Cation dominated but negatively charged Na2SO4,aq-graphene interfaces.

The distribution of ions and their impact on the structure of electrolyte interfaces plays an important role in many applications. Interestingly, recent experimental studies have suggested the preferential accumulation of SO42- ions at the Na2SO4,aq-graphene interface in disagreement with the generally known tendency of cations to accumulate at graphene-electrolyte interfaces. Herein, we resolve the atomistic structure of the Na2SO4,aq-graphene interface in the 0.1-2.0M concentration range using machine learning interatomic potential-based simulations and simulated sum frequency generation (SFG) spectra to reveal the molecular origins of the conundrum. Our results show that Na+ ions accumulate between the outermost and second interfacial water layers whereas SO42- ions accumulate within the second interfacial water layer indicating cation dominated interfaces. We find that the interfacial region (within ∼10 Å of the graphene sheet) is negatively charged due to the sub-stoichiometric Na+/SO42- ratio at the interface. Our simulated SFG spectra show enhancement and a redshift of the spectra in the hydrogen bonded region as a function of Na2SO4 concentration similar to measurements due to SO42--induced changes in the orientational order of water molecules in the second interfacial layer. Our study demonstrates that ion stratification and ion-induced water reorganization are key elements of understanding the electrolyte-graphene interface.