Insights into exfoliation possibility of MAX phases to MXenes. Issue 13 (20th March 2018)

• Record Type: Journal Article
• Authors: Khazaei, Mohammad; Ranjbar, Ahmad; Esfarjani, Keivan; Bogdanovski, Dimitri; Dronskowski, Richard; Yunoki, Seiji
• Is Part Of: Physical chemistry chemical physics. Volume 20:Issue 13(2018)
• Page Start: 8579
• Page End: 8592
• Publication Date: 2018-03-20
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c7cp08645h
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Chemical exfoliation of MAX phases into two-dimensional (2D) MXenes can be considered as a major breakthrough in the synthesis of novel 2D systems. Abstract : 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 Ti2 C, Ti3 C2, Ti4 C3, Ti5 C4, Ti2 N, Zr2 C, Hf2 C, V2 C, V3 C2, V4 C3, Nb2 C, Nb5 C4, Ta2 C, Ta5 C4, Cr2 C, Cr2 N, and Mo2 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.