The rapid progression of industrialization has significantly intensified the contamination of water resources by heavy metal ions, thereby exacerbating the global challenge of water scarcity. Aiming at solving this pressing issue of worldwide freshwater scarcity, nanomaterial and nanotechnology show a pivotal alternative in wastewater treatment. In this study, we construct distinct graphene nanosheets with varying shaped and sized pores (named as graphene crown pores) and assess the protonation of the pore edges to the heavy metal ion removal capacity. Employing molecular dynamics (MD) simulations, we demonstrate that protonated graphene nanopores exhibit exceptional water permeability and outstanding ion rejection rates. Moreover, our free energy calculations confirm that water molecules encounter a lower energy barrier compared to ions when traversing through graphene crown pores. Furthermore, the non-protonated graphene pores allow faster water permeance while compromising the ion rejection, yielding a dissatisfactory performance of metal ion removal. Detailed analysis suggest that the protonated pore endows the pore with a positively charged center, obstructing the passage of heavy metal ions. Therefore, our findings not only propose the protonated graphene crown pores for efficient heavy metal ion removal but also reveal the corresponding molecular mechanism, which is useful for future application of such membranes for heavy metal ion removal.
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