Decoding the Interplay between Topology and Surface Charge in Graphene Oxide Membranes During Humidity Induced Swelling

[Image: see text] Graphene oxide (GO) membranes are known to have a complex morphology that depends on the degree of oxidation of the graphene flake and the membrane preparation technique. In this study, using Grand Canonical Monte Carlo simulations, we investigate the mechanism of swelling of GO membranes exposed to different relative humidity (RH) values and show how this is intimately related to the graphene surface chemistry. We show that the structure of the GO membrane changes while the membrane adsorbs water from the environment and that graphene oxide flakes become charged as the membrane is loaded with water and swells. A detailed comparison between simulation and experimental adsorption data reveals that the flake surface charge drives the water adsorption mechanism at low RH when the membrane topology is still disordered and the internal pores are small and asymmetric. As the membrane is exposed to higher RH (80%), the flake acquires more surface charge as more oxide groups deprotonate, and the pores grow in size, yet maintain their disordered geometry. Only for very high relative humidity (98%) does the membrane undergo structural changes. At this level of humidity, the pores in the membrane become slit-like but the flake surface charge remains constant. Our results unveil a very complex mechanism of swelling and show that a single molecular model cannot fully capture the ever-changing chemistry and morphology of the membrane as it swells. Our computational procedure provides the first atomically resolved insight into the GO membrane structure of experimental samples.