Functional Group Induced Transformations in Stacking and Electron Structure in Mo2CTx/NiS Heterostructures

The two-dimensional transition metal carbide/nitride family (MXenes) has garnered significant attention due to their highly customizable surface functional groups. Leveraging modern material science techniques, the customizability of MXenes can be enhanced further through the construction of associated heterostructures. As indicated by recent research, the Mo2CTx/NiS heterostructure has emerged as a promising candidate exhibiting superior physical and chemical application potential. The geometrical structure of Mo2CTx/NiS heterostructure is modeled and 6 possible configurations are validated by Density Functional Theory simulations. The variation in functional groups leads to structural changes in Mo2CTx/NiS interfaces, primarily attributed to the competition between van der Waals and covalent interactions. The presence of different functional groups results in significant band fluctuations near the Fermi level for Ni and Mo atoms, influencing the role of atoms and electron's ability to escape near the interface. This, in turn, modulates the strength of covalent interactions at the MXenes/NiS interface and alters the ease of dissociation of the MXenes/NiS complex. Notably, the Mo2CO2/NiS(P6_3/mmc) heterostructure exhibits polymorphism, signifying that two atomic arrangements can stabilize the structure. The transition process between these polymorphs is also simulated, further indicating the modulation of the electronic level of properties by a sliding operation.