Abstract

A density functional theory study was performed to analyse the interaction of COCl2 onto A-doped graphene nanosheets (AG, where A: Al, Si, Ti, Cr, Mn, Fe). Adsorption configurations, adsorption energies, electronic properties, and the interaction in a co-adsorption regime were characterised in detail for all the adsorbent-adsorbate complexes. The results show that these materials are excellent COCl2 adsorbents, with adsorption energies of up to 1.1 eV/molecule and remarkable changes in the electronic properties. The changes in the adsorption stability in a co-adsorption regime indicates that TiG and CrG are efficient adsorbents at low and high relative COCl2 concentrations; while, AlG, MnG and FeG will be efficient only at low relative COCl2 concentrations, where the adsorption stability per COCl2 molecule significantly decreases with respect to the single adsorption. Otherwise, the COCl2 adsorption and electronic response in aerobic environments was found to be suitable only for CrG and MnG, where the electronic response is based on the recognition of the [COCl2]delta(+)-dopant-[O-2]delta(-) intermediate. This work allows to propose new graphene-based materials for the adsorption, filtration, and/or collection of toxic COCl2.