Organic contaminants and atmospheric nitrogen at the graphene-water interface: a simulation study

R Thakkar and S Gajaweera and J Comer, NANOSCALE ADVANCES, 4, 1741-1757 (2022).

DOI: 10.1039/d1na00570g

Ordered nanoscale patterns have been observed by atomic force microscopy at graphene-water and graphite-water interfaces. The two dominant explanations for these patterns are that (i) they consist of self- assembled organic contaminants or (ii) they are dense layers formed from atmospheric gases (especially nitrogen). Here we apply molecular dynamics simulations to study the behavior of dinitrogen and possible organic contaminants at the graphene-water interface. Despite the high concentration of N-2 in ambient air, we find that its expected occupancy at the graphene-water interface is quite low. Although dense (disordered) aggregates of dinitrogen have been observed in previous simulations, our results suggest that they are stable only in the presence of supersaturated aqueous N-2 solutions and dissipate rapidly when they coexist with nitrogen gas near atmospheric pressure. On the other hand, although heavy alkanes are present at only trace concentrations (micrograms per cubic meter) in typical indoor air, we predict that such concentrations can be sufficient to form ordered monolayers that cover the graphene-water interface. For octadecane, grand canonical Monte Carlo suggests nucleation and growth of monolayers above an ambient concentration near 6 mu g m(-3), which is less than some literature values for indoor air. The thermodynamics of the formation of these alkane monolayers includes contributions from the hydration free-energy (unfavorable), the free-energy of adsorption to the graphene-water interface (highly favorable), and integration into the alkane monolayer phase (highly favorable). Furthermore, the peak-to- peak distances in AFM force profiles perpendicular to the interface (0.43-0.53 nm), agree with the distances calculated in simulations for overlayers of alkane-like molecules, but not for molecules such as N-2, water, or aromatics. Taken together, these results suggest that ordered domains observed on graphene, graphite, and other hydrophobic materials in water are consistent with alkane-like molecules occupying the interface.

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