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

MXenes are a family of two-dimensional (2D) transition metal carbides, nitrides, and carbonitrides with a general formula of M n+1X n T x , 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 T x 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 (Mo4VC4T x ), 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 M5C4T x MXenes can be synthesized. Additionally, we characterized the optical, electronic, and thermal properties of Mo4VC4T x . This study demonstrates the existence of an additional subfamily of M5X4T x 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.