Origin of Asymmetric Electric Double Layers at Electrified Oxide/Electrolyte Interfaces

[Image: see text] The structure of electric double layers (EDLs) dictates the chemistry and the physics of electrified interfaces, and the differential capacitance is the key property for characterizing EDLs. Here we develop a theoretical model for computing the differential Helmholtz capacitance C(H) of oxide–electrolyte interfaces using density functional theory-based finite-field molecular dynamics simulations. It is found that the dipole of interfacial adsorbed groups (i.e., water molecule, hydroxyl ion, and proton) at the electrified SnO(2)(110)/NaCl interfaces significantly modulates the double layer potential which leads to the asymmetric distribution of C(H). We also find that the dissociative water adsorption prefers the inner sphere binding of counterions, which in turn leads to a higher Helmholtz capacitance, compared with that of the nondissociative case at the interface. This work provides a molecular interpretation of asymmetric EDLs seen experimentally in a range of metal oxides/hydroxides.