The adsorption of ions to aqueous interfaces is a phenomenon that profoundly influences vital processes in many areas of science, including biology, atmospheric chemistry, electrical energy storage, and water process engineering. Although classical electrostatics theory predicts that ions are repelled from water/hydrophobe (e.g., air/water) interfaces, both computer simulations and experiments have shown that chaotropic ions actually exhibit enhanced concentrations at the air/water interface. Although mechanistic pictures have been developed to explain this counterintuitive observation, their general applicability, particularly in the presence of material substrates, remains unclear. Here we investigate ion adsorption to the model interface formed by water and graphene. Deep UV second harmonic generation measurements of the SCN − ion, a prototypical chaotrope, determined a free energy of adsorption within error of that for air/water. Unlike for the air/water interface, wherein repartitioning of the solvent energy drives ion adsorption, our computer simulations reveal that direct ion/graphene interactions dominate the favorable enthalpy change. Moreover, the graphene sheets dampen capillary waves such that rotational anisotropy of the solute, if present, is the dominant entropy contribution, in contrast to the air/water interface.specific ion effects | graphene | SHG spectroscopy | molecular dynamics | adsorption O ver a decade ago, detailed simulations predicted that certain simple ions would exhibit enhanced concentrations at the air/water interface (1), reinvigorating a century-old debate primarily addressing the origin of the famous Hofmeister effects in protein chemistry (2). Experiments subsequently verified these predictions (3, 4). Surface enhancement of simple ions has since been widely studied [e.g., see the review by Jungwirth and Tobias (5)] and attributed to various properties of the ions including size, polarizability, dispersion forces, hydration free energy (6-8), and the degree of interfacial roughness (9-11). Previous temperaturedependent deep UV (DUV) second harmonic generation (SHG) experiments from the Saykally group have determined the enthalpic and entropic contributions to the adsorption of the prototypical pseudohalide, the thiocyanate (SCN − ) ion, showing that a negative enthalpy change drives the ion adsorption, whereas a negative entropy change impedes it (9). Using molecular simulations performed in the same study, the following underlying mechanism was proposed: first, when the ion moves from the bulk to the interface, weakly interacting water molecules are displaced from both the surface and the ion solvent shell into the bulk solution, where they form stronger water-water bonds, leading to the negative enthalpy change. Second, the presence of an ion at the interface dampens its capillary wave fluctuations, leading to the negative entropy change. Although a consensus has yet to be reached regarding the complete theory of interfacial ion adsorption, these collective, detailed studie...
We continue our investigation of the behavior of simple ions at aqueous interfaces, employing the combination of two surface-sensitive nonlinear spectroscopy tools, broadband deep UV electronic sum-frequency generation and UV second harmonic generation, to characterize the adsorption of thiocyanate to the interface of water with toluenea prototypical hydrophobe. We find that both the interfacial spectrum and the Gibbs free energy of adsorption closely match results previously reported for the air–water interface. We observe no relative spectral shift in the higher-energy CTTS transition of thiocyanate, implying similar solvation environments for the two interfaces. Similarly, the Gibbs free energies of adsorption agree within error; however, we expect the respective enthalpic and entropic contributions to differ between the two interfaces, similar to our earlier findings for the air–water versus graphene–water interfaces. Further experiments and theoretical modeling are necessary to quantify the mechanistic differences.
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