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Register a new userElement Replacement Approach by Reaction with Lewis Acidic Molten Salts to Synthesize Nanolaminated MAX Phases and MXenes
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Nanolaminated materials are important because of their exceptional properties and wide range of applications. Here, we demonstrate a general approach to synthesize a series of Zn-based MAX phases and Cl-terminated MXenes originating from the replacement reaction between the MAX phase and the late transition metal halides. The approach is a top-down route that enables the late transitional element atom (Zn in the present case) to occupy the A site in the pre-existing MAX phase structure. Using this replacement reaction between Zn element from molten ZnCl2 and Al element in MAX phase precursors (Ti3AlC2, Ti2AlC, Ti2AlN, and V2AlC), novel MAX phases Ti3ZnC2, Ti2ZnC, Ti2ZnN, and V2ZnC were synthesized. When employing excess ZnCl2, Cl terminated MXenes (such as Ti3C2Cl2 and Ti2CCl2) were derived by a subsequent exfoliation of Ti3ZnC2 and Ti2ZnC due to the strong Lewis acidity of molten ZnCl2. These results indicate that A-site element replacement in traditional MAX phases by late transition metal halides opens the door to explore MAX phases that are not thermodynamically stable at high temperature and would be difficult to synthesize through the commonly employed powder metallurgy approach. In addition, this is the first time that exclusively Cl-terminated MXenes were obtained, and the etching effect of Lewis acid in molten salts provides a green and viable route to prepare MXenes through an HF-free chemical approach.
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New MAX phases Ti2(AlxCu1-x)N and Nb2CuC were synthesized by A-site replacement by reacting Ti2AlN and Nb2AlC, respectively, with CuCl2 or CuI molten salt. X-ray diffraction, scanning electron microscopy, and atomically-resolved scanning transmission electron microscopy showed complete A-site replacement in Nb2AlC, which lead to formation of Nb2CuC. However, the replacement of Al in Ti2AlN phase was only close to complete at Ti2(Al0.1Cu0.9)N. Density-functional theory calculations corroborated the structural stability of Nb2CuC and Ti2CuN phases. Moreover, the calculated cleavage energy in these Cu-containing MAX phases are weaker than in their Al-containing counterparts, indicating that they are precursor candidates for MXene derivation.
Surface terminations for 2D MXene have dramatic impacts on physicochemical properties. The commonly etching methods usually introduce -F surface termination or metallic into MXene. Here, we present a new molten salt assisted electrochemical etching (MS-E-etching) method to synthesize fluorine-free Ti3C2Tx without metallics. Due to performing electrons as reaction agent, the cathode reduction and anode etching can be spatially isolated, thus no metallic presents in Ti3C2Tx product. Moreover, the Tx surface terminations can be directly modified from -Cl to -O and/or -S in one pot process. The obtained -O terminated MXenes exhibited capacitance of 225 and 205 F/g at 1 and 10 A/g, confirming high reversibility of redox reactions. This one-pot process greatly shortens the modification procedures as well as enriches the surface functional terminations. More importantly, the recovered salt after synthesis can be recycled and reused, which brands it as a green sustainable method.
The MAX phases are a family of of ternary layered material with both metal and ceramic properties, and it is also precursor ma-terials for synthesis of two-dimensional MXenes. The theory predicted that there are more than 600 stable ternary layered MAX phases. At present, there are more than 80 kinds of ternary MAX phases synthesized through experiments, and few reports on MAX phases where M is a rare earth element. In this study, a new MAX phase Sc2SnC with rare earth element Sc at the M sites was synthesized through the reaction sintering of Sc, Sn, and C mixtures. Phase composition and microstructure of Sc2SnC were confirmed by X-ray diffraction, scanning electron microscopy and X-ray energy spectrum analysis. And structural stability, mechanical and electronic properties of Sc2SnC was investigated via density functional theory. This study open a door for ex-plore more unknown ternary layered rare earth compounds Ren+1SnCn (Re=Sc, Y, La-Nd, n=1) and corresponding rare earth MXenes.
Chemical exfoliation of MAX phases into two-dimensional (2D) MXenes can be considered as a major breakthrough in the synthesis of novel 2D systems. To gain insight into the exfoliation possibility of MAX phases and to identify which MAX phases are promising candidates for successful exfoliation into 2D MXenes, we perform extensive electronic structure and phonon calculations, and determine the force constants, bond strengths, and static exfoliation energies of MAX phases to MXenes for 82 different experimentally synthesized crystalline MAX phases. Our results show a clear correlation between the force constants and the bond strengths. As the total force constant of an A atom contributed from the neighboring atoms is smaller, the exfoliation energy becomes smaller, thus making exfoliation easier. We propose 37 MAX phases for successful exfoliation into 2D Ti$_2$C, Ti$_3$C$_2$, Ti$_4$C$_3, $Ti$_5$C$_4$, Ti$_2$N, Zr$_2$C, Hf$_2$C, V$_2$C, V$_3$C$_2$, V$_4$C$_3$, Nb$_2$C, Nb$_5$C$_4$, Ta$_2$C, Ta$_5$C$_4$, Cr$_2$C, Cr$_2$N, and Mo$_2$C MXenes. In addition, we explore the effect of charge injection on MAX phases. We find that the injected charges, both electrons and holes, are mainly received by the transition metals. This is due to the electronic property of MAX phases that the states near the Fermi energy are mainly dominated by $d$ orbitals of the transition metals. For negatively charged MAX phases, the electrons injected cause swelling of the structure and elongation of the bond distances along the $c$ axis, which hence weakens the binding. For positively charged MAX phases, on the other hand, the bonds become shorter and stronger. Therefore, we predict that the electron injection by electrochemistry or gating techniques can significantly facilitate the exfoliation possibility of MAX phases to 2D MXenes.
Two-dimensional carbides and nitrides of transition metals, known as MXenes, are a fast-growing family of 2D materials that draw attention as energy storage materials. So far, MXenes are mainly prepared from Al-containing MAX phases (where A = Al) by Al dissolution in F-containing solution, but most other MAX phases have not been explored. Here, a redox-controlled A-site-etching of MAX phases in Lewis acidic melts is proposed and validated by the synthesis of various MXenes from unconventional MAX phase precursors with A elements Si, Zn, and Ga. A negative electrode of Ti3C2 MXene material obtained through this molten salt synthesis method delivers a Li+ storage capacity up to 738 C g-1 (205 mAh g-1) with high-rate performance and pseudocapacitive-like electrochemical signature in 1M LiPF6 carbonate-based electrolyte. MXene prepared from this molten salt synthesis route offer opportunities as high-rate negative electrode material for electrochemical energy storage applications.
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