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Abbreviation (ISO4): Prog Chem      Editor in chief: Jincai ZHAO

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Progress in Chemistry >

2024 , Vol. 36 >Issue 8: 1174 - 1185

DOI: https://doi.org/10.7536/PC231215

Review

In Situ Transformation and Application of MXene

  • Yunshuo Zhang ,
  • Feifei Lin ,
  • Yuzhe Chen ,
  • Ning Ding ,
  • Yulan Wei ,
  • Weiwei Zhao , *
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  • State Key Laboratory of Organic Electronics and Information Displays, Institute of Advanced Materials, Nanjing University of Posts & Telecommunications, Nanjing 210023, China
*e-mail:

Received date: 2024-01-04

  Revised date: 2024-03-14

  Online published: 2024-07-01

Supported by

National Natural Science Foundation of China(62174086)

National Natural Science Foundation of China(62474096)

Outstanding Youth Foundation of Jiangsu Province(BK20240139)

Qinglan Project of Jiangsu Province of China, Postgraduate Research & Practice Innovation Program of Jiangsu Province(SJCX22_0253)

National Science and Technology Innovation Training Program(202310293156E)

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Abstract

MXene is a new class of two-dimensional transition metal carbides and nitrides which serves as a versatile and promising material with a wide range of applications in various fields.Layered MXene has abundant surface end-group functional groups(−F,−O and−OH)and a wide range of compatibility with second-phase materials,showing great potential in the construction of multi-functional,high-performance hybrid materials.Research has found that Ti3C2MXene nanosheets have a disadvantage of easy interlayer stacking during use,which is detrimental to ion/electron transport.The in-situ transformation of MXene provides a new approach to address this issue.During the in-situ transformation process of MXene materials,the loading of the second-phase material is controllable and can effectively suppress the interlayer stacking effect of MXene nanosheets.At the same time,by selecting and controlling the second-phase material,it is possible to achieve the directional construction of multifunctional,high-performance hybrid materials.The in-situ transformed hybrid materials can integrate the large specific surface area,metallic conductivity,high active sites of MXene,and the intrinsic properties of the selected second-phase material.Recently,there has been rapid development in the preparation and application of composite materials based on Ti3C2MXene derivatives,showcasing extensive research prospects in the fields of energy storage,catalysis,sensing,and more.Taking Ti3C2as an example,this article summarizes the preparation and transformation mechanisms of MXene-based in-situ converted hybrid materials(in-situ derived,metal ion hybridization,and MOF material hybridization).It also summarizes the applications of MXene hybrid materials in energy storage(lithium-sulfur batteries,supercapacitors,and hydrogen storage),sensors,and catalysis.The article points out the unresolved issues in MXene in-situ transformation research and outlines the future development directions for scientific research.It hopes to provide new research ideas for scholars in this field and contribute to the development of nanomaterials with functional properties 。

Contents

1 Introduction

2 In-situ transformation of MXene for hybrid materials

2.1 In-situ transformation of MXene

2.2 In-situ reaction of metal ions on the surface of MXene

2.3 Assembly of MOF with MXene

3 Application of MXene derived nanocomposites

3.1 Energy storage

3.2 Sensor

3.3 Catalysis

4 Summary and outlook

Key words： MXene; in-situ transformation; nanomaterials; catalysis; energy storage; sensor

Cite this article

Yunshuo Zhang , Feifei Lin , Yuzhe Chen , Ning Ding , Yulan Wei , Weiwei Zhao . In Situ Transformation and Application of MXene[J]. Progress in Chemistry, 2024 , 36(8) : 1174 -1185 . DOI: 10.7536/PC231215

1 Introduction

MXene is a class of two-dimensional transition metal carbides,nitrides,or carbonitrides with the formula Mn+1XnTx,where M is a transition metal and X is C or N,Txrepresents—OH,—F,and—O surface groups[1⇓~3]。 As an emerging two-dimensional nanomaterial,it can be prepared by selective etching of the A-layer(mostly IIIA and IVA elements)in the MAX phase[4]。 Since Ti3C2MXene materials were first reported in 2011,they have attracted much attention because of their high conductivity,large specific surface area,unique layered structure,abundant surface active sites and excellent chemical stability,showing great potential in ion batteries,supercapacitors,sensing,catalysis and other fields[5][6][7][8][9]。
At present,the research focuses on the preparation and application of accordion-like multilayer MXene(m-MXene)and its two-dimensional ultrathin MXene nanosheets(u-MXene)formed after further exfoliation[10,11][12]。 After selective etching of the a layer in the MAX phase,m-MXene exhibits a folded or layered structure with higher mechanical strength and conductivity[13]。 Because of its unique three-dimensional structure,it is possible to realize the construction of three-dimensional composites based on m-MXene.MXene nanosheets usually refer to the single-layer MXene nanosheets exfoliated from the M-MXene bulk by chemical exfoliation or mechanical exfoliation in the laboratory.These nanosheets have large specific surface area and high active site density,and have a wide range of applications in catalysis and electrochemistry[14,15]。 the layered structure of MXene and The abundant terminal groups(—F,—O and—OH)on its surface make it widely compatible with second phase materials and allow for performance tuning[16]。 However,studies have shown that MXene nanosheets are prone to layer-by-layer stacking effect in the application process,which greatly limits the electron transport,limits the conductivity of the material in the actual use process,and reduces the actual application performance of MXene materials[17,18]。 the in-situ conversion of MXene provides a new way to solve this kind of problem.in the process of in-situ transformation of MXene materials,the loading of the second phase material is controllable and can effectively inhibit the interlayer stacking effect of MXene nanosheets.At the same time,multifunctional and high-performance hybrid materials can be directionally constructed by selecting and regulating the second phase materials.the hybrid materials after in situ conversion can combine the large specific surface area,metallic conductivity,high active sites of MXene and the intrinsic properties of the selected second phase materials.On the other hand,with the help of MXene nano-layered structure,MXene can be used as a platform to construct three-dimensional nanostructures with more active sites and larger specific surface area,which can further improve the performance of second phase materials in energy storage,electrochemical response,catalysis,etc.Therefore,in situ conversion modification of MXene is a feasible method to improve the performance of materials[19⇓~21]。
Taking Ti3C2MXene as an example,this paper first summarizes the preparation and conversion mechanism of hybrid materials based on in situ conversion of MXene,including in situ derivation of MXene,hybridization of MXene with metal ions and MXene with metal-organic framework(MOF);Secondly,the applications of MXene hybrid materials in the fields of energy storage,sensing and catalysis are summarized;Finally,the unsolved problems in this field are pointed out,and the future development direction is prospected 。

2 In situ conversion reaction of MXene to produce hybrid materials

2.1 MXene in situ conversion

MXene is mostly prepared by selective etching of the A layer(mostly group IIIA and IVA elements)in the MAX phase(Fig.1A,B),which has a unique layered structure that exposes the transition metal atoms it contains on the outer surface.this structure is prone to surface in situ transformation reactions such as oxidation,sulfurization,or selenization.in This process,the surface of MXene material reacts to convert the material into a hybrid material composed of the original MXene and metal oxides,sulfides or selenides.This process can be regarded as the in-situ growth of a class of metal compounds on the surface of MXene,which is characterized by the absence of additional transition metal sources,but its epitaxial growth is therefore limited.At the same time,due to the existence of surface van der Waals force,this strong electrostatic force can also make MXene self-assemble to produce hybrid materials[22]。 in the preparation process,composites with different dimensions are produced due to different processes and preparation conditions.These materials are different In morphology,but they all have larger specific surface area and more active sites。
图1 （a）刻蚀Ti3C2示意图; （b）手风琴状Ti3C2的SEM图像[29]; （c）零维（米壳状）TiO2与Ti3C2形成的复合材料的SEM图像[23]; （d）一维TiO2与Ti3C2形成的复合材料的SEM图像[28]; （e）二维TiO2与Ti3C2形成的复合材料的SEM图像[30]

Fig. 1 (a)Schematic diagram of etching Ti3C2; (b)SEM images of accordion-like Ti3C2[29]; (c)SEM image of 0D (rice crust) TiO2 and Ti3C2 composite material[23]; (d)SEM image of 1D TiO2 and Ti3C2 composite material[28]; (e)SEM image of 2D TiO2 and Ti3C2 composite material[30]

2.1.1 Controllable Preparation and Mechanism Analysis of TiO2/MXene Composite

At present,in TiO2/MXene composites,TiO2mainly exist in three dimensions:zero-dimensional(nanoparticles),one-dimensional(nanowires)and two-dimensional(nanosheets),and their preparation methods and material properties are also different 。
For the TiO2/MXene composite formed by zero-dimensional TiO2and MXene nanosheets,the preparation is mainly achieved by the in-situ oxidation of Ti in MXene,and the growth or loading of TiO2nanoparticles on the surface of MXene.Low et al.First prepared accordion-like multilayer Ti3C2（m-Ti3C2）bulk by hydrofluoric acid(HF)etching Ti3C2MXene,and then prepared rice shell-like TiO2/Ti3C2composite by calcination method[23]。 The TiO2nanoparticles were∼25 nm in size and uniformly grown on the Ti3C2lamellar structure(Fig.1 C).Xu et al.Used m-Ti3C2as a starting material to synthesize heterojunction TiO2/Ti3C2layered hybrid materials by hydrothermal oxidation[24]。 After hydrothermal oxidation treatment,the in situ grown TiO2nanocrystals significantly increase the interlayer spacing of the Ti3C2,in which the TiO2nanocrystals grown on the Ti3C2are anatase,and the final TiO2/Ti3C2still maintains a layered structure with a thickness of about 30μm.These layered TiO2/Ti3C2heterojunction materials have a narrow band gap(2.1 eV),contributing to the absorption of visible light.Wang et al.Used HF etching to prepare m-Ti3C2bulk,and a simple one-step hydrothermal oxidation method was used to prepare TiO2nanoparticle/Ti3C2composite with a sandwich structure[25]。 The results show that the oxidation degree of Ti3C2is controlled by hydrothermal time,and the content of TiO2increases with the increase of hydrothermal time.Compared with the pure Ti3C2,the composite material has a significantly increased specific surface area,thereby providing more active sites for the loading and reaction of the second phase material on the surface thereof 。
For the TiO2/MXene composites formed by one-dimensional TiO2and MXene nanosheets,the preparation often uses Ti3C2MXene as Ti source to form TiO2/MXene hybrid materials with two-dimensional nanorod structure by in-situ oxidation 。
Li et al.Realized the in-situ growth of TiO2nanowires on the surface of HF etched m-Ti3C2MXene by alkali oxidation method,and thus successfully prepared a TiO2/Ti3C2composite with urchin-like structure[26]。 The TiO2nanowires are 10–100 nm in diameter and 500 nm–1μm in length,and are uniformly distributed around the Ti3C2nanosheets.Compared with pure Ti3C2or TiO2materials,the TiO2/Ti3C2composite with urchin-like structure has a larger surface area.The increased surface area and defect sites improve the adsorption capacity and detection sensitivity of the membrane for molecules.Sun et al.Used m-Ti3C2MXene solution mixed with KOH solution to prepare TiO2/Ti3C2composite by oxidation[27]。 Among them,a large number of TiO2nanowires were grown in situ on the surface of Ti3C2nanosheets after reaction with KOH solution.The experimental results show that the electrochemiluminescence performance of the material is closely related to the alkaline oxidation time,and the device can be optimized by controlling the alkaline oxidation time.Liu et al.Used the alkali oxidation method to realize the partial in situ conversion of m-Ti3C2MXene and prepared the hierarchical 1D/2D TiO2/Ti3C2heterostructure as the electrode material for deionization[28]。 Among them,the cross-linked TiO2nanowires can further expand the interlayer spacing of MXenes,provide abundant ion transport channels,and also provide additional active sites for high Na+adsorption.The cross-linked TiO2nanowires can also act as a protective layer to mitigate internal Ti3C2oxidation,thereby improving the cycling stability of the TiO2/Ti3C2composite.This work breaks through the limitation of pure MXene materials by forming hybrid materials through in-situ oxidation,and shows broad prospects in the field of seawater desalination 。
For the composites of 2D TiO2and MXene nanosheets,the construction is mainly based on the interaction of the morphology-controlling agent and the in-situ conversion of MXene 。
Li et al.Employed a hydrothermal oxidation method and used NaBF4as a crystal face regulator to successfully realize the in situ growth of TiO2nanosheets on the surface of m-Ti3C2MXene nanosheets(Fig.1e )[30]。 On this basis,MoS2nanosheets were in-situ grown on the TiO2/Ti3C2composite by secondary hydrothermal treatment.The close and uniform coupling among Ti3C2,TiO2,and MoS2nanosheets(NSs)successfully constructed the 2D-2D-2D heterojunction based on the MoS2/TiO2/Ti3C2composite.Using hydrothermal oxidation method,Shahzad et al.Prepared（001）TiO2nanosheet/m-Ti3C2MXene nanocomposite[31]。 Due to the high catalytic activity of the TiO2（001）plane and the extra electron（e-）and hole（h+）generated by the Schottky junction and the low band gap energy(2.4 eV),the composite material has good photocatalytic activity for carbamazepine degradation.This is the first report on the photocatalytic degradation of drugs by MXene or its derivatives,which expands the application range of this kind of materials in the field of photocatalytic degradation of drugs,and also provides an important reference for the design and preparation of new and efficient photocatalytic materials 。

2.1.2 Controllable preparation of TiS2 materials derived from Ti3C2MXene;

Currently,although various methods have been developed to prepare TiS2nanomaterials,it is still challenging to controllably synthesize highly crystalline ultrathin TiS2nanomaterials in a more efficient manner[32]。 The method using MXene materials as precursors provides a new feasible route for the preparation of TiS2nanomaterials.Similar to the oxidation of MXene,the in situ conversion of Ti3C2to TiS2nanomaterials can also be achieved through the sulfidation process,during which the Ti3C2component is often consumed and converted into the target product[32⇓⇓~35]。
Tang et al.Prepared ultrathin TiS2nanosheets by polydopamine(PDA)-assisted in-situ sulfurization process using u-Ti3C2MXene obtained by mixed etching of LiF and HCl as precursor[32]。 The preparation principle is to modify the surface of MXene nanosheets with PVP through the electrostatic attraction between the negatively charged MXene and the protonated polyvinylpyrrolidone(PVP)chain,and the hydrogen bonding interaction between the oxygen-containing groups on the surface of MXene and the strong polar groups of PVP(such as C=O).The strong affinity of PVP for MXene effectively hinders the restacking of Ti3C2.The modified Ti3C2MXene was then freeze-dried and annealed in a H2S atmosphere,during which MXene was sulfurized to obtain carbon-coated TiS2nanosheets(Figure 2A).The TiS2nanosheets were uniformly distributed in the interior of the carbon matrix(Figure 2B),and the Ti3C2component was completely consumed and converted into the target product(Figure 2C).The dispersed TiS2nanosheets have an average size of several hundred nanometers in the form of hexagonal plates.Structurally,the PVP-derived carbon provides the composite with additional specific surface area and abundant pores,and also provides more electrochemical active sites,increasing the electrode/electrolyte contact interface.Huang et al.Successfully converted u-Ti3C2MXene into sandwich-like ultrathin TiS2nanosheets confined by N,S-co-doped porous carbon（TiS2@NSC）through an in situ PDA-assisted vulcanization process[35]。 In which PDA was introduced to the MXene surface,thereby protecting the Ti3C2nanosheets from oxidation and inhibiting their restacking.Moreover,during the sulfidation process,the PDA-derived carbon materials confined the TiS2growth within the 2D nanospace,resulting in a unique sandwich-like structure.This structure is highly favorable for the immobilization of LiPSs(soluble intermediate long-chain polysulfides),thus leading to high utilization of sulfur and uniform distribution of sulfur species 。
图2 （a）PVP衍生碳约束TiS2纳米片（TiS2@CPVP）的合成示意图; （b）TiS2@CPVP的SEM图像; （c）TiS2@CPVP的XRD图像[32]

Fig. 2 (a)Schematic of the synthesis of PVP derived carbon confined TiS2 nanosheets; (b)SEM images of TiS2@CPVP; (c)XRD images of TiS2@CPVP.[32]

2.1.3 Controlled preparation of Ti3C2MXene derived TiSe2 composites

Metal selenides have a weak metal-selenium bond,which is easier to initiate the conversion reaction,thus ensuring a high initial Coulombic efficiency and reversibility.Compared with TiO2（2.2 eV）,TiSe2has a smaller band gap(0.1 eV)and higher electronic conductivity[36,37]。 Compared with TiS2,TiSe2has a larger interlayer spacing(0.601 nm)corresponding to the(001)plane and better electronic conductivity[38]。 Therefore,besides TiO2and TiS2,TiSe2is another potential 2D layered material.The Ti3C2MXene material can be used as a precursor to realize the conversion to a TiSe2material to obtain target products such as a TiSe2and a TiSe2/Ti3C2MXene 。
Qi et al.Synthesized TiSe2/TiO2/C hexagonal prism heterojunction by solid selenization process using u-Ti3C2as precursor[39]。 In this process,Ti3C2and selenium were uniformly mixed,ground and heated to obtain the product(Figure 3A),and the morphologies of the product treated at different temperatures are shown in Figure 3(B),Figure 3(C)and Figure 3(d).With the increase of temperature and time during the treatment,the content of TiSe2in the composite decreased gradually,while the TiO2phase increased.Structurally,the layered structure of TiSe2has a large specific surface area and a mesoporous structure,which is beneficial to ion diffusion,and the large interlayer spacing of the TiSe2and the buffer carbon layer is also beneficial to adapting to volume expansion and improving cycle stability.TiSe2can also induce a built-in electric field at the heterojunction interface and accelerate the electrochemical process.Azadmanjiri et al.Designed and synthesized m-Ti3C2containing half-metal selenium atoms by easy solid phase chemistry,and realized covalent surface modification of two-dimensional nanomaterials to control the properties of such nanomaterials[40]。 Se/Ti3C2formed the TiSe2phase on the Ti3C2layer.The pillar effect stabilizes the MXene structure 。
图3 （a）TiSe2/TiO2/C的合成示意图; （b）450 ℃, （c）550 ℃, （d）650 ℃下处理3 h的TiSe2/TiO2/C的SEM图[39]

Fig.3 (a)Schematic for synthesis of MXene derivative TiSe2/TiO2/C; SEM images of TiSe2/TiO2/C treated at (b)450 ℃, (c)550 ℃, (d)650 ℃[39]

2.2 In-situ reaction of metal ions on MXene surface

MXene can also be used as a substrate for second phase materials instead of reactants to synthesize hybrid materials.In this process,metal ions can be used as precursors for the nucleation and growth of secondary materials,thereby modifying MXene,while the integrity of MXene is well maintained[41,42]。

2.2.1 Preparation and Mechanism of Ni/MXene Composite

Feng et al.Proposed a method of surface Ni modification to improve the microwave absorption properties of m-Ti3C2MXene(Figure 4A )[43]。 The morphology of the prepared composite is shown in Fig.4(B),and the EDS spectrum also confirms the successful preparation of this kind of material(Fig.4 C).The modification of nickel is carried out by the spontaneous chemical reaction of alkalized Ti3C2MXene with Ni2+.In KOH solution,the weak acid end(—OH or—F)on the surface of Ti3C2MXene can react with KOH and alkalize.The alkalized MXene was transferred into a solution containing Ni2+.Because Ni2+is stable only under acidic conditions,Ni2+can deposit spontaneously on the surface of MXene.Wen et al.Reported a spheroidization strategy for assembling double-shell u-MXene@Ni microspheres[44]。 The usual layered MXene is reshaped into three-dimensional microspheres to provide a substrate for the directional growth of Ni nanotips,and the few-layer Ti3C2MXene sheets are adsorbed to the surface of plexiglass microspheres through hydrogen bonding to form a binary complex.Because MXene is negatively charged,Ni2+ions are electrostatically adsorbed on the surface of MXene.Liang et al.Successfully combined two-dimensional Ti3C2MXene nanosheets and one-dimensional Ni nanochains by hydrothermal method to synthesize efficient electromagnetic wave absorbing and shielding composites,and the impedance matching and conductivity of the mixed materials could be easily controlled by changing the content of MXene,which provided a reference for the development of high-performance electromagnetic wave absorbing and shielding materials[45]。
图4 （a）Ti3C2 MXene的碱化和Ni改性过程示意图; Ni修饰MXene的（b）SEM图像和（c）EDS谱[43]

Fig. 4 (a) A schematic illustration of the process of alkalization and Ni-modification of Ti3C2 MXene; (b) SEM image and (c) EDS spectrum of the as-derived Ni-modified MXene[43]

2.2.2 Preparation and Mechanism of Ru/MXene Composite

Bat-Erdene et al.Successfully developed a Ru catalyst supported on B-doped u-MXene[46]。 When the prepared Ti3C2nanosheets were mixed with boric acid and RuCl3·xH2O in aqueous solution,B and Ru3+were easily adsorbed on the surface of the nanosheets due to the abundant surface terminal groups(—F,—O and—OH).After annealing under inert conditions,boron atoms were chemically doped onto the Ti3C2nanosheets,while individual Ru3+ions were thermally reduced to RuO nanoparticles,forming the Ru@B-Ti3C2composite.The material has a good application prospect as an electrocatalyst of an efficient catalytic system.Kong et al.Prepared a novel underwater superoxophobic and superhydrophilic Ru-based electrocatalyst by hydrothermal method using cetyltrimethylammonium bromide-modified u-Ti3C2[47]。 Among them,Ru3+was reduced in situ on the modified MXene,and finally exhibited a wrinkled three-dimensional structure in which uniformly distributed Ru nanoparticles were embedded.Liu et al.Synthesized a series of RuFe alloy catalysts supported on 2D MXene[48]。 the main function of MXene substrate is to prevent the stacking of bimetallic nanoparticles,which can not only maintain the reaction space,alleviate the crowding of active sites,but also improve the utilization of metals.the unique structural and surface properties of MXene,as well as the synergistic effect between RuFe bimetals,provide excellent electrochemical catalytic performance for the RuFe@MXene composite catalyst。

2.3 MOF and MXene assembly

because MXene has the advantage of high active sites,it can form strong bonds with organic ligands and some inorganic compounds of MOF.Therefore,MXene can be used as an adsorbent to provide growth conditions for MOF materials,as a conductive agent to improve the electronic conductivity,and as a spacer to effectively prevent the agglomeration of MOF.In the hybrid process of MOF and MXene,Because MOF has a large specific surface area,easily adjustable pore size and abundant pseudocapacitive redox centers,the controllable adjustment of material properties can be easily achieved by selecting different metal centers and ligands[49⇓~51]。
Xiao et al.Proposed a simple hydrothermal method to deposit Fe-MOF on u-Ti3C2substrate in situ[52]。 the obtained Fe-MOF/MXene showed a strong electrochemical response to As(Ⅲ).Among them,the abundant surface functional groups(—OH,—O,and—F)of MXene form strong bonds with the organic ligands of Fe-MOF,which enables the construction of such composites.In addition,due to the strong coordination interaction between Fe-MOF and As(Ⅲ),and the formation of As—O bond between the hydroxyl group on the surface of MXene and arsenic to remove arsenic,Fe-MOF/MXene shows excellent adsorption performance for As(Ⅲ),showing a strong electrochemical response,which can be used to construct a hypersensitive electrochemical sensor for the determination of arsenic。
Zhang et al.synthesized MXene-MOF composite by self-assembly of Ni-MOF on m-MXene and further Synthesized nickel phosphate-MXene composite for battery-type electrode by in-situ etching[53]。 Among them,the functional groups on the surface of striped Ti3C2nanosheets can be easily deprotonated and attached to the ligand.The ligand will further connect the metal ions,which can facilitate the in situ self-assembly of Ni-MOF spheres on Ti3C2nanosheets through bottom-up synthesis.MXene nanosheets can provide abundant nucleation sites for the formation of MOF nanospheres,so that the MOF nanospheres are uniformly distributed and fully covered.This achievement provides a new idea for the synthesis of similar composites 。

3 Application of nanocomposites based on MXene derived

3.1 Energy storage

in the world,the energy crisis and environmental problems are deteriorating day by day.Electrochemical energy storage technology can effectively store electric energy and release It when needed.it is widely used In various electronic energy storage devices because of its high energy density,high efficiency,long life and repeatable charge and discharge[54⇓⇓~57]。 This part summarizes the applications of MXene-derived nanocomposites in lithium-sulfur batteries,supercapacitors,hydrogen energy storage,etc。

3.1.1 Lithium-sulfur battery

Lithium-sulfur battery is a new type of battery technology,which can be widely used in electronic devices as an energy supply device because of its high energy density,environmental friendliness,low cost and other advantages[58,59]。 The theoretical specific capacities of sulfur cathode and lithium anode are 1675 and 3860 mAh·g-1,respectively,and the theoretical energy density of sulfur lithium battery is up to 2567 Wh·kg-1[60,61]。 However,the practical application of Li-S batteries is restricted by the shuttle effect of the soluble intermediate long-chain polysulfide Li2Sn（4≤n≤8）（LiPSs）,which leads to severe capacity fading and short cycle life[62]。
MXene hybrids have shown very promising applications in achieving high-performance Li-S batteries.the metallic conductivity of MXene hybrids provides fast electron transfer,which facilitates the full utilization of sulfur and ensures the high capacity of Li-S batteries.The MXene surface end has a strong adsorption effect on LiPSs,forming a strong metal−S bond,which can effectively suppress the shuttle effect。
Jiao et al.Proposed a multifunctional catalyst with strong polysulfide adsorption ability,excellent polysulfide conversion activity,high specific surface area,and electronic conductivity by in situ preparation of TiO2/u-MXene heterostructure(Figure 5A )[63]。 The TiO2/MXene heterostructure combines the advantages of large surface area,strong LiPSs trapping ability,high electrocatalytic activity,and electrical conductivity.The TiO2NPs uniformly distributed on the surface of MXene provided many strong LiPSs trapping centers,and the heterostructure interface ensured the smooth diffusion of LiPSs to MXene with high catalytic activity to achieve rapid conversion.Therefore,the assembled interlayer constructed by the TiO2/MXene heterostructure and GN effectively blocks the shuttling of LiPSs and improves the utilization of sulfur,resulting in high cycling stability.The improved Li-S battery can deliver 800 mAh·g-1at 2 C,with 0.028%capacity fade per cycle at 1000 cycles at 2 C and 93%capacity retention after 200 cycles even at a high sulfur loading of 5.1 mg·cm-2(Figure 5B).The MXene-based materials oxidized for different times were loaded on carbon fiber paper(CP)for potentiostatic discharge experiments,and the CP-Ti3C2(4 h)（partially oxidized)electrode had higher activity for the precipitation of Li2S,higher precipitation current,and the precipitation capacity was 162.1 mAh·g-1（Fig.5C–e).The results show that the TiO2-Ti3C2heterostructure with optimized chemical composition and surface properties can effectively contain the shuttle effect of LiPSs due to the excellent adsorption of TiO2,which not only improves the adsorption capacity of LiPSs,but also effectively promotes their rapid conversion in the electrochemical process 。
图5 （a）LiPSs在TiO2-Ti3C2异质结构上的俘获和转化过程示意图;（b）Ti3C2 -GN夹层的Li-S电池循环性能;（c~e）不同异质结构电极上Li2S8溶液在2.02 V下的恒电位放电曲线[63]

Fig. 5 (a) Schematic illustration of LiPSs trapping and conversion process on the TiO2-Ti3C heterostructures; (b) Cycling performance of Li-S cells with Ti3C2 -GN interlayer; (c~e) Potentiostatic discharge profiles of Li2S8 solution at 2.02 V on the electrodes containing different heterostructures[63]

3.1.2 Supercapacitor

supercapacitors,also known as electrochemical Supercapacitors,are high energy density energy storage devices.It realizes charge storage between electrodes mainly through two mechanisms of double-layer capacitance and pseudocapacitance,and realizes fast charge-discharge process,which can provide high power density and long cycle life[64,65]。 Because of its high conductivity,MXene is regarded as a potentially valuable auxiliary material that can change the conductivity of the active element.Pure MXene materials have limited energy storage properties in supercapacitor applications because of their self-stacking between sheets,limited specific surface area,and fewer active accessible sites.Modifying MXene with pseudocapacitive materials such as metal oxides(NO)to enhance the electrochemical energy storage performance of MXene has been proved to be a feasible approach.Hybrid materials of metal oxides such as RuO2,NiO,SnO2,MnO2,Fe3O4,Fe2O3and MXene have been explored as electrodes for supercapacitors[66][67][68][69][70][71]。
For supercapacitor applications,NO@MXene electrode materials have two structural advantages.First,the layered MXene sheet has a large specific surface area,and the NO on the nanosheet opens the inactive surface area caused by restacking,providing more active sites.Secondly,MXene increases the conductivity of NO@MXene electrode,which plays an important role in the electrochemical performance[66,67]。
Jiang et al.Designed an all-pseudocapacitive asymmetric supercapacitor by using the characteristic that u-Ti3C2MXene can work at negative potential in acidic electrolyte and combining it with RuO2positive electrode[66]。 This asymmetric device operates at a voltage window of 1.5 V,which is 2 times wider than that of the symmetric MXene supercapacitor,and it can deliver an energy density of 37µWh·cm-2at a power density of 40 mW·cm-2,retaining 86%of the capacitance after 20 000 charge-discharge cycles.Chavan et al.Synthesized NiO@M-MXene nanocomposite by a simple screen printing method[67]。 At a current density of 1 mol·L-1KOH,6 mA·cm-2,the capacitance value of the 15%NiO@m-MXene material is 1542 F·g-1,which is about 8 times that of the pure MXene material in the same case.Mustafa et al.Proposed a method to synthesize ascorbic acid-treated m-MXene/SnO2flexible electrode[68]。 Treatment of the synthesized three-dimensional SnO2nanoflowers with ascorbic acid activated their surface and provided an attachment site for the MXene sheet.The SnO2nanoflower not only acts as a nanopillar between the layers,but also keeps the proper space between the layers and provides a two-dimensional surface for charge storage.The specific capacitance of the MXene/SnO2hybrid was 643 F·g-1,and 98%capacitance was retained after 1000 charge-discharge cycles 。

3.1.3 Hydrogen energy storage

With the aggravation of energy crisis and environmental problems,hydrogen energy,as a new energy source,has become a reliable solution to reduce dependence on fossil fuels because of its clean,pollution-free,safe,sustainable,environmentally friendly and high energy density[72⇓~74]。 To date,the addition of catalyst has been shown to improve the hydrogenation/dehydrogenation kinetics and reversibility of NaAlH4[75,76]。 Because of its large specific surface area,good conductivity,good structural and chemical stability,MXene is expected to enhance the dehydrogenation performance of NaAlH4,and the zero-valent titanium(Ti0)contained in MXene can be used as the catalytic active site for electron transfer of hydrogen storage active materials,but in the hydrogenation/dehydrogenation process.The binding energy of Ti0varies greatly,indicating that the chemical state of Ti0in the NaAlH4/Ti3C2composite is unstable,so it is necessary to modify MXene to effectively improve the catalytic performance of the catalyst to improve the cycle stability of NaAlH4[77⇓~79]。
Yuan et al.Prepared a two-dimensional nitrogen-doped carbon-coated m-Ti3C2（Ti3C2/NC）catalyst by dopamine self-polymerization and heat treatment,which showed excellent catalytic activity in terms of dehydrogenation kinetics and cycle stability of NaAlH4.The initial dehydrogenation temperature could be reduced to 85°C with the addition of 10%Ti3C2/NC catalyst,which was 70°C lower than that of the pure NaAlH4sample[79]。 The dehydrogenation kinetics of the NaAlH4+10%Ti3C2/NC composite was significantly improved,and the first step of dehydrogenation was completed within 57 min at 100°C.After 15 cycles,the hydrogen capacity is 4.66%(in terms of mass fraction),and the capacity retention rate is as high as 96.3%.Yuan et al.Also successfully synthesized CeF3nanoparticles strongly coupled with m-Ti3C2through a simple hydrothermal reaction（CeF3/Ti3C2）（Fig.6a)and used them to improve the hydrogen absorption and desorption properties of NaAlH4(Fig.6B,d )[78]。 Compared with pure NaAlH4,the initial dehydrogenation temperature can be reduced from 155°C to 87°C with the addition of 10%mass fraction of CeF3/Ti3C2catalyst.The release of hydrogen is as high as 4.95%(Fig.6C).Meanwhile,with the increase of temperature,the dehydrogenation behavior of the NaAlH4+10CeF3/Ti3C2composite is obviously improved(Fig.6e).After 10 consecutive experiments,a high reversibility with a capacity retention of 94.5%could be obtained(Figure 6 f).Among them,the relatively stable Ti-F-Ce structure can effectively improve the stability of Ti0and enhance the hydrogen storage performance of NaAlH4 。
图6 （a）CeF3/Ti3C2制备及应用示意图;储氢性能表征:（b）TPD曲线, （c）体积释放曲线, （d, e）等温脱氢曲线, （f）NaAlH4+10CeF3/Ti3C2复合材料的循环脱氢实验（插图为相应的氢容量保留量）[78]

Fig. 6 (a) Scheme of preparation and application of CeF3/Ti3C2；Hydrogen storage property characterization: (b)TPD curves, (c)Volumetric release curves, (d, e)Isothermal dehydrogenation curves, (f) The cycling dehydrogenation tests of the NaAlH4+10CeF3/Ti3C2 composite(the inset is the corresponding hydrogen capacity retention)[78]

3.2 Sensing

As an important class of sensing devices,gas sensors have been widely used in environmental monitoring,industrial safety,health care,agriculture and other fields because they can detect and monitor a variety of pollutants and harmful gases in the air[80⇓~82]。 Ti3C2MXene has great potential for highly sensitive room-temperature electrochemical detection of gaseous analytes due to its large specific surface area and metal conductivity[83⇓~85]。 However,the interlayer spacing stacking between MXene nanosheets may limit its applicability,and the use of heteroatoms as dopants can help overcome this limitation。
Shuvo et al.Synthesized sulfur-doped u-Ti3C2MXene（S−Ti3C2）by exfoliation method and integrated it into a conductance gas sensor[84]。 The interlayer spacing of MXene nanosheets is greatly increased after sulfur doping.The response upon sulfur doping is enhanced,successfully observing a corresponding increase by a factor of 3∼4 in the range of∼214%of 1 ppm（1 ppm=1×10-6）to∼312%of 50 ppm.The material shows a unique selectivity for toluene,and after doping,the charge distribution of S atoms around the adsorbed gas molecule is altered,and this effect leads to an enhancement of the gas response.Chang et al.Successfully prepared a bimetallic rod-like iron-porphyrine-based MOF(Co-TCPP(Fe))material with innovative features,and hydrogen-bonded with u-Ti3C2MXene to form a Co-TCPP(Fe)/Ti3C2hybrid(Figure 7 A )[86]。 The sensors based on the above hybrid materials exhibit superior room-temperature NO sensing performance(Fig.7 B∼e).Among them,the MOF structure has abundant unoccupied Fe-N4units,providing a good platform for sensing NO.MOF is assembled with MXene to construct Schottky junction,which macroscopically endows the hybrid material with better conductivity and more effective reflection of resistance change.In terms of performance,it has a fast response/recovery speed(95 s/15 s)to NO.At low concentrations of 200 ppb（1 ppb=1×10-9）,the response to NO can be recorded,showing a higher sensitivity(Fig.7d).The response of the sensor remains at about 82%of the initial value for 10 d,showing good stability(Figure 7 f).More importantly,the response of the Co-TCPP(Fe)/Ti3C2sensor to NO(Ra/Rg=2.0,10 ppm)is much higher than that of other exhaled gases(Figure 7 G),showing promising potential for selective discrimination of target gases in the medical research field 。
图7 （a）Co-TCPP(Fe)、Ti3C2及Co-TCPP(Fe)/Ti3C2的合成工艺示意图；（b）10 ppm NO暴露于原始Co-TCPP(Fe)、Ti3C2、TCPP(Fe)/Ti3C2-20、TCPP(Fe)/Ti3C2-20和Co-TCPP(Fe)/ Ti3C2-20后的典型响应曲线; （c）10 ppm NO暴露于Co-TCPP (Fe)/Ti3C2后的典型响应曲线; （d）室温下Co-TCPP(Fe)/Ti3C2-20传感器对10 ppm NO的实时响应-恢复曲线; （e）室温下不同相对湿度（0% ~ 70%），传感器对10 ppm NO的响应; （f）传感器在室温下暴露于10 ppm NO时的长期稳定性; （g）传感器对浓度为10 ppm和20 ppm的各种气体的选择性[86]

Fig. 7 (a) Synthesis process of Co-TCPP(Fe),Ti3C2,and Co-TCPP(Fe)/Ti3C2; (b) Typical response curves after 10 ppm NO exposure to pristine Co-TCPP(Fe)，Ti3C2，TCPP(Fe)/ Ti3C2-20，TCPP(Fe)/Ti3C2-20 and Co-TCPP(Fe)/Ti3C2-20; (c) Typical response curves after 10 ppm NO exposure to Co-TCPP(Fe)/Ti3C2; (d) Real-time response-recovery curve of the Co-TCPP(Fe)/Ti3C2-20 based sensor toward 10 ppm NO at room temperature; (e) The response of the sensor toward 10 ppm NO at different relative humidities ranging from 0% to 70% at room temperature; (f) Long-term stability of the sensor exposed toward 10 ppm NO at room temperature; (g) The selectivity of the sensor to various gases at concentrations of 10 ppm and 20 ppm [86]

3.3 Catalyze

Catalysis refers to the addition of a catalyst to accelerate the rate of a chemical reaction or to reduce the energy required for a reaction.it is widely used in chemical industry production,energy conversion,environmental protection and other fields because It can improve reaction efficiency,reduce energy consumption and reduce environmental pollution[87⇓~89]。 Because of its large specific surface area and abundant surface groups,MXene is conducive to the dispersion and anchoring of various catalysts,and increases the active sites for the construction of three-dimensional structure of catalysts.At the same time,the conductivity of MXene enhances the electrochemical response of composites,which is a suitable support for various catalytic materials,showing its potential application in the field of catalysis[90]。
Wang et al.Constructed three-dimensional interconnected CoMoS2/Ti3C2composites by in-situ vertical growth of MoS2nanosheets on the surface and interlayer of m-Ti3C2through a simple one-step hydrothermal method(Fig.8 a,B )[16]。 The isotherms of Ti3C2and CoMoS2/Ti3C2show reversible type IV isotherms,and the hysteresis loop is not obvious,indicating that they have mesopores(Fig.8 C),and the average pore diameter of CoMoS2/Ti3C2is calculated to be about 4 nm(Fig.8 d).The tangled CoMoS2nanosheets vertically grown on the surface and between the layers of Ti3C2resulted in an increased specific surface area.Due to the rich active phase and open structure of the composite,CoMoS2/Ti3C2exhibits a higher rate constant（1.12 mol·mol-1·h-1）than CoMoS2（0.4 mol·mol-1·h-1）in the HDS of diphenylthiophene(DBT)at 300°C and 4 MPa H2.This achievement shows great potential in the further development of efficient hydroprocessing catalysts for the processing and desulfurization of heavy hydrocarbon resources such as coal-based oil and asphalt-derived heavy oil.The MXene hybrid material also has a good application prospect in the（NO3-RR）of nitrate electrocatalytic reduction reaction for ammonia production.Li et al.Successfully dispersed and anchored CuPc on u-MXene to construct a molecular catalyst,which significantly improved the activity and selectivity of CuPc molecules in NO3-RR[91]。 The electrochemical active area measurements showed that the MXene in CuPc@MXene increased the conductivity and exposed abundant active sites for NO3-RR.The 10%CuPc@MXene exhibited excellent ammonia selectivity(94.0%)and high nitrate conversion(90.5%),and remained stable in seven recycling experiments 。
图8 （a）CoMoS2/Ti3C2结构示意图; （b）Ti3C2 MXene、CoMoS2及CoMoS2/Ti3C2合成原理图; CoMoS2/Ti3C2的加氢脱硫催化性能:Ti3C2 MXene、CoMoS2及CoMoS2/Ti3C2-200的（c）氮气吸附-解吸等温线和（d）孔径分布图[16]

Fig. 8 (a)Schematic of the structure of CoMoS2/Ti3C2; (b)Schematic of the synthesis of Ti3C2 MXene, CoMoS2, and CoMoS2/Ti3C2; Catalytic performance of as-prepared samples:(c)Nitrogen adsorption-desorption isotherms and (d)pore size distribution plots of Ti3C2 MXene, CoMoS2 and CoMoS2/Ti3C2-200[16]

4 Summary and Prospect

In this paper,taking Ti3C2MXene as an example,the preparation of hybrid materials based on in situ conversion of MXene(in situ derivatization,metal ion hybridization and MOF hybridization)and the conversion mechanism are summarized,and the applications of MXene hybrid materials in energy storage(lithium-sulfur batteries,supercapacitors and hydrogen energy storage),gas sensing and catalysis are summarized.Although hybrid materials based on in situ conversion of MXene show broad application potential,there are still many scientific problems and technical difficulties that need to be solved urgently,and further exploration in this field still needs to be carried out from the following four aspects 。
(1)In the current work,the mechanism of in situ conversion of MXene to hybrid materials is mainly based on the characterization and testing of experimental materials,so it is still necessary to further explore the structure and composition regulation,and to further understand the structure evolution and composition regulation mechanism of in situ conversion of MXene.This includes the understanding of the phase transformation behavior of MXene materials during in-situ conversion,the regulation of lattice structure,and the optimization of the composition of hybrid materials.The exact regulation of functional properties needs to be derived through theoretical calculations and models.(2)An in-depth understanding of the influence of size effect and interface regulation in MXene-based hybrid materials is needed.This includes understanding the interaction between nanomaterials and other functional components,as well as exploring the effects of interface structure,interface energy level regulation and interface charge transfer on the properties of hybrid materials.Controllable optimization of hybrid material properties can be achieved by optimizing interface engineering.(3)Up to now,nanomaterials have shown great strength in many fields such as nanotechnology,drug delivery and biomedicine,energy storage,environmental protection,Internet of Things and sensing,5G communication,etc.However,the hybrid materials converted by MXene in situ mainly focus on energy storage,sensing and catalysis.Future research can try to rely on the excellent platform characteristics of MXene to transform into functional materials in other fields in situ,carry out performance test comparison and system characterization,and clarify the structure-activity relationship.(4)The existing research on in situ conversion of MXene mainly focuses on the use of Ti3C2as a precursor,and since the discovery of MXene(Ti3C2)in 2011,more than 30 different types of MXene have been synthesized.In the future research,it can be extended to the in-situ transformation and application of various MXene materials such as Nb2C,Nb4C3,V2C,V4C3,Mo2TiC2and so on 。
in situ conversion of MXene has many advantages in the formation of hybrid materials and applications,such as simplicity,high efficiency,good adjustability,adaptability to a variety of second phase materials,and resource saving.With the deepening of research in this direction,it is expected to realize the controllable synthesis of various hybrid materials and promote multiple applications in multiple fields。

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