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

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Progress in Chemistry >

2024 , Vol. 36 >Issue 9: 1336 - 1348

DOI: https://doi.org/10.7536/PC240120

Review

Research Progress and Challenges in Infrared Applications of MXene Materials

  • Yubin Li 1 ,
  • Guoliang Dai 2 ,
  • Jie Fan 1 ,
  • Hong Xiao , 2, *
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  • 1 School of Textile Science and Engineering, Tiangong University, Tianjin 300387, China
  • 2 Systems Engineering Institute, Academy of Military Sciences (AMS), Beijing 100010, China
*e-mail:

Received date: 2024-01-23

  Revised date: 2024-04-06

  Online published: 2024-07-01

Supported by

National Natural Science Foundation of China(52173191)

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Abstract

MXene is a two-dimensional transition metal carbon/nitrogen compound or carbon-nitrogen compound obtained from MAX phase materials by chemical etching followed by ultrasonic or intercalation treatment.It has the properties of two-dimensional atomic layer structure,abundant components,metallic conductivity,large specific surface area and active surface,etc.It has distinct infrared absorption in the near-infrared and mid\far-infrared bands,and has attracted extensive attention from researchers in recent years in a number of infrared applications,such as infrared camouflage,photothermal conversion,and photovoltaic effect.in this paper,the properties of MXene materials in the infrared band are reviewed in detail,including the high absorbance and localized surface plasmon resonance effect in the near-infrared band and the infrared low-emission properties in the mid/far-infrared band.Further based on its infrared properties,the research progress of its applications in popular fields such as infrared camouflage,broadband absorber,passive radiant heating,photothermal conversion and photovoltaic effect is summarized.Finally,the main problems of the current research on MXene materials in the infrared field and the future development direction are prospected。

Contents

1 Introduction

2 Infrared properties of MXene

2.1 Near-infrared optical properties

2.2 Middle/far infrared optical properties

3 Research on infrared application of MXene

3.1 Broadband absorber

3.2 Infrared camouflage

3.3 Photothermal conversion

3.4 Passive radiation heating

3.5 Infrared photoelectric detection

4 Conclusion and outlook

Key words： MXene; infrared; infrared camouflage; photothermal conversion; passive radiant heating; photovoltaic effect

Cite this article

Yubin Li , Guoliang Dai , Jie Fan , Hong Xiao . Research Progress and Challenges in Infrared Applications of MXene Materials[J]. Progress in Chemistry, 2024 , 36(9) : 1336 -1348 . DOI: 10.7536/PC240120

1 Introduction

MXene is a two-dimensional transition metal carbon/nitride or carbonitride with a layered structure[1⇓~3]。 Monolayer MXene is obtained from precursor MAX phase material by chemical etching followed by ultrasonic or intercalation treatment,and its general chemical formula is represented by Mn+1XnTx,where M refers to transition metal(Ti,Hf,Zr,Nb,V,Cr,Sc,etc.),X refers to C or N,n is generally 1–3,and Tx refers to surface active group（O2-,F-,OH-,etc. )[4,5][6⇓⇓~9]。 Since its first discovery by Gogotsi in 2011,it has rapidly become a research hotspot,and its etching process and multi-layer lift-off process are becoming more and more mature[10][11]。 At present,more than 150 kinds of MAX phase materials have been reported,of which more than 50 kinds of MXene materials have been found and successfully exfoliated[12]。 Due to its rich active groups,high specific surface area and excellent mechanical,electrical,thermal and optical properties,MXene has been widely studied in the fields of energy storage,electromagnetic shielding,optoelectronics,catalysis,infrared camouflage,purification,biomedicine and so on[13][14][15][16][17][18][19⇓~21]。 in recent years,the research of MXene in the infrared field has developed rapidly.According to the statistical results of Web of Science,the statistical analysis chart of the number of documents retrieved with MXene and MXene&infrared as keywords is shown in Figure 1.the number of scientific research documents shows a continuous increasing trend,while the overall number of MXene documents shows a slight decreasing trend.the proportion of MXene materials in the infrared application field is increasing.MXene has different infrared characteristics in different infrared bands,and has been rapidly developed in infrared camouflage,passive radiation heating,photothermal conversion,biological hyperthermia and other applications[22][23⇓⇓⇓⇓~28]。 in this paper,the infrared properties of MXene materials are analyzed,and the application research progress in various fields based on its infrared properties in recent years is summarized,and the existing problems and future development directions are prospected。
图1 关键词MXene和MXene & Infrared文献数量统计图

Fig. 1 Statistical chart of the number of literature including keywords MXene and MXene&Infrared

2 Infrared properties of MXene.

Any object above absolute zero will continuously radiate infrared electromagnetic waves,and the electromagnetic wave radiation of 0.76~1000μm is usually called infrared[29][30,31]。 Civil infrared radiation is generally divided into three bands:near-infrared(0.76~3μm),mid-infrared(3~25μm)and far-infrared(25~1000μm)[32]。 However,when infrared rays propagate in the atmosphere,they will be attenuated by the absorption or scattering of water vapor,solid particles and CO2in the atmosphere,and only in three infrared atmospheric windows,namely 0.76~2.6μm(near infrared),3~5μm(middle infrared)and 8~14μm(far infrared),can they propagate without interference(Figure 2 )[33][34,35]。 Therefore,these three infrared atmospheric windows are the focus of infrared research fields such as infrared camouflage,photothermal conversion,and intelligent personal thermal management。
图2 电磁波谱图

Fig. 2 Electromagnetic spectrum

MXene material has different infrared characteristics in the near infrared and middle/far infrared bands in the atmospheric window.It is found that the real part of the dielectric constant of the Ti3C2Tx MXene film changes from positive to negative at about 1.3μm with the increase of infrared wavelength,and the dielectric response changes to metallic response(Fig.3D )[22]。 Correspondingly,the MXene film shows strong absorption in the ultraviolet/visible region from 0.3 to 0.76μm and in the near-infrared wavelength range from 0.76 to 1.2μm,while the absorption is greatly reduced above 1.2μm.According to Kirchhoff's law,the directional infrared emissivity of an object in thermal equilibrium is equal to the infrared absorptivity,which indicates that the Ti3C2Tx MXene has a lower infrared emissivity in the middle/far infrared band with a wavelength of more than 1.2μm.However,it is worth noting that not all MXene has the characteristics of high absorption/high emission in the near infrared and low absorption/low emission in the middle/far infrared.For example,the infrared emissivity of Nb2CTx film in the middle/far infrared(3~25μm)band is as high as 0.6,and the emissivity of MoTi2C3Tx film in the middle and far infrared band is close to that of Ti3C2Tx film,which is about 0.3(Table 1 )[36]。 Therefore,the infrared properties and applications of MXene materials described below in this paper are represented by Ti3C2Tx,which are widely studied at present 。
图3 Ti3C2Tx MXene的近红外和中远红外光学性质：（a）椭圆形Ti3C2TxMXene 耦合的模拟吸收光谱和LSPR的电场强度图[43]；（b）MXene 纳米片的计算吸收光谱[44]；（c）MXene的可见光\近红外高吸收率、低红外发射率示意图；（d）真空抽滤Ti3C2TxMXene膜的介电常数实部（ε1）和虚部（ε2）（负的 ε1 值表示金属响应）；（e）MXene膜的红外吸收光谱[22]；（f）MXene、GO、石墨烯、不锈钢薄膜和MMT在508 ℃热源上的红外图像[46]

Fig. 3 NIR and mid- and far-infrared optical properties of Ti3C2Tx MXene, (a) Simulated absorption spectra of elliptical Ti3C2Tx MXene couplings and electric field intensity maps of LSPR[43]; (b) Calculated absorption spectra of MXene nanosheets [44] （Copyright 2021, Royal Society of Chemistry）; (c) Schematic diagram of visible/near-infrared high absorptivity, low infrared emissivity of MXene; (d) Vacuum pumped Ti3C2Tx MXene film with real (ε1) and imaginary (ε2) parts of the dielectric constant (negative ε1 values indicate metal response); (e) infrared absorption spectra of the MXene film [22] (Copyright 2023, Springer); (f) infrared images of MXene, GO, graphene, stainless steel film, and MMT on a heat source of 508 ℃[46](Copyright 2021, Wiley)

表1 Infrared emissivity of different MXene[36]

Table 1 Infrared emissivity of different MXene[36]

MAX Phase MXene visible image infrared emissivity
0.76~1.2 μm 3~5 μm 8~14 μm
Ti2AlC Ti2CTX 0.86 0.35 0.20
Nb2AlC Nb2CTX 0.74 0.62 0.57
V2AlC V2CTX 0.72 0.37 0.29
Ti0.4Nb1.6AlC Ti0.4Nb1.6CTX 0.67 0.53 0.50
Ti1.6Nb0.4AlC Ti1.6Nb0.4CTX 0.79 0.42 0.25
Ti3AlC2 Ti3C2TX 0.62 0.10 0.06
Ti3AlCN Ti3CNTX 0.61 0.21 0.13
Nb4AlC3 Nb4C3TX 0.87 0.65 0.47
V4AlC3 V4C3TX 0.75 0.40 0.24
Mo2Ti2AlC3 Mo2Ti2C3TX 0.57 0.42 0.31

2.1 Near infrared optical properties

Localized surface plasmon resonance(LSPR)of MXene is similar to that of noble metals(gold,silver,copper,etc.),that is,the photon frequency in the near-infrared band matches the electronic vibration frequency of MXene nanoparticles,MXene has a strong absorption of photon energy,and a strong resonance absorption peak appears in the near-infrared spectrum[37⇓⇓~40][41][42]。 Goncalves et al.Theoretically analyzed the near-infrared optical properties of Ti3C2Tx MXene nanosheets(Figure 3A),and calculated the absorption cross-section using the dielectric constant of the existing experimental data,and found the quadrupole surface plasmon resonance phenomenon in Ti3C2Tx MXene nanoparticles for the first time[43]。 Mokkath et al.Performed quantum mechanical simulation using time-varying density functional theory to study the electric field confinement and local surface plasmon resonance of monolayer Ti3C2Tx MXene nanoclusters containing surface groups such as O2-and F-,and found that surface plasmon resonance and broadband absorption spectra appeared in the near-infrared region(Figure 3B )[44]。 On this basis,Muhammed et al.Continued to study the surface plasmon resonance effect of M element(Ti or V)and surface groups on M2CTx MXene nanosheets,and found that the strongest and narrowest LSPR infrared absorption peak appeared with the largest out-of-plane dipole moment of Ti2CFO MXene nanosheets[45]。 Due to the excellent optical properties of MXene in the near infrared,there is increasing interest in using it as a plasma substrate,broadband absorber。

2.2 Middle/far infrared optical properties

Compared with the research of MXene in the near infrared,it tends to be applied in the middle/far infrared,and the theory of low emissivity in the infrared is still lack of in-depth exploration.The MXene material shows low emissivity in both the mid-infrared(3–5μm)and far-infrared(8–14μm)bands in the infrared atmospheric window,and the far-infrared has a lower emissivity than the mid-infrared,but the Ti3C2Tx MXene is less than 0.2(Fig.3e )[36]。 In addition,due to the different processes of MXene etching,intercalation and film formation,the infrared emissivity is different[47]。 Li et al.Found that the Ti3C2Tx MXene film has low mid-infrared emissivity(0.1)and high visible light absorptivity(0.9),which is an intrinsic black solar absorption material with excellent spectral selectivity(Figure 3C )[22]。 In addition,it is found that the infrared emissivity is directly affected by the orientation and end groups of Ti3C2Tx MXene nanosheets,which can be controlled by improving the etching process and optimizing the design of surface groups.The ultrathin flexible film of Ti3C2Tx MXene with a thickness of 1μm was prepared by vacuum filtration film formation by Li et al.,and the emissivity in the far-infrared(7–14μm)band was close to that of stainless steel materials,reaching 0.19(Fig.3F),which was much lower than that of other two-dimensional nanomaterials such as graphene oxide(GO),montmorillonite(MMT)and graphene(Table 2 )[46]。 in addition,due to the unique high conductivity,easy processability and surface characteristics of MXene materials,MXene can be compounded with different emissivity materials or regulated In a high range of infrared emissivity by means of external electric field and structural state change[48,49]。 The low infrared emissivity and high adjustability of MXene provide feasibility for many infrared fields,such as photothermal conversion,multi-spectral camouflage,heat insulation and anti-counterfeiting,passive radiation heating and infrared identification。
表2 Infrared emissivity of MXene and common two-dimensional nanomaterials (background temperature 510.9 ℃)[46]

Table 2 Infrared emissivity of MXene and common 2D nanomaterials(background temperature 510.9℃)[46]

material visible image Thicknesses/μm Tr/℃ Tdecrese/℃ emissivity/7~14 μm
MXene 45 181 319.9 0.19
Graphene 45 223 287.9 0.33
GO 10 294 216.9 0.65
MMT 35 421 89.9 0.88
Stainless steel 30 159 351.9 0.14

3 Study on Infrared Application of MXene

3.1 Broadband absorber

Metamaterial absorbers are generally developed using noble metals such as gold,silver,and tungsten as periodic conducting unit materials to achieve uniform absorptivity over a wide spectral range and are insensitive to polarization and angle changes[50⇓~52]。 Because of the metal-like surface plasmon resonance and excellent processability of MXene,it can replace precious metals to develop MXene-based metamaterial absorbers[53⇓~55]。
A typical MXene-based metamaterial absorber is composed of a three-layer structure(MXene/SiO2/metal layer).Due to the local surface plasmon resonance(LSPR)effect,the top periodically arranged MXene metasurface can make the incident light penetrate through the interior of the silica substrate,and the bottom metal layer can perfectly reflect the incident light to improve the light capture through the multiple reflection effect.Abou Houran et al.Designed a broadband metamaterial absorber with high tunability and high absorption based on Ti3C2Tx MXene[56]。 The top of the absorber is composed of a sub-wavelength periodic MXene thin layer nanometasurface,and the middle and bottom layers are made of silica glass substrate and silver(Ag),respectively(Fig.4A,B).After optimizing the structure size of each part,the absorber shows an absorption rate of more than 80%in a wide range of 1.15~2.5μm(Fig.4C).Chaudhuri et al.Fabricated a broadband plasmonic metamaterial absorber using Ti3C2Tx MXene(Fig.4D),which exhibited strong localized surface plasmon resonance in the near-infrared band[57]。 By using the intrinsic optical properties of MXene and the scattering enhancement effect at the resonance,a high absorption rate of more than 90%can be achieved over a large operating bandwidth(~1.55μm).the MXene-based metamaterial near-infrared broadband absorber accelerates the application research of MXene in the fields of optoelectronic materials,photothermal conversion,sensing,biomedical imaging and other nanophotonics。
图4 （a）MXene超表面吸收器示意图；（b）MXene超表面吸收器面板三维图；（c）MXene超表面吸收器近红外吸收率[56] ；（d）MXene超材料吸收器三维示意图；（e）吸收器垂直截面电场图（λ~ 1.85 μm）；（f）MXene及不同衬底材料模拟吸收光谱[57]

Fig. 4 (a) Schematic diagram of MXene supersurface absorber; (b) 3D view of MXene supersurface absorber panel; (c) NIR absorptivity of MXene supersurface absorber [56] (Copyright 2023, Elsevier Science); (d) 3D schematic diagram of MXene metamaterial absorber; (e) Electric field map of vertical cross section of absorber (λ~ 1.85 μm); (f) Simulated absorption spectra of MXene and different substrate materials[57] (Copyright 2018, American Chemical Society)

3.2 Infrared camouflage

Unlike the active detection principle of visible light and radar,which uses reflected signals to obtain effective information,infrared detection is more passive and necessary because any object above absolute zero will emit infrared radiation energy[58,59]。 It is an effective way to reduce the infrared radiation intensity of the target and the difference between the infrared radiation of the background environment by controlling the surface temperature and infrared emissivity of the target[59⇓~61]。

3.2.1 Infrared low emissive material

The two film-forming processes of MXene materials are vacuum filtration and coating(Fig.5A,d)[62⇓~64]。 The mid-infrared emissivity of 1μm-thick ultrathin Ti3C2Tx MXene film prepared by vacuum filtration can reach 0.19,which is a potential infrared low-emissivity material(Fig.5B,C )[46]。 The infrared emissivity and mechanical properties can be further improved by more regular and dense film structures and materials.Ma et al.Used the coating method to prepare a more regular and compact Ti3C2Tx MXene film(Fig.5e),the far-infrared emissivity at 7–14μm reached 0.14(Fig.5F,G),and the conductivity（8000 S∙cm-1）and mechanical properties of the Ti3C2Tx MXene film were also significantly improved[65]。 Deng et al.Prepared highly densified and oriented MXene coatings by using catecholamine molecular micro-crosslinked platelet Ti3C2Tx MXene to improve its rheological properties[66]。 Due to the higher compactness and fewer structural defects of the prepared MXene coating,compared with the vacuum filtration Ti3C2Tx MXene membrane,the MXene coating has higher conductive（4431 S∙cm-1）,and when the thickness is 3μm,the mid-infrared emissivity of the prepared MXene coating and the vacuum filtration MXene membrane(0.171)is close to 0.179.Liu et al.Combined a series of catechol-based water-soluble polyacrylate polymers with Ti3C2Tx MXene through a facile colloidal self-assembly method to prepare a strong and multifunctional MXene nano-biomimetic film with pearl-like structure,with infrared emissivity<0.2 in the infrared band of 2.5–15.4μm,and mechanical strength and toughness of 123.61 MPa and 1.81 MJ·m-3,respectively[67]。
图5 （a）MXene制备及抽滤成膜示意图[72]；（b、c）真空抽滤MXene薄膜飞机模型和手掌的红外伪装热成像图[22]；（d）涂层制备MXene膜示意图；（e）涂层制备MXene膜照片；（f、g）12.2 μm涂层制备MXene膜在手掌与人面部的红外热成像图[65]；（h）三明治状复合材料结构图；（i）三明治状复合材料横向红外热成像图[72]；（j）头足类动物皮肤信号变化概念图；（k）MXene 机器人皮肤随应变变化示意图；（l）MXene机器人皮肤模拟电场分布图[76]

Fig. 5 (a) Schematic diagram of MXene preparation and filtration into film[72] (Copyright 2023, Wiley); (b, c) Infrared camouflage thermography of vacuum-filtered MXene film airplane model and palm [22] (Copyright 2023, Springer); (d) Schematic diagram of coating-prepared MXene film; (e) Photographs of the coating-prepared MXene film; (f, g) Infrared thermography of the 12.2 μm coating-prepared MXene film in the palm of the hand and human face[65] (Copyright 2023, Elsevier); (h) structural diagram of sandwich-like composite; (i) transverse infrared thermography of sandwich-like composite [72] (Copyright 2023, Wiley); (j) conceptual diagram of cephalopod skin signal variation; (k) schematic diagram of MXene robot skin variation with strain; (l) simulated electric field distribution of MXene robot skin [76] (Copyright 2022, Wiley)

3.2.2 Infrared low emission MXene composite

In order to improve the problems of poor thermal insulation performance and poor spectral selectivity of single MXene film,MXene composites can be developed by adding other components[68⇓~70]。 At present,thermal insulation materials and phase change materials are mainly added on the basis of MXene film to improve its overall infrared camouflage performance[71]。
Jing et al.Developed a three-layer composite made of crosslinked polyimide aerogel,phase change composite erythritol(mE)and infrared low-emissivity Ti3C2Tx MXene film,which can realize long-term infrared camouflage under high temperature conditions[72]。 The PI aerogel in the lower layer plays the role of thermal insulation through the layered structure,the phase change material in the middle layer plays the role of dynamic temperature regulation through latent heat absorption and sensible heat,and the MXene film in the top layer provides low infrared emissivity(Figure 5h).The emissivity in the specific wavelength range of 3~5 and 8~14μm is 0.315 and 0.253,respectively.The composite has excellent high temperature thermal camouflage performance(Fig.5i)and electromagnetic shielding performance.In addition,it is found that the thermochromic coating added on the surface of the composite material can adaptively change color to achieve the synergistic camouflage of infrared and visible light.Li et al.Prepared a hybrid aerogel by using Ti3C2Tx MXene and reduced graphene oxide,introduced octadecyl phase change material into the lower layer of MXene/RGO aerogel,and coated a thermochromic coating on its surface to prepare a three-layer composite material that can be camouflaged synergistically in the visible/infrared band[73]。 Due to the dynamic temperature regulation effect of the phase change material and the good thermal insulation performance of the porous aerogel material,the composite material can reduce the temperature difference between the measured target and the surrounding environment by 0.9 deg C,and realize good infrared camouflage performance at the temperature of 0-50 deg C.In addition,at present,the Ti3C2Tx MXene mainly used is dark and has high visible light absorption rate,so the light-colored MXene with excellent infrared performance can be selected to prepare infrared camouflage materials through further exploration of MXene with different colors,so as to reduce the problem of poor infrared camouflage performance caused by high visible light absorption and rapid temperature rise 。

3.2.3 Infrared emissivity dynamic adjustable material

infrared variable emissivity materials are expected to adapt to The current complex battlefield environment.the Infrared emissivity of MXene materials is expected to be regulated by surface end group modification,substrate optimization,ion intercalation and other processes[74]。
Lu et al.Fabricated an electrochromic device with the ability of dynamic infrared radiation adjustment by using the principle of ion intercalation of Ti3C2Tx MXene materials[75]。 Compared with the traditional electrochromic device,the solution synthesis method of the device is simple in preparation process,does not need to introduce an additional metal electrode as a conductive layer,and is convenient for large-scale application.The maximum emissivity changes are 0.31,0.24,and 0.23 in the 3–5μm,8–14μm,and 2.5–18μm bands,respectively,through the free O-terminal group changes induced by Li-ion intercalation/de-intercalation.Inspired by cephalopod skin(Figure 5j),Li et al.Used two-dimensional Ti3C2Tx MXene materials to prepare a robot skin with adjustable emissivity by interface engineering[76]。 the MXene fold texture of the robot skin can maintain a good interface effect with the elastic rubber substrate,and the reversible folding/flattening process can realize the reversible conversion between low infrared emissivity(≈0.3 in the flattening stage)and high infrared emissivity(0.8 in the folding stage)(Fig.5K,l)。

3.3 Photothermal conversion

Photothermal conversion is a process that converts sunlight into heat[77⇓⇓~80]。 in order to improve the photothermal conversion efficiency of the material,the ideal photothermal conversion material should have high selective absorption in the wide solar spectral range(0.3~2.5μm)and low emissivity in the infrared band(2.5~20μm)to suppress the thermal radiation loss of the material[81,82]。 MXene has excellent spectral selective absorption characteristics,high absorptivity(more than 90%)in visible and near-infrared bands,and low emissivity(0.1)in mid-infrared bands.It is an ideal photothermal replacement material and plays an important role in thermal energy storage,building insulation,seawater desalination,sterilization,cancer therapy and other fields[83⇓⇓⇓~87]。
Zuo et al.Fabricated an MXene/PEG composite with both photothermal conversion and thermal energy storage capabilities by using Ti3C2Tx MXene nanosheets as the substrate to encapsulate PEG PCMs(Figure 6A )[88]。 Due to The localized surface plasmon resonance effect of the MXene nanosupport material in the near-infrared band,the composite PCM achieves an excellent photothermal conversion efficiency of 94.5%in the visible/near-infrared region.the high specific surface area and photothermal conversion efficiency of MXene have also attracted great attention of researchers in near-infrared photothermotherapy[89]。 Yu et al.Used a fluorine-free method to synthesize a biocompatible Ti3C2Tx MXene efficient photothermal agent,and the prepared MXene QD had an extinction coefficient of up to 52.8 Lg-1•cm-1at 808 nm and a photothermal conversion efficiency of 52.2%;in addition,the photothermal agent also had good biocompatibility[90]。 Lu et al.Used polydopamine(PDA)to modify the surface of two-dimensional niobium carbide（Nb2C）MXene below 80 nm,and prepared a near-infrared photothermal agent with high stability and low toxicity(Fig.6B )[91]。 the photothermal agent showed extremely high photothermal conversion efficiency and tissue penetration depth under near-infrared infrared-II and 1064 nm laser irradiation,and could perform high-precision in vivo thermal ablation of tumors in mice.By rationally designing the composition of 2D MXenes and exploring their related physicochemical properties,the application prospects of 2D MXenes have been greatly broadened,especially in cancer phototherapy。
图6 （a） MXene/PEG复合材料的光热转换和热储能示意图[88]；（b）基于二维 Nb2C MXene近红外-Ⅱ光热疗法的多功能纳米平台[91]

Fig. 6 (a) Schematic diagram of photothermal conversion and thermal energy storage of MXene/PEG composites[88] (Copyright 2016, Royal Society of Chemistry); (b) Multifunctional nanoplatform based on two-dimensional Nb2C MXene near infrared-Ⅱ photothermal therapy[91] (Copyright 2021, Royal Society of Chemistry)

3.4 Passive radiation heating

With the frequent occurrence of global extreme climate and the increasing emphasis on low-carbon sustainable development,people have found a new strategy of more energy-saving and environmental protection in the external temperature regulation(air conditioning)and personal thermal management[92⇓⇓⇓~96]。 Compared with the large area heating of the space around the human body,effective personal thermal management can increase the setting range of the ambient temperature and avoid a large waste of global energy[97⇓⇓~100]。 Passive radiant heating textiles offer the feasibility of improving human thermal comfort without increasing energy costs[101⇓⇓~104]。
Based on the unique low mid-infrared emissivity of MXene material,Dong et al.Sprayed the Ti3C2Tx MXene material on the polyester polyurethane blended fabric to prepare an MXene composite polyester polyurethane blended fabric(MP fabric)for passive personal thermal management(Fig.7 a )[105]。 Compared with traditional fabrics(polyester fabrics,cotton fabrics,etc.),the prepared MP fabric can increase the temperature of human skin by 2.68℃(Fig.7B),which can effectively inhibit the thermal radiation loss of human body.For MXene passive heating fabric,people have carried out a wide range of exploration on the substrate,and found that the infrared transparent nano-polyethylene material as the substrate has more excellent passive radiation performance[106⇓~108]。 Shi et al.Used Ti3C2Tx MXene to modify nano-polyethylene textiles and prepared ultra-thin passive radiation heating MXene/nanoPE textiles with a thickness of 12μm(Fig.7 C )[109]。 Due to the infrared transparency of the nanoPE substrate,the infrared emissivity(7~14μm)εof the fabric MXene side and nanoPE side are 0.176 and 0.267,respectively,which are much lower than that of the cotton textile(0.931).The temperature of real human skin covered by MXene/nanoPE textile is 4.9℃higher than that covered by cotton fabric(Fig.7 d),which has better passive radiation heating performance.Because of the diversified color requirements of clothing,the color characteristics of different MXene materials can be studied in the later stage to improve the single color problem of passive radiation heating fabrics in Ti3C2Tx MXene and accelerate its popularization and application 。
图7 （a）Ti3C2Tx MXene与PU/PET织物的制备示意图；（b）覆盖不同织物的人造皮肤实时温度[105]；（c）MXene与纳米PE纺织品的制备示意图及被动辐射加热原理；（d）覆盖不同织物的人造皮肤实时温度（室内环境、27 ± 0.5 ℃）[109]

Fig. 7 (a) Schematic of the preparation of Ti3C2Tx MXene with PU/PET fabrics; (b) Real-time temperature of artificial skin covering different fabrics [105] (Copyright 2023, American Chemical Society); (c) Schematic of the preparation of MXene with nano-PE textiles and the principle of passive radiant heating; (d) Real-time temperature of artificial skin covering different fabrics (indoor environment, 27 ± 0.5 ℃) [109] (Copyright 2021, American Chemical Society)

3.5 Infrared photoelectric detection

infrared photoelectric detection is a process in which the conductivity of a photoelectric sensing material changes after absorbing the infrared radiation transmitted by an object under an atmospheric window,and the infrared radiation characteristics of the object are visualized after the electrical signal is processed.It is mainly used in biomedicine,night vision,precise image sensing,remote sensing,communications,visual simulation and other fields[110⇓~112][113⇓~115]。 By using the conductivity and plasma resonance of MXene,high absorption can be achieved in the near-infrared band,which can effectively improve the photoelectric performance of photoelectric detection elements[116,117]。 However,at present,MXene materials can not convert their own signals through selective absorption of infrared radiation,and it is expected to expand the effective regulation of MXene materials in infrared detection performance through ion intercalation and surface end group modification in the later stage。
Liu et al.Fabricated a heterostructure self-powered photodiode operating in the visible/near-infrared region(Figure 8 a)by using the high plasmon resonance absorption effect of niobium carbide（Nb2CTx）MXene heterostructure in the near-infrared band and lead triiodide methylammonium（MAPbI3）perovskite with a matched ribbon structure,which has a broadband photoelectric detection function[118]。 The diode has a good linear response to visible light,with a responsivity of 0.25 A/W and a time response of less than 4.5μs(Figure 8 B).In the near-infrared range,the switching ratio（103）and response time(<30 ms)are faster than those of the pure planar niobium carbide（Nb2CTx）MXene(Fig.8 C,d).Shen et al.Found that the abundant surface end group—OH of Ti3C2Tx MXene provided the feasibility for the formation of van der Waals hydrogen-bonded heterostructure with organic photosensitive materials(RNA),thus effectively improving the near-infrared photodetection performance(Fig.8e )[119]。 The prepared heterostructure Ti3C2Tx-RAN near-infrared photodetector based on the combination of organic/inorganic van der Waals forces has a larger on-off ratio of Ti3C2Tx-RAN than that of the Au-RAN photoluminescence device under the irradiation of infrared lasers with different wavelengths of 915,1064,and 1122 nm,and especially under the excitation of 1064 nm laser,the on-off ratio of the Ti3C2Tx-RAN photoluminescence device is 6.25 times that of the Au-RAN photoluminescence device(Figure 8 f).In addition,it has good mechanical properties and cycle stability 。
图8 （a）MAPbI3/Nb2CTx 界面外电荷转移和SP示意图；（b）器件在532 nm LED照明下的上升和衰减时间；（c）器件在1064 nm 激光强度下电流；（d）与时间相关的电流显示上升和衰减时间[118]；（e）异质结构Ti3C2Tx-RAN 近红外光电探测器结构示意图；（f）Au-RAN PD 和 Ti3C2Tx-RAN PD的通断比比较[119]

Fig. 8 (a) Schematic of charge transfer and SP outside the MAPbI3/Nb2CTx interface; (b) Rise and decay times of the device under the illumination of a 532 nm LED; (c) Device current at 1064 nm laser intensity; (d) Temporal dependent current to show the rise and decay time [118] (Copyright 2022, American Chemical Society) (e) Schematic of the structure of the heterostructured Ti3C2Tx-RAN near-infrared photodetector; (f) Comparison of the on/off ratios of the Au-RAN PDs and Ti3C2Tx-RAN PDs [119] (Copyright 2022, Wiley)

4 Conclusion and prospect

as an excellent two-dimensional layered material,MXene has many excellent properties,such As high specific surface area,high conductivity,high mechanical strength,hydrophilicity and tunability of surface active groups.Great progress has been made in battery materials,supercapacitors,optoelectronic devices,water purification,biomedicine,electromagnetic shielding and other fields,but the infrared properties and applications of MXene have just started,and it is becoming a new research direction for researchers.However,there are still some problems in the development of MXene in the field of infrared application(Fig.9)。
图9 MXene红外领域发展存在的问题

Fig. 9 Problems in the development of the MXene in infrared field

(1)MXene materials have poor oxidation stability in humid and aerobic environment.titanium carbide MXene will form Titanium dioxide after being oxidized,which greatly reduces its infrared optical properties and limits its application in the infrared field.Solving the oxidation problem of MXene materials is the key to the rapid development of the infrared field。
(2)There is still a lack of theoretical research on the basic properties of MXene materials in the middle/far infrared band,and it is expected to provide more systematic infrared optical properties for the infrared application of MXene materials through the overall exploration of different MXene materials and different surface groups in the later stage。
(3)the surface state and conductivity of MXene film have a great influence on the infrared performance of MXene material.Through the further optimization of MXene film formation process and structure,the development speed of MXene in infrared camouflage,broadband absorber and other infrared fields can be effectively accelerated。
(4)Titanium carbide MXene has the problems of high absorbance and poor thermal insulation in the field of infrared camouflage due to its intrinsic dark color,which easily leads to the increase of the temperature of MXene camouflage layer and the increase of the overall infrared radiation,affecting the infrared camouflage performance。
(5)In the field of personal thermal management,titanium carbide MXene is mainly used to prepare passive radiation heating fabrics at present,which has the problem of ineffective color diversification.In the later stage,the color of passive radiation heating fabrics can be expanded to accelerate its popularization and application process。
(6)The photothermal conversion system of MXene is mainly used in thermal energy storage,seawater desalination,hyperthermia and other emerging fields.The application stability in different extreme environments(biological environment,high heat,high salt,high humidity,etc.)Needs further exploration。
(7)In the field of infrared optoelectronics,it is still the key development direction to study the selective absorption of infrared radiation by MXene for effective optoelectronic signal conversion。
(8)By using the ion intercalation and surface end group modification of MXene materials,it is expected to achieve the synergistic effect of infrared(selective regulation of emissivity in different infrared bands),visible light and electromagnetic shielding,and intelligent adaptive dynamic camouflage。
to sum up,although there are many challenges in the development of MXene materials in the infrared field,with the continuous discovery of new characteristics,new structures and new components of MXene materials,it is believed that the research on MXene materials in the infrared field will continue To mature。

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