in detecting subtle human

activities and other weak pressure with high sensitivity. The study opened new way for the

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potential exploitation of MXenes in portable wearable sensing devices in healthcare monitoring

and human behavioral analysis.

3.4 Photoluminescent sensors

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Photoluminescence is an effective technique which have often employed in optical,

biomedical and cellular imaging areas. Generally, low photoluminescence of 2D MXenes in

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aqueous medium restricts their application in such fields. However, recent advancements in
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materials sciences have made it possible to construct highly sensitive optical MXene based
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quantum dots (MQDs) for bio-imaging applications [56]. The small band gaps of Ti3C2TX (OH:

0.05 eV and F: 0.1 eV) enable the enlargement of their bandgap through quantum effects and
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help in achieving strong photoluminescence emission. By a facile hydrothermal treatment, Ti3C2-

MQDs were prepared at 100ºC, 120ºC and 150ºC designated as MQDs-100, MQDs-120 and
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MQDs-150 respectively. MQDs-100 and MQDs-120 were applied as a biocompatible multicolor

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imaging probe for photoluminescent detection of RAW264.7 cell lines suggesting novel

applications of MXene materials in optical sensing. Further, the study suggested high

biocompatibility of MQDs for sustained viability of cells. High temperature MQDs-150 were

used to detect Zn2+ ions through luminescence quenching mechanism generated through the

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amorphous nature of as prepared MQDs. In a recent study, an intracellular photoluminescent

ratiometric pH sensor was developed using Ti3C2-MQDs for detection of cell metabolism [57].

MCF-7 cells were taken as target and Ti3C2-MQDs exhibited excitation wavelength due to size

dependant inter-band transition of carriers and surface defect sites. A pH-dependent blue

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photoluminescent signal with a quantum yield of 7.13% was obtained and Ti3C2-MQDs were

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developed as a ratiometric photoluminescence probe to monitor the intracellular pH of the target.

In addition, Ti3C2Tx was used as electroluminescent (ECL) sensor for the detection of nucleotide

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mismatch in human urine samples [58]. The Ti3C2 based solid state ECL sensor was prepared on

GCE where Ti3C2Tx facilitated the immobilization of Ru(bpy)3/2+ on the electrode surface. The

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MXene sensor was investigated using tripropylamine (TPA) as a representative ECL co-reactant.
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Practical applicability of the sensor for p53 gene single nucleotide mismatch detection showed

high utility of MXene materials in cancer diagnosis and biomedical applications.

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3.5 Other advanced sensors

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Owing to unique metallic characteristics, MXene materials have shown great potential in
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terahertz (THz) sensing. THz waves penetrate easily through most non-metallic materials which

make them ideally suitable for imaging and onsite screening applications. In a typical study,
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potential of MXenes as THz detecting materials was systematically studied by performing

density functional theory (DFT) calculations on Ti3C2 [59]. In particular, THz optical properties,
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the electronic band structures and the thermoelectric figure of merit (ZT) of monolayer and
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stacked Ti3C2Tx were extensively studied (Figure 5). Results suggested excellent light extinction

and optical absorption flakes in the THz range (0.0012–0.012 eV) was observed in Ti3C2

regardless of its stacking conformation. However, with feasible production process and great

optical absorption capacity, stacked Ti3C2-MXenes were found more suitable to achieve

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reasonable sensitivity as THz adsorption material compared to monolayer Ti3C2. Furthermore,

despite larger THz absorption coefficient of stacked graphene flakes than that of stacked Ti3C2

flakes, the stacked Ti3C2-MXene exhibited superior THz absorption than stacked graphene

flakes. It can be ascribed to the higher electronic density of states of Ti3C2 around the Fermi

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energy level in contrast to the electronic states in stacked graphene flakes. Thermoelectric

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calculations suggested a high ZT value for stacked Ti3C2 which is sufficiently enough to be

applied in THz detectors. Such extraordinary features of MXene hold great promise for their

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application in fabricating THz sensing devices including terahertz bolometers and

photothermoelectric detectors.

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Figure 5
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Further, a MXene (Ti3C2Tx) based ultra-advance sensing system namely surface enhanced

Raman spectroscopy (SERS) has been developed which enhances the Raman signals of
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molecules adsorbed on the SERS substrate [60]. Enhancement in Raman signal can be ascribed
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to the electromagnetic and chemical mechanisms. However, SERS substrates depend on

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plasmonic effects in electromagnetic hotspots and highly concentrated charges originating from

surface roughness. In a recent work, a cost effective air-gun, spray-coating method was used for
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fabricating MXene (Ti3C2Tx) SERS substrate for Raman signal enhancement of dye Rhodamine

6G. According to the mechanism, SERS occurred at the hotspots due to the interband transition
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of the functional groups of MXene to the vacant energy states followed by a charge transfer to
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the adsorbed dye Rhodamine 6G. Subsequently, a relaxation caused emission of photons which

were detected as Raman scattering. The synergy between electromagnetic and chemical

enhancements of Ti3C2Tx substrates showed the high possibilities of MXenes in biochemical

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molecular sensing using SERS sensors. Ti3C2Tx demonstrated SERS effect in aqueous colloidal

solutions of Rhodamine 6G at 10-7 M concentration.

4. Conclusion and future outlook

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Despite very short life span, MXenes have gained considerable popularity due to their unique

layered morphology and exotic metallic/catalytic properties. Sensing strategies based on the use

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of MXene materials have been considered as highly advanced detection schemes in multiple

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areas including health, environment, medicine etc. The long term stability of the developed

MXene sensors/biosensors offers high reproducibility of results over long period of time which

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could be highly beneficial to implement these sensors for various diagnostic purposes. However,
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titanium carbide is the only explored MXene in the field of sensing as the reports on other

transition metal MXene based detection systems are very rare. Considering amazing sensing
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features of the material, the current situation demands extensive scientific efforts to exploit other

transition metal based MXenes in sensing technology. Although few reports on electrochemical
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enzymatic MXene biosensors for small biomolecules are available, there is a great need to
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further develop other significant biosensing platforms. Large surface area and high
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biocompatibility of MXenes drive great motivation to design advance nano(bio)hybrid systems

with bioreceptors like aptamers (DNA/miRNA), antigen-antibody (Ag-Ab), whole cells, protein
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and enzymes which can allow facile immobilization of biomolecules onto its surface to act as
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sensitive detection interface. Such advancements in the design of MXene biosensors will lead to

develop suitable state-of-the-art detection methodologies using techniques such as fluorescence,

luminescence, colorimetry and of course electrochemical for highly selective detection of various

biomarkers for early disease identification and point-of-care diagnostic applications. However,

achieving stability and desired signal to noise ratio for such sensors are of great challenge.

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Fabrication of MXene based electrodes for electrochemical fuel cells is also an interesting area

for generating high power densities in energy storage devices [61]. Furthermore, developing

MXene based efficient adsorption interface for highly reactive gases such as H2S and NO2 and

gases with low adsorption energies such as acetone is an interesting task to be focused on.

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Development of wearable electronics for room temperature gas sensing will contribute greatly to

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various healthcare diagnostics and environmental applications. In addition, designing new

MXene based skin inspired sensors other than titanium carbide with large tunable strain, high

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sensitivity, high stretchability and low device dimension to be easily integrated into wearable

nanoelectronics is highly challenging. Advancements in wearable strain sensors will lead to

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detect ultra weak pressure such as artery pulses or other low strain physical stimuli. Mechanism
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optimization of such wearable strain sensors will be highly beneficial for studying human

motion, robotic systems and prosthetic devices. High optical absorbance of MXene in THz range
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directs its efficient use in bolometric sensors, photothermoelectric devices, p-n junction diode
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systems, pyroelectric sensors and THz antennas for various security and chemical/medical
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diagnostic purposes. However, developing new MXene based THz sensors with ultrahigh

sensitivity needs persistent efforts which still remains as a great challenge. Good optical
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properties and high biocompatibility of MQDs exhibited their effective utilization in cellular

imaging for biomedical applications. However, cytotoxicity of MXene materials is a vital topic
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to be addressed before their commercial implementation. The cytotoxic effects of MXenes are
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considered to be higher for cancerous cells and are said to produce highly toxic reactive oxygen

species (ROS) during oxidative stress [62]. Lack of the knowledge about the biological activities

of MXenes seeks extensive research and development for their applications in bioscience and

drug-delivery systems. Moreover, there is a lot of possibilities for further improvement to

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fabricate MXene based advanced SERS devices for signal enhancement and detection of various

molecules [60]. Primarily, it can be achieved through optimizing the synthesis conditions for the

production of substrate materials, having control on substrate deposition and finally by tuning

their electromagnetic and chemical properties.

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Polar solvents generally meet with the criteria of preparing good dispersion solutions of

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MXenes owing to their somewhat similar behavior with the polar terminating groups in MXenes

which provides a high strength of nonspecific dispersion interactions [63]. Based on this fact,

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dispersion stability can extend the functional applications of MXene such as 3D folding or

producing novel MXene nanohybrids with polymer/other layer materials/carbon nanomaterials

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for fabricating more advanced sensing devices for a number of applications. Overall, MXene
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materials hold multiple promising applications in various sectors of technology and generated a

great enthusiasm towards their exploitation as next generation detection devices. Thus, we
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anticipate an impressive research to be carried out in this rising area in near future with high
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detection sensitivities.
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Notes

The authors declare no competing financial interest.

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Acknowledgement

This work was supported by Chinese Academy of Sciences (CAS) through President’s
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International Fellowship Initiative for Postdoctoral Researcher Dhanjai (2015PM002), the

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National Natural Science Foundation of China (No. 21777012), the Program of Introducing

Talents of Discipline to Universities (B13012) and the Program for Changjiang Scholars and

Innovative Research Team in University (IRT_13R05).

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Table 1: MXene based electrochemical sensors

MXene Sensor Analyte Detection method Detection limit Detection range Detection References

Potential

GOx-Au-MXene- Glucose Amperometry 5.9 µM 0.1–18 mM −0.40 V 38

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naf/GCE

Hb-naf-MXene/GCE H2O2 Amperometry 0.02 µM 0.1–260 µM −0.35 V 39

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Hb-naf-MXene/GCE NO2- Amperometry 0.12 µM 0.5 µM- 11.8 mM −0.69 V 40

TiO2-Hb-naf- H2O2 Amperometry 14.0 nM 0.1–380 µM −0.35 V 41

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MXene/GCE

Hb-MXene-GO/Au H2O2 DPV 1.95 µM 2 µM-1 mM -0.08 42

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MXene-PtNP/GCE H2O2 Amperometry 448 nM 490 µM - 53.6 mM 0V 43

MXene-PtNP/GCE AA, DPV 0.25 µM, Upto 750 µM > + 250 V 43

DA, 0.26 µM,

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UA, 0.12 µM,

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APAP 0.13 µM,

MXene/GCE H2O2 Chronoamperometry 0.7 nM - −0.5 V 44

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Tyr-MXene-chi/GCE Phenol Amperometry 12 nM 0.05-15.5 µM -0.04 V 45

alk-MXene/GCE Cd2+, SWADSV 98 nM, 0.1–1.5 µM -1.2 V (deposition 46

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Pb2+, 41 nM, potential)

Cu2+, 32 nM,
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Hg2+ 130 nM
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MXene/GCE BrO3- DPV 41 nM 50 nM–5 µM ~0.60-0.55 V 47

AChE-Chi- Malathion DPV 0.3 × 10−14 M 1×10−14-1×10−8M +0.65 V 48

MXene/GCE

MXene-FET DA FET 100×10−9 M 100×10−9-50×10−6 M +0.3 V (p type 49

FET)

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Figure 1: (a) Illustration of etching of A layers from corresponding MAX phases [4], (b)
Systematic process of preparation of graphite like 2D MXenes [5], (c) Scanning electron
micrograph of layered 2D MXene [41]. Reprinted with permission from references [4], [5] and
[41].

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Figure 2: (a) Cyclic voltammetric behavior and (b) amperometric response of Hb-naf-
MXene/GCE biosensor with increasing concentration of H2O2 -0.35 V [39]. Reprinted with
permission from reference [39].

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Figure 3: (a) Ti2CO2 MXene based sensor for NH3 detection [51], (b) adsorption energies of
different gases at MXene surface [51], (c) Schematic sensing mechanism of NH3 at Ti3C2
MXene [53]. Reprinted with permission from reference [51] and [53].

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Figure 4: MXene-CNTs nanocomposite based peizoresistive strain sensor for phonation and
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substantial movement detection; (a) photograph of a Ti3C2Tx-MXene/CNT strain sensor attached
to the throat of a person, (b-d) responsive curves recorded while speaking “carbon”, “sensor”,
and “MXene”, (e) photograph of the sensor attached to the human knee, (f−h) resistance
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responses of the sensor in detecting human leg movement: walking, running, and jumping, [54].
Reprinted with permission from reference [54].
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Figure 5: Optical absorption spectra of (a) monolayer and (b) stacked Ti3C2-MXene flakes in
THz range, (c) comparison of electronic density of monolayer and stacked Ti3C2 flakes with
stacked graphene flakes (green dashed line), (d) ZT spectra of Ti3C2 flakes, (e) Thermoelectric
characterization of a THz sensor [59], Reprinted with permission from reference [59].

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Highlights

• MXenes: early transition metal carbides, nitrides and carbonitrides with unique layered

morphology.

• Emerging new generation platform for sensing and biosensing.

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• MXene based detection devices other than titanium (Ti) are very rare.

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• Exploitation of new MXene materials in sensing technology is highly anticipated.

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