Competitive Anion/Water and Cation/Water Interactions at Electrified Copper/Electrolyte Interfaces Probed by in Situ X-ray Diffraction

The full 3D structure of a copper/electrolyte interface is studied by means of in situ surface X-ray diffraction (SXRD) methods. Chloride anions chemisorb on Cu(100) in 10 mM HCI at high potentials under formation of a p(1 X 1)-Cl adlayer: This anionic chemisorption layer serves as a structural template for the lateral ordering of water molecules and hydronium cations in the near-surface liquid electrolyte. Evidence for this interfacial geometry is mainly derived from the intensity distribution of surface-sensitive X-ray diffraction data along the (10L)-adlayer rod. The characteristic oscillating intensity distribution along the (10L) rod is due to a centered bilayer system consisting of the anionic inner Helmholtz layer (IHL) of chemisorbed chloride and the cationic outer Helmholtz layer (OHL). The latter is constituted in the present case by hydronium cations that preferentially populate 4-fold hollow sites of the underlying chloride lattice. IHL and OHL are separated by an extra interfacial water layer. Anions and cations in the IHL and OHL compete for these water species as part of their solvation shell. The Cl/water/hydronium bilayer can be considered as a prototypical model system where the anions and cations in the coupled bilayer system are sharing the interfacial water as part of their solvation shell. In this respect, the Cl-/water/hydronium bilayer considerably differs from the previously studied Cl-/water/K+ system where the interfacial water was clearly assigned to the solvation shell of the alkali metal cation in the OHL. The absence of strongly solvated alkali metal cations in the OHL leads to an increase in the in-plane and out-of-plane exchange dynamics of water and hydronium cations as manifested by an isotropic atomic displacement parameter that is notably higher for the Cl-/water/hydronium than for the more static Cl-/water/K+ system. A comprehensive comparison of our results with other state-of-the-art SXRD studies strongly suggests that the adsorption of partly solvated cations on-top of an anion-modified metal electrode surface has to be considered as a specific cation adsorption phenomenon since the particular structure of the formed bilayer system as well as the involved interfacial dynamics clearly depend on the chemical nature of the anions and cations involved in the structure formation.