A First-Principles Study on the Vibrational and Electronic Properties of Zr-C MXenes

Abstract

Within the framework of density functional theory calculations, the structural, vibrational, and electronic properties of ZrnCn − 1 (n = 2, 3, and 4) and their functionalized MXenes have been investigated. We find that the most stable configurations for Zr-C MXene are the ones that the terminal groups F, O, and OH locate on the common hollow site of the superficial Zr layer and its adjacent C layer. F and OH-terminated Zr3C2 and Zr4C3 have small imaginary acoustic phonon branches around Γ point while the others have no negative phonon modes. The pristine MXenes (Zr2C, Zr3C2 and Zr4C3) are all metallic with large DOS contributed by the Zr atom at the Fermi energy. When functionalized by F, O and OH, new hybridization states appear and the DOS at the Fermi level are reduced. Moreover, we find that their metallic characteristic increases with an increase in n. For (ZrnCn − 1)O2, Zr2CO2 is a semiconductor, Zr3C2O2 is a semimetal, and Zr4C3O2 becomes a metal.

Recent advances in synthesis and properties of zirconium‐based MXenes for application in rechargeable batteries

“…Electronic properties of pristine MXene such as Zr 2 C, Zr 3 C 2, and Zr 4 C 3 and its functionalized hybrids are calculated by using density functional theory (DFT) approximation by Wang et al 46 They found that the pristine MXenes are metallic in nature, which holding higher DOS introduced by Zr atom, basically superficial Zr layer situated in Fermi energy. Higher Zr DOS peaks in Fermi level is producing an instability to the pristine Zr‐C MXene, reveals that there needs a functionalization with chemical groups.…”

“…Vibrational stabilities of pristine and functionalized ZrC MXene is calculated by using phonon spectra by Wang et al 46 They have found that in the г point, the pristine and functionalized Zr n C n −1 having a quadratic flexural acoustic phonon branch same as that of other 2D materials. Zr 2 C, Zr 3 C 2 , and Zr 4 C 3 do not contains any imaginary components of frequency and it holding dynamic stability.…”

Transition Metal Layer Substitution in Mo2CS2 MXene for Improving Li Ion Surface Kinetics

“…The most studied MXene is titanium carbide, Ti 3 C 2 , − which was also the first to be discovered , in 2011. Since then, zirconium carbide, Zr 2 C, has garnered attention ,− after it was experimentally synthesized by etching Al 3 C 3 from layered Zr 3 Al 3 C 5 structures. However, the studies of Zr 2 C as an anode electrode in ion batteries have been limited to O, OH, F, and S surface termination atoms, while a more extensive study of its use as an anode electrode in Li and non-Li ion batteries was conducted by Papadopoulou et al in 2022 …”

Alkali-metal(Li, Na, and K)-adsorbed MoSi2N4 monolayer: an investigation of its outstanding electronic, optical, and photocatalytic properties

“…MXenes (include 2D transition metal nitrides, carbides, and carbonitrides) are a rapidly developing family of 2D materials with nearly 30 members experimentally synthesized and dozens of them investigated theoretically [9,10]. They are widely applied in various applications because of their unique physiochemical properties, including outstanding electronic [11], photocatalytic [12], and mechanical [13] properties. Recently, Hong et al [14], during the chemical vapor deposition growth of nanolayered MoN 2 , introduced elemental Si to passivate its surface.…”