Layered
carbides are fascinating compounds due to their enormous
structural and chemical diversity, as well as their potential to possess
useful and tunable functional properties. Their preparation, however,
is challenging and forces synthesis scientists to develop creative
and innovative strategies to access high-quality materials. One unique
compound among carbides is Mo2Ga2C. Its structure
is related to the large and steadily growing family of 211 MAX phases
that crystallize in a hexagonal structure (space group P63/mmc) with alternating layers of edge-sharing M
6
X octahedra and layers of
the A-element. Mo2Ga2C also
crystallizes in the same space group, with the difference that the A-element layer is occupied by two A-elements,
here Ga, that sit right on top of each other (hence named “221”
compound). Here, we propose that the Ga content in this compound is
variable between 2:2, 2:1, and 2: ≤1 (and 2:0) Mo/Ga ratios.
We demonstrate that one Ga layer can be selectively removed from Mo2Ga2C without jeopardizing the hexagonal P63/mmc structure. This is realized
by chemical treatment of the 221 phase Mo2Ga2C with a Lewis acid, leading to the “conventional”
211 MAX phase Mo2GaC. Upon further reaction with CuCl2, more Ga is removed and replaced with Cu (instead of fully
exfoliating into the Ga-free Mo2CT
x
MXene), leading to Mo2Ga1–x
Cu
x
C
still crystallizing with space group P63/mmc, however, with a significantly larger c-lattice parameter. Furthermore, 211 Mo2GaC
can be reacted with Ga to recover the initial 221 Mo2Ga2C. All three reaction pathways have not been reported previously
and are supported by powder X-ray diffraction (PXRD), electron microscopy,
X-ray spectroscopy, and density functional theory (DFT) calculations.