Cation Dominated but Negatively Charged Na2SO4,aq-Graphene Interfaces

TL;DR

This study uses machine learning simulations and spectroscopy to reveal that in Na2SO4 aqueous solutions, sulfate ions accumulate within the interfacial water layers, leading to negatively charged graphene interfaces despite the cation dominance.

Contribution

It provides the first atomistic insight into the structure of Na2SO4-graphene interfaces, explaining the sulfate ion accumulation and interfacial charge distribution.

Findings

Sulfate ions accumulate within the second interfacial water layer.

Na+ ions accumulate between the outermost and second water layers.

Interfacial region is negatively charged due to ion ratio imbalance.

Abstract

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 $SO_4^{2-}$ ions at the $Na_2SO_{4,aq}$-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 $Na_2SO_{4,aq}$-graphene interfaces in the 0.1-2.0 M 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 water layers whereas $SO_4^{2-}$ ions accumulate within the second interfacial water layer indicating cation dominated interfaces. We find that the interfacial region (within ~10 ${\AA}$ of the graphene sheet) is negatively charged due to sub-stoichiometric $Na^+$/$SO_4^{2-}$ ratio at the interface. Our simulated SFG spectra show enhancement and a red-shift of the spectra in the hydrogen bonded region as a function of $Na_2SO_4$ concentration similar to measurements due to $SO_4^{2-}$-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.