Computational Dissection of Two-Dimensional Rectangular Titanium Mononitride TiN: Auxetics and Promises for Photocatalysis

Recently, two-dimensional (2D) transition-metal nitrides have triggered an enormous interest for their tunable mechanical, optoelectronic, and magnetic properties, significantly enriching the family of 2D materials. Here, by using a broad range of first-principles calculations, we report a systematic study of 2D rectangular materials of titanium mononitride (TiN), exhibiting high energetic and thermal stability due to in-plane d–p orbital hybridization and synergetic out-of-plane electronic delocalization. The rectangular TiN monolayer also possesses enhanced auxeticity and ferroelasticity with an alternating order of Possion’s Ratios, stemming from the competitive interactions of intra- and inter- TiN chains. Such TiN nanosystem is a n-type metallic conductor with specific tunable pseudogaps. Halogenation of TiN monolayer downshifts the Fermi level, achieving the optical energy gap up to 1.85 eV for TiNCl­(Br) sheet. Overall, observed electronic features suggest that the two materials are potential photocatalysts for water splitting application. These results extend emerging phenomena in a rich family 2D transition-metal-based materials and hint for a new platform for the next-generation functional nanomaterials.