Covalent surface modifications and superconductivity of two-dimensional metal carbide MXenes

Modifying MXene surfaces Unlike graphene and transition-metal dichalcogenides, two-dimensional transition-metal carbides (MXenes) have many surface sites that can be chemically modified. Etching of the aluminum layer of a parent MAX phase Ti3AlC2 layered material with hydrofluoric acid leads to the MXene Ti3C2 with various surface terminations. Molten salts can achieve uniform chloride terminations, but these are difficult to further modify. Kamysbayev et al. show that etching of MAX phases in molten cadmium bromide leads to bromide-terminated MXenes that can then be substituted with oxygen, sulfur, selenium, tellurium, and NH groups as well as with vacancy sites. The surface groups can alter electronic transport. For example, the Nb2C MXenes exhibit surface group–dependent superconductivity. Science, this issue p. 979 Substitution and elimination reactions in molten inorganic salts modified two-dimensional transition-metal carbide surfaces. Versatile chemical transformations of surface functional groups in two-dimensional transition-metal carbides (MXenes) open up a previously unexplored design space for this broad class of functional materials. We introduce a general strategy to install and remove surface groups by performing substitution and elimination reactions in molten inorganic salts. Successful synthesis of MXenes with oxygen, imido, sulfur, chlorine, selenium, bromine, and tellurium surface terminations, as well as bare MXenes (no surface termination), was demonstrated. These MXenes show distinctive structural and electronic properties. For example, the surface groups control interatomic distances in the MXene lattice, and Tin+1Cn (n = 1, 2) MXenes terminated with telluride (Te2−) ligands show a giant (>18%) in-plane lattice expansion compared with the unstrained titanium carbide lattice. The surface groups also control superconductivity of niobium carbide MXenes.