First principles modeling of composites involving TiO2 clusters supported on M2C MXenes

Abstract

First-principles calculations based on the density functional theory are performed to investigate the formation of titania/MXene composites taking (TiO2)5/M2C (M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W) as case of study. The present systematic analysis confirms a favorable, high exothermic interaction, which promotes important structural reconstructions of the (TiO2)5 cluster along with a charge transfer from the MXene to titania. MXenes composed of d3 transition metals promote the strongest interaction, deformation energy, and charge transfer, followed by d4 and d5 M2C MXenes. We provide evidence that the formation of these (TiO2)5/M2C composites is governed by charge transfer, leading to scaling relations. Using the metal composing MXene electronegativity and the MXene d-band center, we also establish linear correlations that can be used to predict the interaction strength of (TiO2)5/M2C composites just from the knowledge of the MXene composition. It is likely that the present trends hold for other TiO2/MXene composites.