Linking Electric Double Layer Formation to Electrocatalytic Activity

Sensitivity Analysis of Electrochemical Double Layer Approximations on Electrokinetic Predictions: Case Study for CO Reduction on Copper

“…Although the high sensitivity in predicted activation energies observed in this work can be discouraging, opportunities arise as tuning the EDL environment is predicted to impact electrocatalytic selectivity and activity. Electrolyte engineering strategies for electrocatalysis have been studied, such as altering the identity of the ion and using ionic liquids and mixed solvents. ,,,,,− This analytical approach, alongside experimental efforts, can rationally use these opportunities to advance electrocatalytic system design. This work also motivates additional efforts to determine double-layer structures and dielectric properties, for which classical force-field molecular dynamics are well-suited methods. ,,, …”

The Anomalous Behavior of Cesium in the Electrical Double Layer: an In-Situ X-ray Spectroscopy Study on Graphene

“…Displacement of Cs + by SO4 2and formation of Ion pairs between cesium and sulfate ions is the most likely explanation for all three observed phenomena (sudden decrease in intensity, decrease in BE and increase in FWHM of Cs 4d doublet), as caused by decrease of the interfacial Cs + concentration by replacement of adsorbed Cs + by sulfates. The ion pairs of Cs + and SO4 2ions share a solvation shell, decreasing the formal charge of the cluster 33,34 This leads to a decrease of the iterfacial e-field and therefore halts accelation of kinetic electrons that escape the electrolyte, leading to an apparent increased binding energy.…”

Rational design of local microenvironment for electrocatalytic water splitting

“…1a). 36 The Helmholtz model laid the foundation for our early understanding of electrochemical interfaces. However, the model only considers the electrostatic repulsion experienced by counterions, without considering the mixed diffusion of ions in solution caused by thermal motion and the interaction between the solvent and electrode, and the differential capacitance predicted by the model depends on the dielectric constant of the solvent electrolyte and the thickness of the double layer, independent of charge density, which contradicts the minimum value of differential capacitance observed in dilute solutions.…”