Currently, however, there are relatively few such atomically layered solids. [ 2–5 ] Here, we report on 2D nanosheets, composed of a few Ti 3 C 2 layers and conical scrolls, produced by the room temperature exfoliation of Ti 3 AlC 2 in hydrofl uoric acid. The large elastic moduli predicted by ab initio simulation, and the possibility of varying their surface chemistries (herein they are terminated by hydroxyl and/or fl uorine groups) render these nanosheets attractive as polymer composite fi llers. Theory also predicts that their bandgap can be tuned by varying their surface terminations. The good conductivity and ductility of the treated powders suggest uses in Li-ion batteries, pseudocapacitors, and other electronic applications. Since Ti 3 AlC 2 is a member of a 60 + group of layered ternary carbides and nitrides known as the MAX phases, this discovery opens a door to the synthesis of a large number of other 2D crystals. Arguably the most studied freestanding 2D material is graphene, which was produced by mechanical exfoliation into single-layers in 2004. [ 1 ] Some other layered materials, such as hexagonal BN, [ 2 ] transition metal oxides, and hydroxides, [ 4 ] as well as clays, [ 3 ] have also been exfoliated into 2D sheets. Interestingly, exfoliated MoS 2 single layers were reported as early as in 1986. [ 5 ] Graphene is fi nding its way to applications ranging from supercapacitor electrodes [ 6 ] to reinforcement in composites. [ 7 ] Although graphene has attracted more attention than all other 2D materials combined, its simple chemistry and the weak van der Waals bonding between layers in multilayer structures limit its use. Complex, layered structures that contain more than one element may offer new properties because they

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Two‐Dimensional Nanocrystals Produced by Exfoliation of Ti 3 AlC 2

The family of 2D transition metal carbides, carbonitrides and nitrides (collectively referred to as MXenes) has expanded rapidly since the discovery of Ti3C2 in 2011. The materials reported so far always have surface terminations, such as hydroxyl, oxygen or fluorine, which impart hydrophilicity to their surfaces. About 20 different MXenes have been synthesized, and the structures and properties of dozens more have been theoretically predicted. The availability of solid solutions, the control of surface terminations and a recent discovery of multi-transition-metal layered MXenes offer the potential for synthesis of many new structures. The versatile chemistry of MXenes allows the tuning of properties for applications including energy storage, electromagnetic interference shielding, reinforcement for composites, water purification, gas- and biosensors, lubrication, and photo-, electro- and chemical catalysis. Attractive electronic, optical, plasmonic and thermoelectric properties have also been shown. In this Review, we present the synthesis, structure and properties of MXenes, as well as their energy storage and related applications, and an outlook for future research. More than twenty 2D carbides, nitrides and carbonitrides of transition metals (MXenes) have been synthesized and studied, and dozens more predicted to exist. Highly electrically conductive MXenes show promise in electrical energy storage, electromagnetic interference shielding, electrocatalysis, plasmonics and other applications.

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2D metal carbides and nitrides (MXenes) for energy storage

Recently a new, large family of two-dimensional (2D) early transition metal carbides and carbonitrides, called MXenes, was discovered. MXenes are produced by selective etching of the A element from the MAX phases, which are metallically conductive, layered solids connected by strong metallic, ionic, and covalent bonds, such as Ti2AlC, Ti3AlC2, and Ta4AlC3. MXenes ­combine the metallic conductivity of transition metal carbides with the hydrophilic nature of their hydroxyl or oxygen terminated surfaces. In essence, they behave as “conductive clays”. This article reviews progress—both ­experimental and theoretical—on their synthesis, structure, properties, intercalation, delamination, and potential applications. MXenes are expected to be good candidates for a host of applications. They have already shown promising performance in electrochemical energy storage systems. A detailed outlook for future research on MXenes is also presented.

25th Anniversary Article: MXenes: A New Family of Two‐Dimensional Materials

The isolation of graphene in 2004 from graphite was a defining moment for the “birth” of a field: two-dimensional (2D) materials In recent years, there has been a rapidly increasing number of papers focusing on non-graphene layered materials, including transition-metal dichalcogenides (TMDs), because of the new properties and applications that emerge upon 2D confinement Here, we review significant recent advances and important new developments in 2D materials “beyond graphene” We provide insight into the theoretical modeling and understanding of the van der Waals (vdW) forces that hold together the 2D layers in bulk solids, as well as their excitonic properties and growth morphologies Additionally, we highlight recent breakthroughs in TMD synthesis and characterization and discuss the newest families of 2D materials, including monoelement 2D materials (ie, silicene, phosphorene, etc) and transition metal carbide- and carbon nitride-based MXenes We then discuss the doping and functionalization of 2

Recent Advances in Two-Dimensional Materials beyond Graphene

Preceramic polymers were proposed over 30 years ago as precursors for the fabrication of mainly Si-based advanced ceramics, generally denoted as polymer-derived ceramics (PDCs). The polymer to ceramic transformation process enabled significant technological breakthroughs in ceramic science and technology, such as the development of ceramic fibers, coatings, or ceramics stable at ultrahigh temperatures (up to 2000°C) with respect to decomposition, crystallization, phase separation, and creep. In recent years, several important advances have been achieved such as the discovery of a variety of functional properties associated with PDCs. Moreover, novel insights into their structure at the nanoscale level have contributed to the fundamental understanding of the various useful and unique features of PDCs related to their high chemical durability or high creep resistance or semiconducting behavior. From the processing point of view, preceramic polymers have been used as reactive binders to produce technical ceramics, they have been manipulated to allow for the formation of ordered pores in the meso-range, they have been tested for joining advanced ceramic components, and have been processed into bulk or macroporous components. Consequently, possible fields of applications of PDCs have been extended significantly by the recent research and development activities. Several key engineering fields suitable for application of PDCs include high-temperature-resistant materials (energy materials, automotive, aerospace, etc.), hard materials, chemical engineering (catalyst support, food- and biotechnology, etc.), or functional materials in electrical engineering as well as in micro/nanoelectronics. The science and technological development of PDCs are highly interdisciplinary, at the forefront of micro- and nanoscience and technology, with expertise provided by chemists, physicists, mineralogists, and materials scientists, and engineers. Moreover, several specialized industries have already commercialized components based on PDCs, and the production and availability of the precursors used has dramatically increased over the past few years. In this feature article, we highlight the following scientific issues related to advanced PDCs research: (1) General synthesis procedures to produce silicon-based preceramic polymers.
(2) Special microstructural features of PDCs.
(3) Unusual materials properties of PDCs, that are related to their unique nanosized microstructure that makes preceramic polymers of great and topical interest to researchers across a wide spectrum of disciplines.
(4) Processing strategies to fabricate ceramic components from preceramic polymers.
(5) Discussion and presentation of several examples of possible real-life applications that take advantage of the special characteristics of preceramic polymers. Note: In the past, a wide range of specialized international symposia have been devoted to PDCs, in particular organized by the American Ceramic Society, the European Materials Society, and the Materials Research Society. Most of the reviews available on PDCs are either not up to date or deal with only a subset of preceramic polymers and ceramics (e.g., silazanes to produce SiCN-based ceramics). Thus, this review is focused on a large number of novel data and developments, and contains materials from the literature but also from sources that are not widely available.

Polymer-Derived Ceramics: 40 Years of Research and Innovation in Advanced Ceramics

The heat capacities, thermal-expansion coefficients, thermal and electrical conductivities of Nb2AlC (actual Nb:Al:C mole fractions: 0.525±0.005, 0.240±0.002, and 0.235±0.005, respectively), Ti2AlC and (Ti, Nb)2AlC (actual Ti:Nb:Al:C mole fractions: 0.244±0.005, 0.273±0.005, 0.240±0.003, and 0.244±0.005, respectively) were measured as a function of temperature. These ternaries are good electrical conductors, with a resistivity that increases linearly with increasing temperatures. The resistivity of (Ti, Nb)2AlC is higher than the other members, indicating a solid-solution scattering effect. The thermal-expansion coefficients, in the 25 °C to 1000 °C temperature range, are comparable and fall in the narrow range of 8.7 to 8.9 × 10−6 K−1, with that of the solid solution being the highest. They are all good conductors of heat, with thermal conductivities in the range between 15 to 45 W/m K at room temperature. The electronic component of the thermal conductivity is the dominant mechanism at all temperatures for Nb2AlC and (Ti, Nb)2AlC. The conductivity of Ti2AlC, on the other hand, is high because the phonon contribution to the conductivity is nonnegligible.

Thermal and electrical properties of Nb2AlC, (Ti, Nb)(2)AlC and Ti2AlC

Fabrication and electrical and thermal properties of Ti2InC, Hf2InC and (Ti,Hf)2InC

The chemical stability of an amorphous silicon carbonitride ceramic, having the composition 057SiC·043Si3N4·049C is studied as a function of nitrogen overpressure at 1873 K The ceramic suffers a weight loss at pN2 < 35 bar (1 bar = 100 kPa), does not show a weight change from 35 to 11 bar, and gains weight above 11 bar The structure of the ceramic changes with pressure: it is crystalline from 1 to 6 bar, amorphous at ∼10 bar, and is crystalline above ∼10 bar The weight-loss transition, at 35 bar, is in excellent agreement with the prediction from thermodynamic analysis when the activities of carbon, SiC, and Si3N4 are set equal to those of the crystalline forms; this implies that the material crystallizes before decomposition The amorphous to crystalline transition that occurs at ∼10 bar, and which is accompanied by weight gain, is likely to have taken place by a different mechanism A nucleation and growth reaction with the atmospheric nitrogen is proposed as the likely mechanism The supersaturation required to nucleate α-Si3N4 crystals is calculated to be 30 kJ/mol

Crystallization of polymer-derived silicon carbonitride at 1873 K under nitrogen overpressure

Effect of boron on the thermodynamic stability of amorphous polymer-derived Si-(B)-)C-N ceramics

Computational thermodynamics is applied to two important and closely related phenomena in phase transformations, namely nucleation and coarsening. In both phenomena the surface energy plays a key role. The effect of surface energy on a two-phase equilibrium as well as the activation energy for forming a critical nucleus are both derived for the general multicomponent case. A simplified coarsening equation is derived for the general multicomponent case.

Jerzy A. Golczewski

Papers

Thermal and electrical properties of Nb2AlC, (Ti, Nb)(2)AlC and Ti2AlC

Fabrication and electrical and thermal properties of Ti2InC, Hf2InC and (Ti,Hf)2InC

Crystallization of polymer-derived silicon carbonitride at 1873 K under nitrogen overpressure

Effect of boron on the thermodynamic stability of amorphous polymer-derived Si-(B)-)C-N ceramics

Applications of computational thermodynamics: Group 3: Application of computational thermodynamics to phase transformation nucleation and coarsening