Synthesis of Mo4VAlC4 MAX Phase and Two-Dimensional Mo4VC4 MXene with Five Atomic Layers of Transition Metals

ACS Nano. 2020 Jan 28;14(1):204-217. doi: 10.1021/acsnano.9b07708. Epub 2019 Dec 17.

Abstract

MXenes are a family of two-dimensional (2D) transition metal carbides, nitrides, and carbonitrides with a general formula of Mn+1XnTx, in which two, three, or four atomic layers of a transition metal (M: Ti, Nb, V, Cr, Mo, Ta, etc.) are interleaved with layers of C and/or N (shown as X), and Tx represents surface termination groups such as -OH, ═O, and -F. Here, we report the scalable synthesis and characterization of a MXene with five atomic layers of transition metals (Mo4VC4Tx), by synthesizing its Mo4VAlC4 MAX phase precursor that contains no other MAX phase impurities. These phases display twinning at their central M layers which is not present in any other known MAX phases or MXenes. Transmission electron microscopy and X-ray diffraction were used to examine the structure of both phases. Energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and high-resolution scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy were used to study the composition of these materials. Density functional theory calculations indicate that other five transition metal-layer MAX phases (M'4M″AlC4) may be possible, where M' and M″ are two different transition metals. The predicted existence of additional Al-containing MAX phases suggests that more M5C4Tx MXenes can be synthesized. Additionally, we characterized the optical, electronic, and thermal properties of Mo4VC4Tx. This study demonstrates the existence of an additional subfamily of M5X4Tx MXenes as well as a twinned structure, allowing for a wider range of 2D structures and compositions for more control over properties, which could lead to many different applications.

Keywords: MAX phase; MXene; properties; structure; synthesis; two-dimensional.