二维MXene材料——Ti3C2Tx在钠离子电池中的研究进展

作为第一个被制备出来的MXene材料,Ti₃C₂T_x独特的二维层状结构使其具有良好的电学、光学、力学与热电等性质,在电化学储能领域展现出巨大的潜力。由于钠储量在地球中较为丰富且远高于锂储量,因此钠离子电池具有成本低等优点,成为近几年储能领域的研究热点。主要围绕Ti₃C₂T_x的特性,介绍了其通过插层、造孔等改性方法以及与单质、金属氧化物、金属硫化物结合构成复合材料作为钠离子电池电极材料的研究进展。最后指出应采取基于钠离子脱嵌或反应的更有针对性的优化方法提升总体的电化学性能。     

超级电容器用二维Ti3C2Tx过渡金属碳/氮化物材料的研究进展

近年来二维过渡金属碳/氮化物(MXene)材料由于其独特的物理/化学性能,在储能领域引起广泛的关注。其中以二维Ti3C2Tx材料的研究最为普遍。MAX相是一类三元氮化物和/或碳化物,其化学式为Mn+1AXn (n=1~3),M代表过渡金属元素(如Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo等),X是碳和/或氮,A主要是IIIA或IVA族元素。根据n不同,MAX相的晶体结构包括3种类型。MAX相中,M?X和M?A键强度都很高。无法通过剪切或其它机械方法分层剥离。由于M?A键比M?X键具有更高的化学活性,可以通过化学刻蚀M?A键并辅助剥离方法获得单层/少层的MXenes材料。表面基团随机分布,对电化学性能有重要的影响。调控表面基团的种类和数量是当前研究的重要内容。本工作介绍了MXene相的基本结构,分析了相结构与性能的关系。总结了通过离子插入、热处理、表面改性、电极设计和元素掺杂等手段改善MXene相材料电化学性能的研究进展,简要介绍了MXenes与碳材料、氧化物、聚合物复合在超级电容器领域中的应用进展。对MXene相材料的结构、制备及电化学性能等方面进行了综述,指出了MXene相材料用于超级电容器领域存在的主要问题及未来的发展方向。     

Broadband electromagnetic absorption of Ti3C2Tx MXene/WS2 composite via constructing two-dimensional heterostructure

Ti₃C₂T_x MXene, an emerging two-dimensional (2D) ceramic material, has rich interfaces and strong conductive networks. Herein, we have successfully built a heterostructure between Ti₃C₂T_x MXene and WS₂ to improve electromagnetic absorption performance. X-ray diffraction and X-ray photoelectron spectroscopy were used to determine the successful synthesis of Ti₃C₂T_x/WS₂ composite. Field emission scanning electron microscopy and transmission electron microscopy images show that WS₂ nanosheets are evenly dispersed on the accordion-like Ti₃C₂T_x MXene. Importantly, Ti₃C₂T_x MXene/WS₂ composite has sufficiently high dielectric loss and impedance matching due to self-adjusting conductivity and 2D heterostructure interfaces. As a result, the Ti₃C₂T_x/WS₂ composite has a minimum reflection loss (RL_min) of −61.06 dB at 13.28 GHz. Besides, it has a broad effective absorption bandwidth (EAB) of 6.5 GHz, with EAB >5.0 GHz covering a wide range of thickness. Such impressive results may provide experience for the application of Ti₃C₂T_x ceramics and 2D materials.     

酚醛树脂/Ti3C2TxMXene导电复合材料制备与性能

通过氢氟酸溶液刻蚀Ti3AlC2 MAX粉末制得Ti3C2TxMXene纳米片。然后,采用溶液共混的方法制备了酚醛树脂/Ti3C2TxMXene导电复合材料。通过X射线衍射、扫描电子显微镜等手段对其结构、微观形貌及性能进行表征。结果表明:Ti3C2TxMXene纳米片均匀分散在酚醛树脂里面,形成良好的导电通路。探讨Ti3C2TxMXene纳米片的用量对复合材料的导电性能和力学性能的影响。结果表明:酚醛树脂/Ti3C2TxMXene导电复合材料的电导率,冲击强度和拉伸强度随Ti3C2TxMXene纳米片含量的增加而逐渐增加;当Ti3C2TxMXene纳米片的含量为1.2%时,酚醛树脂/Ti3C2TxMXene导电复合材料的综合性能最优,此时酚醛树脂/Ti3C2TxMXene导电复合材料的电导率为4.36×104 S/m,冲击强度和弯曲强度分别为23.9 kJ/m2和65.9 MPa。     

Ti3C2Tx/Ni/TiO2复合粉体的制备及吸波性能研究

采用热处理的方法制备出二维层状Ti3C2Tx/Ni/TiO2复合粉体,并利用TG-DSC、SEM、XRD和XPS对样品进行表征分析,通过矢量网络分析仪测试样品的电磁参数并模拟计算不同涂层厚度下样品的反射损耗值(RL).结果表明:随着热处理温度的升高,样品中TiO2质量含量增加;当热处理温度为300℃时,在频率f=17....     

Effects of expandable graphite on char morphology and pyrolysis of epoxy based intumescent fire-retardant coating

The current study was designed to investigate the effects of expandable graphite (EG) on fire protection properties of intumescent fire-retardant coating for steel structures. Several formulations of intumescent coating were prepared and tested according to ISO 834 for char expansion. The chars were found without cracks and bonded with the steel substrate. The results showed that the coating slowly degraded during the test and char remained in contact with vertically tested coated substrate. The coated substrates were also tested for weather resistance using humid and ultraviolet environment. The char was characterized by using FESEM, XRD, FTIR, TGA, and XPS analysis. FESEM examined char morphology of the coatings after furnace fire test. XRD and FTIR showed the presence of graphite, borophosphate; boron oxide and sassolite in the char. TGA and DTGA results disclosed that EG improved the residual mass of coating. XPS analysis showed the percentages of carbon and oxygen are 48.50 and 43.45 in char of formulation with 12.8% EG. The results of weathering test coatings showed decreased in char expansion because of a humidity and UV light. The formulation with 9.8% EG showed the maximum char expansion and high residual mass among the formulations investigated in this study. The weathering tested coated samples showed their capability of fire protection.     

Microstructure and tribological behavior of Ti3C2Tx MXene reinforced chemically bonded silicate ceramic coatings

MXenes – In recent decades, great attention has been paid to the fast-growing two-dimensional (2D) transition metal carbides and nitrides, in terms of their prominent mechanical and electrical properties. The tribological essence of MXene has not yet been entirely investigated, although researches on MXene were conducted in all aspects of its applications. Hence, a newly compound 2D MXene (Ti₃C₂T_x) is exploited to reinforce the wear resistance of the chemically bonded silicate ceramic coatings, which are utilized to protect component surfaces under severe conditions. The structural features, hardness, and tribological behaviors of the targeted coatings are investigated and analyzed. Results show that the micro-hardness of the coatings increases to 156.9 HV_0.5 when added 1.2 wt% MXene. The increment of microhardness extraordinarily reaches 33.3%, compared with the original. The coating with 1.2 wt% MXene also indicates a 31.6% decrement of the coefficient of friction (COF) and a 73% reduction of the wear rate respectively. Furthermore, fatigue is found to be the main reason of the wear mechanism, through exploring the surface morphologies of wear traces and counterpart balls.     

Synthesis,characterization and antifungal property of Ti3C2Tx MXene nanosheets

Although the antibacterial properties of MXene nanosheets containing Ti₃C₂T_x are known, their antifungal properties have not been well studied. Herein, we present for the first time a report on the antifungal properties of Ti₃C₂T_x MXene. The Ti₃C₂T_x MXene was obtained by first exfoliating MAX phase of Ti₃AlC₂ with concentrated hydrofluoric acid, then the Ti₃C₂T_x was intercalated and deliminated by ethanol treatment and ultrasonication process. The delaminated Ti₃C₂T_x MXene nanosheets (d-Ti₃C₂Tx) were characterized using field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray (EDX), X-ray diffraction spectroscopy (XRD), and Raman spectroscopy. It was found that Ti₃C₂T_x MXene was characterized by lamellar structure alternating with layers of Ti, Al and C. The EDX results revealed that the delaminated Ti₃C₂T_x MXene nanosheets were composed of Ti, C, Si, O, F, and a trace amount of Al. The XRD and Raman spectra further indicated the elimination of Al and the formation of two-dimensional Ti₃C₂T_x MXene nanosheets. The antifungal activity of the delaminated Ti₃C₂T_x MXene was determined against Trichoderma reesei using the modified agar disc method. Observation using inverted phase contrastmicroscopy revealed inhibited fungus growth with the absence of hyphae around the discs treated wtih MXene. The surrounding of the control groups without an inclusion of MXene was found with large number of hyphae and spores. In addition, the spores of the fungi treated with the samples containing d-Ti₃C₂T_x MXene nanosheets did not germinate even after 11 days of culture. The results demonstrated disruption to the hemispheric structural formation of fungi colony, inhibition of hyphae growth and cell damage for fungi grown on the d-Ti₃C₂T_x MXene nanosheets. These new findings suggest that d-Ti₃C₂T_x MXene nanosheets developed in this work could be a promising anti-fungi material.     

The influence of ceramic additives on intumescence and thermal activity of epoxy coatings for steel

The article presents results of the research on the influence of graphite/kaolin and graphite/titanium oxide systems on thermal properties, intumescence degree and the integrity of the structure of intumescent protective films based on epoxy resins for steel. The TG/DTG/DSC analysis showed that graphite/kaolin system shifted the decomposition reaction of epoxy resin towards higher temperatures, even by about 30°C. Fire endurance tests and the SEM analysis confirmed these results because more thermally resistant (T_500°C reached after 37.5 min for 1.1 coating thickness), swollen (about 20 times) and homogeneous coatings were obtained. The presented results suggest that ceramic fire retardants can successfully cooperate with organic components in intumescent protective coatings for steel elements.     

Novel strategy for molybdenum disulfide nanosheets grown on titanate nanotubes for enhancing the flame retardancy and smoke suppression of epoxy resin

A novel hybrid consisting of a molybdenum disulfide (MoS₂) coating on a titanium dioxide nanotube (TNT) surface (MoS₂–TNT) was synthesized by a hydrothermal method. The MoS₂, TNTs, and MoS₂–TNT hybrid were incorporated into epoxy resin (EP) to study their effects on its thermal performance and flame retardancy. Thermogravimetric analysis results show that the char yield at 700 °C of EP–MoS₂–TNTs was obviously increased compared with that of the EP–MoS₂ or EP–TNTs; this indicated that MoS₂–TNTs had a good carbonization effect. The limiting oxygen index, cone calorimetry, and smoke density tests showed that MoS₂–TNTs effectively improved the flame retardancy and smoke suppression of EP. This was attributed to the physical barrier effect of MoS₂ and the adsorption of TNTs. Moreover, the flame retardancy and smoke suppression of the EP–MoS₂–TNTs were better than those of the EP–MoS₂ or EP–TNTs alone with the same amount of addition; this indicated that there was a synergistic effect between MoS₂ and TNTs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46064.     

Adsorption of selected dyes on Ti3C2Tx MXene and Al-based metal-organic framework

MXene and metal organic framework (MOF) were used as the main adsorbents to remove synthetic dyes from model wastewater. Methylene blue (MB) and acid blue 80 (AB) were used as the model cationic and anionic synthetic dyes, respectively. To investigate the physicochemical properties of the adsorbents used, we carried out several characterizations using microscopy, powder X-ray diffraction, a porosimetry, and a zeta potential analyzer. The surface area of MXene and MOF was 9 and 630 m² g⁻¹, respectively, and their respective isoelectric points were approximately pH 3 and 9. Thus, MXene and MOF exhibited high capacity for MB (~140 mg g⁻¹) and AB (~200 mg g⁻¹) adsorption, respectively due to their electrostatic attractions when the concentrations of the adsorbents and adsorbates were 25 and 10 mg L⁻¹. Furthermore, the MOF was able to capture the MB due mainly to hydrophobic interactions. In terms of the advantages of each adsorbent according to our experimental results, MXene exhibited fast kinetics and high selectivity. Meanwhile, the MOF had a high adsorption capacity for both MB and AB. The adsorption mechanisms of both adsorbents for the removal of MB and AB were clearly explained by the results of our analyses of solution pH, ionic strength, and the presence of divalent cation, anion, or humic acids, as well as other characterizations (i.e., Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy). According to our results, MOF and MXene can be used as economical treatments for wastewater containing organic pollutants regardless of charge (e.g., MB and AB), and positively charged one (e.g., MB), respectively.     

Decorating MXene with tiny ZIF-8 nanoparticles: An effective approach to construct composites for water pollutant removal

MXenes have attracted increasing research enthusiasm owing to their unique physical and chemical properties. Although MXenes exhibit exciting potential in cations adsorption due to their unique surface groups, the adsorption capacity is limited by the low specific surface area and undeveloped porosity. Our work aims at enhancing the adsorption performance of a well-known MXene, Ti₃C₂T_x, for methylene blue (MB) by decorating tiny ZIF-8 nanoparticles in the interlayer. After the incorporation of ZIF-8, suitable interspace in the layers resulting from the distribution of tiny ZIF-8 appears. When employing in MB, the adsorption capacity of composites can reach up to 107 mg·g^-1 while both ZIF-8 (3 mg·g^-1) and Ti₃C₂T_x (9 mg·g^-1) show nearly no adsorption capacity. The adsorption mechanism was explored, and the good adsorption capacity is caused by the synergistic effect of ZIF-8 and Ti₃C₂T_x, for neither of them is of suitable interspace or surface groups for MB adsorption. Our work might pave the way for constructing functional materials based on the introduction of nanoparticles into layered materials for various adsorption applications.     

Stretchable,mechanically resilient,and high electromagnetic shielding polymer/MXene nanocomposites

The increasingly disturbing electromagnetic wave pollution has intensified research for high-performance shielding materials to protect humans and the environment. It remains a great challenge to combine high electromagnetic interference (EMI) shielding performance with mechanical robustness and stretchability. These crucial features have been simultaneously achieved in this work by using a facile method to prepare elastomer/MXene nanocomposites. An EMI shielding effectiveness of 49 dB was obtained from a 1-mm thick nanocomposite film at 19.6 vol% of MXene; the film has a density of 1.25 g/cm³. The outstanding electrical conductivity of MXene – 4350 ± 125 S·cm⁻¹ – provided free charge carriers in the matrix to absorb electromagnetic signals, leading to the dominance of absorption mechanism over reflection mechanism. Owing to a nanofiller modification step, the nanocomposite films demonstrated not only outstanding EMI shielding but sufficient strength and stretchability. A nanocomposite at 14.0 vol% exhibited Young's modulus of 15.85 ± 0.75 MPa and tensile strength 25.94 ± 0.81 MPa with elongation at break of 170 ± 5.6%, which relates to high stretchability. These impressive properties make our nanocomposites suitable for use in harsh environments as well as applications in stretchable devices, protective clothing, aerospace, aircraft, and automotive industries.     

一步法合成二维Ti3C2及其电化学性能研究

二维过渡金属碳/氮化物（MXene）是一种新型二维材料,可通过从MAX相前体中选择性刻蚀 A 原子层获得。在传统制备MXene的方法中,常用的刻蚀剂是氢氟酸。然而高浓度氢氟酸的使用,不可避免会带来安全问题,甚至破坏MXene的晶体结构,从而限制本征物理化学性能。从典型的碳化物前体Ti₃AlC₂出发,使用 NH₄BF₄作为刻蚀剂,有效降低体系中酸的使用量;在反应过程中,刻蚀 A 层的同时,\mathrm{N}{\mathrm{H}}_{\mathrm{4}}^{+}进入堆垛层间,扩大层间距,弱化层间作用力。因此,仅通过简单手摇就可以实现高效剥离,得到具有完整晶体结构的二维Ti₃C₂。进一步测试了Ti₃C₂的电化学性能,结果显示,所得的Ti₃C₂具有优异的性能（扫描速率为5 mV?s^-1时为503 F?g^-1）和循环稳定性（在5 A?g^-1下循环10⁴次后电容保持率为95.8%）。本文为Ti₃C₂纳米片的合成及应用提供了新的思路。     

In-situ self-assembly of sandwich-like Ti3C2 MXene/gold nanorods nanosheets for synergistically enhanced near-infrared responsive drug delivery

As a novel two-dimensional material, Ti₃C₂ MXenes has attracted lots of attention in biomedical filed for its large surface area and excellent near-infrared (NIR) responsiveness. In this paper, an in-situ growth and self-assembly approach was employed to combine gold nanorods (GNRs) with Ti₃C₂ nanosheets to prepare intelligent sandwich-like Ti₃C₂@GNRs/PDA/Ti₃C₂ nanohybrids. Compared with Ti₃C₂ nanosheets, in-situ growth Ti₃C₂@GNRs possessed excellent photothermal conversion efficiency (45.89%), caused by the distinguished photothermal synergy between GNRs and Ti₃C₂ nanosheets. Moreover, the high specific surface area of Ti₃C₂ MXene and outstanding adhesion performance of PDA endowed Ti₃C₂@GNRs/PDA/Ti₃C₂ nanohybrids with superior drug loading ability for doxorubicin hydrochloride (DOX) (95.88%). Besides, Ti₃C₂@GNRs/PDA/Ti₃C₂ nanohybrids displayed distinct pH/NIR responsive drug release properties upon NIR irradiation owing to the strong π-π stacking interaction between Ti₃C₂@GNRs/PDA/Ti₃C₂ and DOX, along with the excellent NIR-responsiveness of Ti₃C₂@GNRs/PDA/Ti₃C₂. This paper offers a practicable method to prepare Ti₃C₂ MXene-based nanoplatform with synergistically enhanced NIR drug release behavior, brilliant biocompatibility and high drug loading efficiency, which is expected to be applied in remote cancer therapy.     

Electrochemical storage mechanism of interstratification-assembled Ti3C2Tx MXene/NiCo-LDHs electrode in alkaline,acid and neutral electrolytes

Different kinds of two-dimensional hybrid electrodes have high theoretical capacitance and energy density. However, the origin of the electrochemical storage mechanism still remains elusive in alkaline, acid and neutral electrolytes. Herein, the interstratification-assembled Ti₃C₂T_x MXene/NiCo-LDHs electrodes were successfully prepared and studied in different electrolytes by in-situ Raman spectroscopy. The results show that H₂O molecules in neutral electrolyte combine with –OH at the end of Ti₃C₂T_x MXene during charging, and debonding occurs during discharge. Similarly, this reaction also occurs in the discharge process with NiCo-LDHs and provides smaller pseudocapacitance characteristics. Although this pseudocapacitance reaction also occurs in acidic and alkaline electrolytes, however, the difference is that the hydrogen ions will promote the electrochemical performance of Ti₃C₂T_x MXene and has a certain corrosion consumption effect on NiCo-LDHs, but generally improve the electrochemical performance of Ti₃C₂T_x MXene/NiCo-LDHs. Interestingly, the OH^? in alkaline electrolyte can promote the electrochemical performance of NiCo-LDHs, and produce a new electrochemical reaction with –F between the layers of Ti₃C₂T_x MXene, which greatly improves the overall electrochemical performance of this hybrid electrodes. As a result, Ti₃C₂T_x MXene/NiCo-LDHs electrodes have the best electrochemical performance in alkaline electrolyte with capacitance of 283 F g^?1, energy density of 14.2 Wh kg^?1 and power density of 3007.1 W kg^?1. This work lays a foundation for the preparation of high-performance two-dimensional hybrid electrochemical energy storage devices.     

P-doped MoS2/Ni2P/Ti3C2Tx heterostructures for efficient hydrogen evolution reaction in alkaline media

By combining the advantages of doping to change the electronic structure of molybdenum disulfide (MoS₂), transition metal phosphides, and MXene, we proposed the idea of designing and preparing a new type of composite material, P-doped MoS₂/Ni₂P/Ti₃C₂T_x heterostructures (denoted as P@MNTC), to serve as the hydrogen evolution reaction (HER) catalyst of electrochemical water splitting. The as-prepared P@MNTC heterostructures show a significant HER activity with an overpotential of 120 mV at 10 mA cm^–2 in alkaline electrolyte, with decreasing 105 and 125 mV compared with those of MoS₂ and MXene, respectively. The density functional theory indicates that the P doping and synergy effect of Ti₃C₂T_x can enhance the activation of MoS₂ and thus promote dissociation and absorption of H₂O during HER process. This strategy provides a promising way to develop high-efficiency MoS₂- and Ti₃C₂T_x-based composite catalysts for alkaline HER.     

Preparation and characterization of polymer‐Ti3C2Tx (MXene) composite nanofibers produced via electrospinning

MXene, a recently‐discovered family of two‐dimensional (2D) transition metal carbides and/or nitrides, have attracted much interest because of their unique electrical, thermal, and mechanical properties. In this study, poly(acrylic acid), poly(ethylene oxide) (PEO), poly(vinyl alcohol) (PVA), and alginate/PEO were electrospun with delaminated Ti₃C₂ (MXene) flakes. The effect of small additions of delaminated Ti₃C₂ (1% w/w) on the structure and properties of the nanofibers were investigated and compared with those of the neat polymer nanofibers using scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, and Fourier transform infrared spectroscopy. Ti₃C₂ had an effect on the solution properties of the polymer and a greater effect on the average fiber diameter. The Ti₃C₂T_x/PEO solution exhibited the largest change in viscosity and conductivity with an 11% and 73.6% increase over the base polymer, respectively. X‐ray diffractograms demonstrated a high degree of crystallization for Ti₃C₂/PEO and a slight decrease in crystallinity for Ti₃C₂/PVA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45295.     

Manganese dioxide nanosheets decorated on MXene (Ti3C2Tx) with enhanced performance for asymmetric supercapacitors

The incorporation of nanosized pseudocapacitive materials and structure design are general strategies to enhance the electrochemical performance of MXene-based materials. Herein, the decoration of manganese dioxide (MnO₂) nanosheets on MXene (Ti₃C₂T_x) surfaces was prepared by a facile liquid phase coprecipitation method. Ti₃C₂T_x is initially modified by polydopamine (PDA) coating to ensure the homogeneous distribution of MnO₂ nanosheets and tight and close connections between MnO₂ and the Ti₃C₂T_x backbone. Due to the obtained three-dimensional (3D) nanostructure, facilitating electron transport within the electrode and promoting electrolyte ion accessibility, the δ-MnO₂@Ti₃C₂T_x-0.06 electrode yields superior electrochemical performances, such as a rather large areal capacity of 1233.1 mF cm^?2 and high specific capacitance of 337.6 F g^?1 at 2 mV s^?1, as well as high cyclic stability for 10000 cycles. Furthermore, δ-MnO₂@Ti₃C₂T_x-0.06 composites are employed as positive electrodes, and activated carbon (AC) materials act as negative electrodes with an aqueous electrolyte of 1 M Na₂SO₄ to assemble asymmetric supercapacitors. The prototype device is reversible at cell voltages from 0 to 1.8 V, and manifests a maximum energy density of 31.4 Wh kg^?1 and a maximum power density of 2700 W kg^?1. These encouraging results show enormous possibilities for energy storage applications.     

Improved dielectric and mechanical properties of Ti3C2Tx MXene/silicone rubber composites achieved by adding a few boron nitride nanoplates

MXenes have attracted great attentions in the fabrication of dielectric polymer composites because of their excellent electrical conductivity. However, the high dielectric loss tangent would suppress the application of such polymer-based composites. Incorporating insulating fillers might be a solution. Herein, Ti₃C₂T_x MXene/silicone rubber (SR) composites incorporated with boron nitride (BN) nanoplates were prepared. The homogeneous distribution of fillers was obtained in the composites, which was also thermally stable up to 400 °C. Dielectric constant of 7.06 (2.54 times of pure SR) and dielectric loss tangent of 0.00131 were achieved when the filling contents of MXene and BN in SR composite were 1.2 wt% and 5 wt%, respectively. The improved dielectric constant can be ascribed to the enhanced interfacial polarization and the formation of conductive network, while the low dielectric loss tangent can be due to the insulating interlayers of BN which could inhibit the transfer of free electrons from conductive fillers to the insulating polymer matrices. BN/MXene/SR composites displayed improved mechanical properties (tensile stress of 671 kPa and elongation at break of 353%) and good flexibility (elastic modulus of 540 kPa) due to the low filling content of fillers. This work is promising for preparing dielectric polymer composites in applications of electronic devices.