Organic solvent transport through reduced graphene oxide membranes with controlled oxygen content

Recent advancements in membranes based on 2-dimensional (2D) materials have enabled precise control over angstrom-scale pores, providing a unique platform for studying diverse mass transport mechanisms. In this work, we systematically investigate the transport of solvent vapors through 2D channels made of graphene oxide (GO) laminates with precisely controlled oxygen content. Using in-situ chemical reduction of GO with vitamin C, we fabricated reduced GO membranes (VRGMs) with oxygen content systematically decreased from 31.6% (pristine GO) to 24.0% (VRGM-maximum reduction). Vapour permeability measurements showed a distinct correlation between oxygen functional groups and solvent transport behaviour. Specifically, non-polar hexane exhibits 114% of enhanced permeance through the reduced membranes with larger graphitic domains, while the permeance of water decreases by 55%. With the support of density functional theory (DFT) simulations, we modelled the hydrogen-bond and dispersion complexes between the solvents and GO and calculated the complexation energies. The simulation results suggest that polar molecules interact with the oxygen functional groups of GO via a hydrogen-bond network, supporting in-plane transport. In contrast, van der Waals forces drive the transport of low-polarity solvents along the graphitic domains of the 2D channel in reduced GO membranes. Our findings provide potential strategies for future design of organic solvent nanofiltration membranes. Strong polar molecules interact with oxygen functional groups of GO via a hydrogen bond network supporting in-plane transport. In comparison, van der Waals forces drive the transport of low-polarity solvents along the graphitic domains of the 2d channel in reduced graphene oxide membranes.