二维纳米材料MXene的研究进展

MXene是一类新型碳/氮化物二维纳米层状材料,一般是利用化学刻蚀的手段通过选择性刻蚀掉前驱体MAX相中的A原子层而得到。其通式可表示为M_(n+1)X_nT_x,其中M代表早期过渡族金属,X代表碳和/或氮,T_x代表MXene在刻蚀过程中产生的附着在其表面的官能团(-OH、-F、=O、等)。采用一定的手段将多层MXene剥落,可获得类石墨烯形貌的单层MXene。MXene除了具备传统二维材料的性能外,还兼具良好的导电性、亲水性、透光性、柔韧性以及能量储存性能,在复合材料、润滑剂、环境污染治理、电池、电容器、催化、传感器、抗菌等领域具有潜在的应用价值。文章总结了MXene的制备、结构、性能和应用等方面的最新成果,并展望了其今后的研究方向。     

MXene材料的制备、电化学储能性能研究现状

本文对比了二维过渡金属碳(氮)化合物(MXene)的制备方法(氢氟酸刻蚀法、高温刻蚀法和化学气相沉积法);分析了层间距、表面基团和测试环境对MXene材料电化学储能性能的影响,探讨了其结构与电化学储能性能的关系,揭示了不同基体的物理化学性质、微观结构以及基体组成对MXene基复合材料电化学性能的影响.对MXene目前在储能领域应用上存在的问题及未来的发展方向进行了展望.     

二维MXene膜的构筑及在水处理应用中的研究进展

MXene是一类新型的过渡金属碳/氮化物二维层状材料,通过选择性刻蚀掉MAX相中的A原子层制备而成。由于MXene具有特殊的微观结构和优异的理化性质,可用于高性能膜分离材料的构筑,并逐渐在废水处理和海水淡化等领域展现出良好的应用前景。但MXene在实际水处理过程中还存在不小的局限性。如MXene膜在水溶液中易发生溶胀现象,膜抗污染能力弱,分离机制也尚未有统一定论。本文归纳了近年来MXene纳米片、二维MXene膜材料的制备方法,例举了MXene膜的改性路径及其在水处理应用领域的最新报道,提出了MXene膜对水中污染物的分离机制,并对其当前急需解决的问题和未来的发展方向做出展望,为基于MXene高性能膜材料的设计和应用提供参考。      

二维MXene材料在超级电容应用的研究进展

二维过渡金属碳/氮化物(MXene)具有类石墨烯的结构,微观上呈现片层状和多种表面基团,因此具有良好的导电性、离子传输和高亲水性能,并且成为超级电容器的理想电极材料。但MXene层与层容易坍塌、堆叠与官能团的存在,不利于作为电极材料的性能。通过热处理、离子插层和与碳复合等方法提高其电化学性能拥有巨大的应用前景。首先总结了MXene材料的制备方法,然后概述了表面改性和结构优化等对MXene超级电容器的电化学性能的影响,展望了MXene材料在超级电容器上的研究前景。     

新型二维层状材料MXene在超级电容器上的研究与应用进展

二维过渡族金属碳化物/氮化物(MXene)是二维材料家族的新兴成员,通过液相刻蚀等方法移除MAX相的A层得来。独特的二维结构及表面化学组成,使其表现出了良好的金属导电性、亲水性、优异的柔韧性及离子可插层性,在超级电容器研究与应用领域展现了巨大的潜力,受到了广泛关注。但是MXene仍存在诸多问题。首先,片层容易发生堆叠,极大降低了材料与电解液的有效接触面面积;在刻蚀过程中,化学键断裂处具有较高的活性,极易反应生成表面基团,表面基团的存在对电化学性能有较大影响;合成路线中强腐蚀液的使用也会造成安全、环境等诸多问题。对MXene的结构、性质、制备方法等进行了简要概述,总结了近年来MXene在超级电容器领域的研究进展和方向,旨在从中发现解决MXene诸多问题思路,以期为制备高性能MXene超级电容器电极材料提供参考。     

二维MXene材料在气体传感器领域的应用进展

MXene材料是由前过渡金属碳、氮化物组成的无机化合物,二维MXene及其复合材料具有类石墨烯层状结构、高比表面积、优异的导电性和丰富的表面活性位点,近年来在材料领域成为研究热点。本文聚焦二维MXene材料在气体传感器领域的应用前景,从MXene和气敏性能等角度进行了综述,重点对MXene及其(无机/有机)复合材料用作气敏材料的制备方法和传感器性能进行了综述,并提出了二维MXene用于气敏领域在材料设计策略、敏感机理等方面存在的机遇和挑战,为该类新兴材料在气敏领域的潜在应用提供借鉴。     

三元层状碳氮化合物(MAX相)及其衍生二维纳米材料(MXene)研究趋势与展望

近年来, 三元层状碳氮化合物(MAX相)及其衍生二维纳米材料MXene受到了科学界的广泛关注。MAX相的晶体结构由M_n+1X_n结构单元与A元素单原子面交替堆垛排列而成, 兼具金属和陶瓷的诸多优点, 在高温结构材料、摩擦磨损器件、核能结构材料等领域有较大的应用潜力。MAX相的A层原子被刻蚀之后获得成分为M_n+1X_nT_x(T_x为表面基团)的二维纳米材料, 即MXene, 具有丰富的成分组合以及可调谐的物理化学性质, 在储能器件、电磁屏蔽、电子器件等领域表现出良好的应用前景。本文简要介绍近年来国内外MAX相和MXene材料领域在成分与结构、合成方法、性能与应用研究等方面的研究动态, 据此展望未来几年该类新颖材料的发展方向。     

二维材料MXene的储能性能与应用

能量存储和转化器件是现代社会的重要基础。随着清洁能源、便携式电子设备及电动汽车的快速发展,人们对储能器件性能的要求越来越高。储能材料是决定储能器件性能的重要因素。通常,储能材料需满足具有可逆的氧化还原反应、易于电解液离子脱嵌、尽可能多地提供氧化还原位点、良好的导电能力等要求。近年来,二维材料因比表面积大、离子传输路径短等特点而得到广泛关注,在储能领域也具有巨大的发展潜力。只有原子量级厚度的二维材料,表面活性位点多,力学性能优良,正契合储能器件对电极材料的要求。MXene是一类新型二维材料,通式为Mn+1XnTx,其中M代表过渡族金属元素,X为碳和/或氮,T代表MXene在制备过程中产生的官能团(-F、-OH、-O等),n一般为1～4。自2011年首次报道以来,MXene在储能领域就被寄予厚望。MXene含有碳原子层,所以具有类似石墨烯的良好导电性;而过渡金属层使其表现出类似过渡金属氧化物的性能;同时,表面多样的官能团赋予MXene良好的亲水性。这种独特的性能组合,使得MXene电荷响应速度快,具有赝电容特征且循环性能稳定,成为储能领域的研究焦点。另外,便携式储能器件要求更高的体积容量与体积能量密度,而MXene与碳基电极材料相比堆积密度高,可有效降低器件体积,拓展应用范围。目前,MXene及其复合材料已经在超级电容器、锂/钠/镁离子二次电池、锂硫电池、锌-空气电池、储氢等诸多储能领域展现出实用价值。但是,MXene容易发生塌陷和堆垛,影响其作为电极材料的性能。因此,需将MXene进行插层、改性、掺杂或与其他材料复合,以阻止MXene堆叠,减小离子扩散阻力,并增加离子吸附位点,从而提高其电化学性能。而且,不同的能量存储和转化装置对MXene的合成方法和结构特征有不同的要求,鉴于MXene能源应用相关研究的大量呈现,有必要对其进行全面总结与分析,以期推动MXene在该领域的发展。本文旨在综述MXene在制备、结构、性能及其在储能方面的最新研究动态与发展方向,并讨论面临的挑战。     

二维材料MXenes的储能性能与应用

能量存储和转化器件是现代人类生活的重要物质基础。随着便携式电子设备及电动汽车的快速发展,人类对储能器件性能的要求也越来越高。勿容置疑,储能器件的性能表现取决于储能材料的开发和利用。通常,对储能材料的要求有以下四点:(1)具有可逆的氧化还原反应;(2)易于电解液离子进出;(3)尽可能多地提供氧化还原位点;(4)良好的导电能力。近年来,二维材料以其比表面积大、离子传输路径短等特点在储能领域展现出巨大优势。二维材料只有原子层量级的厚度,表面活性位点多,机械性能优良,正好契合储能器件对材料性能的要求。MXene是一类新型二维材料,于2011年首先被发现,通式可表示为M_(n+1)X_n T_x,其中M代表过渡族金属元素,X为碳和/或氮,T代表MXene在制备过程中产生的官能团(-F,-OH,-O等);n一般为1、2、3。自被发现起,MXene就在储能材料中被寄予厚望。MXene具有导电性好、电荷响应速度快、比表面积大,以及具有赝电容的特征且循环寿命稳定的优点。这是因为:MXene含有碳层,所以具有类似石墨烯的良好导电性,又有过渡金属层,可表现出类似过渡金属氧化物的性能。同时,表面多变的官能团赋予MXene亲水性。这种完美契合储能材料要求的性质,使得MXenes的研究逐渐成为热点。另外,便携式储能器件对体积容量/能量密度指标要求越来越高,而MXene堆积密度高,可有效降低储能器件的体积,提升体积/能量密度,拓展其应用范围。目前,MXene及其复合材料已经在超级电容器、锂/钠/镁离子二次电池、锂硫电池、锌-空气电池、储氢等多个储能领域展现出实用价值。但是,纯MXene容易发生塌陷和堆垛,影响其作为电极材料的性能。因此需将MXene进行插层/改性、掺杂处理或者与其它材料复合,以减小离子扩散阻力,增加离子的吸附位点,从而阻止MXene堆叠,提高其电化学性能。而且,不同的能量存储和转化装置对MXene的合成方法和结构特征具有不同的要求。同时,MXene的成分、形貌与结构对其储能性能影响巨大。因此需要对该材料体系进行全面总结与分析,以期推动MXene在能量储存和转化领域的发展。本文旨在综述MXene在制备、结构、性能及其在储能方面的最新研究进展,并展望其今后的发展方向和该领域面临的挑战。     

二维材料MXene在水处理领域的应用

MXene是一类新兴二维(2D)结构的过渡金属碳/氮化物材料,具有独特的层状结构、亲水性、高导电性和催化活性等特点,在水处理领域受到越来越多的关注.首先介绍了MXene及其合成方法,综述了MXene在吸附、光催化和膜分离等方面的应用.其次讨论了MXene的结构调控、表面改性以及复合等对MXene吸附性能的影响机制和有效异质结的形成、活性晶面的暴露以及贵金属沉积等对MXene基光催化剂催化性能的影响机制;详述了构建高效分离污染物、淡化海水的MXene基分离膜的方法.最后归纳并分析了目前MXene在水处理领域应用中存在的问题,对如何设计性能优异的MXene基水处理材料提出了展望.     

Self-assembled Ti3C2Tx-MXene/PTh composite electrodes for electrochemical capacitors

Recently, MXene are being extensively utilized as an electrode material for electrochemical capacitors owing to its excellent electrochemical performance. Furthermore, its excellent properties are enhanced by compounding it with other materials as the electrode material of electrochemical capacitor. In this study, MXene has been obtained by selective etching, Polythiophene (PTh) was prepared by chemical oxidative polymerization, and MXene/PTh composites with different mass ratios have been synthesized by the vacuum filtration self-assembly method. MXene nanosheets have the comprehensive function of combining PTh nanoparticles, and acting as flexible substrates. PTh nanoparticles can provide high pseudo-capacitance and inhibit the stacking of MXene, thus achieving a good synergistic effect. The results demonstrate that the M/PTh-3 composite has the best capacitance with a maximum value of 265.96 F g^?1. The specific capacitance remains at 91.5% even after 500 cycles, which demonstrates that the composite electrode is a promising material for the high-performance electrochemical capacitor applications.

     

二维晶体材料MXene的电化学应用研究进展

MXene是一种类石墨烯结构的新型二维过渡金属碳化物或碳氮化物,通过氟盐和盐酸或氢氟酸刻蚀前驱体MAX相中的活泼金属元素得到,其化学通式为Mn+1XnT(n=1,2,3…),T表示表面所附着的官能团(-H、-F或-OH)。得益于其表面的官能团,MXene在储能方面应用较为广泛。通过表面改性、离子插层,增加MXene晶面间距,提高离子传输效率,以优化MXene在电化学方面的应用。综述了以Ti3C2为代表的MXene的制备方法、理论研究以及在锂离子电池、锂硫电池、超级电容器等方面的应用研究进展,展望了MXene在电化学领域的应用前景和未来的研究方向。     

Investigation of adjacent spacing dependent microwave absorption properties of lamellar structural Ti3C2Tx MXenes

Ti₃C₂Tx MXenes and their composites play a vital role in the research on microwave absorbing materials. Herein, the different interlamellar spaces of Ti₃C₂Tx MXene materials were prepared by an etching process. The dependence of the microwave absorbing properties of the Ti₃C₂Tx MXene nanosheets on different interlamellar spaces was studied. The complex permittivity, dielectric loss, impedance matching characteristic and the minimum reflection loss (RL) value with the variation in interlamellar space were systematically investigated. Results showed that 40% ratio paraffin-bonded composites (S3) have a strong electromagnetic wave absorption performance and large effective absorbing bandwidth. The maximum RL reaches −36.3 dB at 4.67 GHz with the thickness of 4.5 mm, ascribed to its a high dielectric loss and good impedance matching characteristics. The RL value of Ti₃C₂Tx MXenes is strongly dependent on the inter-lamellar space. The enhanced microwave absorption originates from the unique 2-D structure, good impedance matching characteristics, and enhanced space-charge polarization effects. This work provides a new avenue for exploring high-performance microwave absorbers based on MXene materials.     

导电二维碳化钼MXene材料的制备与理论研究

以Mo、Y、Al和C元素粉为原料, 用放电等离子烧结技术(SPS)在1550 ℃合成了新颖的(Mo_2/3Y_1/3)₂AlC MAX相, 并用较温和的化学刻蚀方法剥离得到相应手风琴状形貌的MXene。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和能谱分析(EDS)手段对材料的化学组成、微观结构等进行了表征, 确定最终产物为表面带有官能团的Mo_1.33CT₂ MXene。同时利用第一性原理密度泛函理论计算方法研究了新颖(Mo_2/3Y_1/3)₂AlC MAX相以及对应的Mo_1.33CT₂ MXene的电子结构和性能, 计算结果表明两者均呈现出金属特性, 有望应用于储能、生物传感器和电催化等方面。     

Hydrophobic,Flexible, and Lightweight MXene Foams for High‐Performance Electromagnetic‐Interference Shielding

Ultrathin, lightweight, and flexible electromagnetic‐interference (EMI) shielding materials are urgently required to manage increasingly serious radiation pollution. 2D transition‐metal carbides (MXenes) are considered promising alternatives to graphene for providing excellent EMI‐shielding performance due to their outstanding metallic electrical conductivity. However, the hydrophilicity of MXene films may affect their stability and reliability when applied in moist or wet environments. Herein, for the first time, an efficient and facile approach is reported to fabricate freestanding, flexible, and hydrophobic MXene foam with reasonable strength by assembling MXene sheets into films followed by a hydrazine‐induced foaming process. In striking contrast to well‐known hydrophilic MXene materials, the MXene foams surprisingly exhibit hydrophobic surfaces and outstanding water resistance and durability. More interestingly, a much enhanced EMI‐shielding effectiveness of ≈70 dB is achieved for the lightweight MXene foam as compared to its unfoamed film counterpart (53 dB) due to the highly efficient wave attenuation in the favorable porous structure. Therefore, the hydrophobic, flexible, and lightweight MXene foam with an excellent EMI‐shielding performance is highly promising for applications in aerospace and portable and wearable smart electronics.     

Self‐Assembly of Transition Metal Oxide Nanostructures on MXene Nanosheets for Fast and Stable Lithium Storage

Recently, a new class of 2D materials, i.e., transition metal carbides, nitrides, and carbonitrides known as MXenes, is unveiled with more than 20 types reported one after another. Since they are flexible and conductive, MXenes are expected to compete with graphene and other 2D materials in many applications. Here, a general route is reported to simple self‐assembly of transition metal oxide (TMO) nanostructures, including TiO₂ nanorods and SnO₂ nanowires, on MXene (Ti₃C₂) nanosheets through van der Waals interactions. The MXene nanosheets, acting as the underlying substrate, not only enable reversible electron and ion transport at the interface but also prevent the TMO nanostructures from aggregation during lithiation/delithiation. The TMO nanostructures, in turn, serve as the spacer to prevent the MXene nanosheets from restacking, thus preserving the active areas from being lost. More importantly, they can contribute extraordinary electrochemical properties, offering short lithium diffusion pathways and additional active sites. The resulting TiO₂/MXene and SnO₂/MXene heterostructures exhibit superior high‐rate performance, making them promising high‐power and high‐energy anode materials for lithium‐ion batteries.     

2D Materials Decorated with Ultrathin and Porous Graphene Oxide for High Stability and Selective Surface Activity

2D black phosphorus (BP) and MXenes have triggered enormous research interest in catalysis, energy storage, and chemical sensing. Unfortunately, the low stability of these materials under practical operating conditions remains a critical bottleneck, particularly as they are prone to oxidization under moisture. In this work, the design and application of stable 2D heterostructures obtained from decorating BP and MXene (Ti₃C₂T_x) with few-layer holey graphene oxide (FHGO) membranes are presented. In the resulting heterostructured systems, FHGO serves as a multifunctional passivation layer that shields BP or MXene from oxidative degradation, while allowing the selective diffusion of target gas molecules through its micropores and toward the underlying 2D material. Through a case study of dilute NO₂ sensing, it is demonstrated that these heterostructures show a greatly enhanced sensing performance under humid conditions, where fast sensing speed and response are consistently observed, and high stability is impressively retained upon repetitive sensing cycles for 1000 min. These results corroborate the efficacy of material decoration with porous FHGO membranes and suggest that this is a generalizable strategy for reliable high-performance applications of 2D materials.     

W‐Based Atomic Laminates and Their 2D Derivative W1.33C MXene with Vacancy Ordering

Structural design on the atomic level can provide novel chemistries of hybrid MAX phases and their MXenes. Herein, density functional theory is used to predict phase stability of quaternary i‐MAX phases with in‐plane chemical order and a general chemistry (W_2/3M²_1/3)₂AC, where M² = Sc, Y (W), and A = Al, Si, Ga, Ge, In, and Sn. Of over 18 compositions probed, only two—with a monoclinic C2/c structure—are predicted to be stable: (W_2/3Sc_1/3)₂AlC and (W_2/3Y_1/3)₂AlC and indeed found to exist. Selectively etching the Al and Sc/Y atoms from these 3D laminates results in W_1.33C‐based MXene sheets with ordered metal divacancies. Using electrochemical experiments, this MXene is shown to be a new, promising catalyst for the hydrogen evolution reaction. The addition of yet one more element, W, to the stable of M elements known to form MAX phases, and the synthesis of a pure W‐based MXene establishes that the etching of i‐MAX phases is a fruitful path for creating new MXene chemistries that has hitherto been not possible, a fact that perforce increases the potential of tuning MXene properties for myriad applications.