2D titanium carbonitrides and their hydroxylated derivatives: Structural, electronic properties and stability of MXenes Ti3C2-xNx and Ti3C2-xNx(OH)2

Abstract: 3D titanium carbonitrides TiCxNy possess excellent physical, chemical, and mechanical properties, attractive for various industrial applications. Most recently, the uncommon nano-sized layers of 2D-like titanium carbonitrides were fabricated from MAX phases. Herein, the structural, electronic properties and stability of these new compounds as well as their hydroxylated derivatives - so-called MXenes Ti3C2-xNx and Ti3C2-xNx(OH)2 are probed by means of SSC-DFTB calculations. The genesis of the properties is discussed in the sequence: binary MXenes Ti3C2 (Ti3N2) -> their hydroxylated forms Ti3C2(OH)2 (Ti3N2(OH)2) -> pristine MXene Ti3C2-xNx -> hydroxylated Ti3C2-xNx(OH)2. Our results show that the examined materials are metallic-like. The most favorable type of OH-covering is presented by the occupation of the hollow sites between three neighboring carbon (nitrogen) atoms. The formation of 2D MXene carbonitrides with random distribution of C and N atoms was found to be thermodynamically more favorable.