Molecular simulations of the adsorption of aniline from waste-water

Molecular simulations of adsorption processes have received considerable attention. Despite the attention, exploration of the literature shows serious limitations, among which solvent and temperature effects are the most important. In this work, we propose a computational approach to study the adsorption of aniline (as an example of pollutant) from wastewater using coronene as adsorbent. We identified all possible adsorption sites using classical molecular dynamics for further optimization at the ωB97XD/aug-cc-pVDZ level of theory. Three different solvation schemes have been explored: implicit solvation of aniline + coronene, explicit solvation of aniline + coronene, and implicit-explicit solvation of aniline + coronene. For the explicit solvation, we used six water molecules, while the implicit solvation is performed using the PCM (polarizable continuum medium) solvation model. For each of the four cases (gas phase and the three solvation schemes), the adsorption free energy is evaluated as function of temperature from 200 K to 400 K. The results show that solvation has a considerable effects on the adsorption free energy. Furthermore, we noted that the adsorption free energy varies from -39.5 kJ mol^-1 at 200 K to 27.7 kJ mol^-1 at 400 K using the implicit-explicit solvation of aniline + coronene. This result highlights the importance of considering temperature effects in molecular simulations study of adsorption processes.