Enhancement of the selectivity of MXenes (M 2 C, M = Ti, V, Nb, Mo) via oxygen-functionalization: promising materials for gas-sensing and -separation.

Two-dimensional graphene-like materials, namely MXenes, have been proposed as potential materials for various applications. In this work, the reactivity and selectivity of four MXenes (i.e. M2 C (M = Ti, V, Nb, Mo)) and their oxygen-functionalized forms (i.e. O-MXenes or M2 CO2 ) toward gas molecules were investigated by using the plane wave-based Density Functional Theory (DFT) calculations. Small gas molecules, which are commonly found in flue gas streams, are considered herein. Our results demonstrated that MXenes are very reactive. Chemisorption is a predominant process for gas adsorption on MXenes. Simultaneously dissociative adsorption can be observed in most cases. The high reactivity of their non-functionalized surface is attractive for catalytic applications. In contrast, their reactivity is reduced, but the selectivity is improved upon oxygen functionalization. Mo2 CO2 and V2 CO2 present good selectivity toward NO molecules, while Nb2 CO2 and Ti2 CO2 show good selectivity toward NH3 . The electronic charge properties explain the nature of the substrates and also interactions between them and the adsorbed gases. Our results indicated that O-MXenes are potential materials for gas-separation/capture, -storage, -sensing, etc. Furthermore, their structural stability and SO2 -tolerant nature are attractive properties for using them in a wide range of applications. Our finding provides good information to narrow down the choices of materials to be tested in future experimental work.