Investigation of the pH-mediated fabrication process of pure and polyethyleneimine-crosslinked graphene oxide membranes for desalination and heavy metal ion separation

Graphene oxide (GO) membranes have been extensively investigated and employed in separating various ions and molecules due to their superior physicochemical properties. However, the inconsistency in their pore structure, difficulty in the precise tuning of their d-spacing, and instability in aqueous solution – especially at extreme pH values – might hinder their separation efficiency. In this research, we systematically investigated the pH-mediated fabrication process of graphene oxide membranes and evaluated the properties of the resulting membranes. Findings from scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses show that a higher fabrication pH results in a thicker GO layer and an enlarged d-spacing due to the deprotonation of the GO's carboxyl groups. Furthermore, pH-assisted crosslinking between polyethyleneimine (PEI) and GO sheets were facilitated and the chemical analysis results suggest that in acidic environments, the dominant reaction involves C–N bond formation at the basal plane, whereas under alkaline conditions, N–C[dbnd]O (amide) bond formation at the edges is more prevalent. This, in return, accordingly shifted the trend in SEM and XRD, where a thinner GP layer and a decreased d-spacing were observed at a higher fabrication pH due to the deprotonation of the incorporated PEI's amine groups. These findings contributed to the nanofiltration (NF) performance of the membranes against different inorganic salts and heavy metal ions. It was discovered that the GP_pH11 membrane formed at pH 11 has the highest Pb²⁺ rejection of >95%, making it a suitable material for heavy metal ions removal.