Grand-Canonical Variational Theory of Oscillatory Fields at Electrified Metal-Solution Interfaces

Published: Aug. 16, 2024

The oscillatory fields near the electrode surface are not considered in classical models of electrical double layer (EDL), while holding immense importance for stability, activity, and selectivity interfacial reactions. Here, we develop a unified theoretical framework EDL under constant potential conditions, combining an orbital-free DFT treatment electrons on metal side statistical field theory charged fluids electrolyte side. resulting grand is hybrid functional electron density, electric potential, solvent polarization, referred to as density-potential-polarization (DPPFT). Built DPPFT, model Ag(110)-KPF6 aqueous interface parameterized with experimental capacitance (Cdl) data. calibrated then employed study influence electronic, ion, properties structure capacitance. Cdl profiles at different crystal faces various solutions rationalized coherently. We reveal that intensified ion layering leads elevated capacitances zero charge (PZC) narrowed ionic peaks profile. Contrary models, DPPFT allows co-ions have appreciable density surface, opening avenue decipher origin anomalous anion effects electrochemical CO2 reduction. presented adds much-needed realism modelling EDLs.

Language: Английский

Competition between ion-ion electrostatic correlations and hydrodynamic slip radically changes diffusioosmosis

Chemical Science, Journal Year: 2024, Volume and Issue: 15(44), P. 18476 - 18489

Published: Jan. 1, 2024

We have developed a mathematical model that predicts hydrodynamic slip can eliminate the diffusioosmotic flow reversal due to electrostatic correlations.

Language: Английский