RESUMO
To prevent eutrophication, controlling the phosphate concentration levels is one of the most important issues in surface water management. One of the most utilized methods is phosphate adsorption. However, its application faces a bottleneck due to the unclear understanding of adsorption and interaction mechanisms. The present work unlocks the phosphorus adsorption mechanisms in three-dimensional reduced graphene oxide with different reduction levels and pore sizes to remove phosphate from water using experiments and multiscale simulations. Experiments were performed to evaluate the influence of pH, ionic strength, and temperature on the adsorption. Molecular Dynamics and Ab Initio simulations evaluated the influence of the pore size and oxidation degrees of the materials. We show that the adsorption capacity of the materials increases with increasing pH and ionic strength and decreasing temperature. It is observed that the more oxidized the material and the less compact the structure, the better the adsorption. These results are theoretically explained in terms of the interaction of functional groups and the clustering of phosphate ions, which results in better adsorption in materials with larger pores. The underlying mechanisms for the 3D-reduced graphene oxide performance were confirmed by spectroscopy analysis. All the results show that 3D-reduced graphene oxide can sorb phosphate in different complex water remediation systems with characteristics that can be modulated by changing the material synthesis method.
RESUMO
Modeling water and other liquids in computational simulations requires a large set of parameters. Many works have been devoted to finding new, improved water models, with almost all of them designed for bulk systems. Here, we use carbon nanotubes as a play model to investigate the effects of introducing flexibility in water force fields during molecular dynamics simulations of nanoconfined water. We explore six different models to show that viscosity, diffusion, and dipole orientation are vastly influenced by the flexibility and the family of force fields used. Particularly, we found the level of confinement (decreasing the nanotube's diameter) to increase discrepancies in the description of the dipole alignment. In smaller (10,10) nanotubes, the flexible version of the transferable intermolecular potential with three points (TIP3P/Fs) features a high directionality, while its rigid counterpart shows a more distributed dipole orientation. Both viscosity and diffusion are also extremely dependent on the force-field family, with the flexible version of the simple point charge (SPC/Fw) featuring the lower confidence interval.