Investigations of two-dimensional transition-metal chalcogenides (TMCs) have recently revealed interesting physical phenomena, including the quantum spin Hall effect, valley polarization and two-dimensional superconductivity , suggesting potential applications for functional devices. However, of the numerous compounds available, only a handful, such as Mo- and W-based TMCs, have been synthesized, typically via sulfurization, selenization and tellurization of metals and metal compounds. Many TMCs are difficult to produce because of the high melting points of their metal and metal oxide precursors. Molten-salt-assisted methods have been used to produce ceramic powders at relatively low temperature and this approach was recently employed to facilitate the growth of monolayer WS and WSe. Here we demonstrate that molten-salt-assisted chemical vapour deposition can be broadly applied for the synthesis of a wide variety of two-dimensional (atomically thin) TMCs. We synthesized 47 compounds, including 32 binary compounds (based on the transition metals Ti, Zr, Hf, V, Nb, Ta, Mo, W, Re, Pt, Pd and Fe), 13 alloys (including 11 ternary, one quaternary and one quinary), and two heterostructured compounds. We elaborate how the salt decreases the melting point of the reactants and facilitates the formation of intermediate products, increasing the overall reaction rate. Most of the synthesized materials in our library are useful, as supported by evidence of superconductivity in our monolayer NbSe and MoTe samples and of high mobilities in MoS and ReS. Although the quality of some of the materials still requires development, our work opens up opportunities for studying the properties and potential application of a wide variety of two-dimensional TMCs.

The higher the chemical diversity and structural complexity of two-dimensional (2D) materials, the higher the likelihood they possess unique and useful properties. Herein, density functional theory (DFT) is used to predict the existence of two new families of 2D ordered, carbides (MXenes), M'2M″C2 and M'2M″2C3, where M' and M″ are two different early transition metals. In these solids, M' layers sandwich M″ carbide layers. By synthesizing Mo2TiC2Tx, Mo2Ti2C3Tx, and Cr2TiC2Tx (where T is a surface termination), we validated the DFT predictions. Since the Mo and Cr atoms are on the outside, they control the 2D flakes' chemical and electrochemical properties. The latter was proven by showing quite different electrochemical behavior of Mo2TiC2Tx and Ti3C2Tx. This work further expands the family of 2D materials, offering additional choices of structures, chemistries, and ultimately useful properties.

A combination of density functional theory (DFT) calculations and experiments is used to shed light on the relation between surface structure and Li-ion storage capacities of the following functionalized two-dimensional (2D) transition-metal carbides or MXenes: Sc2C, Ti2C, Ti3C2, V2C, Cr2C, and Nb2C. The Li-ion storage capacities are found to strongly depend on the nature of the surface functional groups, with O groups exhibiting the highest theoretical Li-ion storage capacities. MXene surfaces can be initially covered with OH groups, removable by high-temperature treatment or by reactions in the first lithiation cycle. This was verified by annealing f-Nb2C and f-Ti3C2 at 673 and 773 K in vacuum for 40 h and in situ X-ray adsorption spectroscopy (XAS) and Li capacity measurements for the first lithiation/delithiation cycle of f-Ti3C2. The high-temperature removal of water and OH was confirmed using X-ray diffraction and inelastic neutron scattering. The voltage profile and X-ray adsorption near edge structure of f-Ti3C2 revealed surface reactions in the first lithiation cycle. Moreover, lithiated oxygen terminated MXenes surfaces are able to adsorb additional Li beyond a monolayer, providing a mechanism to substantially increase capacity, as observed mainly in delaminated MXenes and confirmed by DFT calculations and XAS. The calculated Li diffusion barriers are low, indicative of the measured high-rate performance. We predict the not yet synthesized Cr2C to possess high Li capacity due to the low activation energy of water formation at high temperature, while the not yet synthesized Sc2C is predicted to potentially display low Li capacity due to higher reaction barriers for OH removal.

Rechargeable non-lithium-ion (Na(+), K(+), Mg(2+), Ca(2+), and Al(3+)) batteries have attracted great attention as emerging low-cost and high energy-density technologies for large-scale renewable energy storage applications. However, the development of these batteries is hindered by the limited choice of high-performance electrode materials. In this work, MXene nanosheets, a class of two-dimensional transition-metal carbides, are predicted to serve as high-performing anodes for non-lithium-ion batteries by combined first-principles simulations and experimental measurements. Both O-terminated and bare MXenes are shown to be promising anode materials with high capacities and good rate capabilities, while bare MXenes show better performance. Our experiments clearly demonstrate the feasibility of Na- and K-ion intercalation into terminated MXenes. Moreover, stable multilayer adsorption is predicted for Mg and Al, which significantly increases their theoretical capacities. We also show that O-terminated MXenes can decompose into bare MXenes and metal oxides when in contact with Mg, Ca, or Al. Our results provide insight into metal ion storage mechanisms on two-dimensional materials and suggest a route to preparing bare MXene nanosheets.