Abstract

The characterization of electrical double layers is important since the interfacial electric field and electrolyte environment directly affect the reaction mechanisms and catalytic rates of electrochemical processes. In this work, we introduce a spectroscopic method based on a Stark shift ruler that enables mapping the electric field strength across the electric double layer of electrode/electrolyte interfaces. We use the tungsten-pentacarbonyl(1,4-phenelenediisocyanide) complex attached to the gold surface as a molecular ruler. The carbonyl (CO) and isocyanide (NC) groups of the self-assembled monolayer (SAM) provide multiple vibrational reporters situated at different distances from the electrode. Measurements of Stark shifts under operando electrochemical conditions and direct comparisons to density functional theory (DFT) simulations reveal distance-dependent electric field strength from the electrode surface. This electric field profile can be described by the Gouy-Chapman-Stern model with Stern layer thickness of ∼4.5 Å, indicating substantial solvent and electrolyte penetration within the SAM. Significant electro-induction effect is observed on the W center that is ∼1.2 nm away from the surface despite rapid decay of the electric field (∼90%) within 1 nm. The applied methodology and reported findings should be particularly valuable for the characterization of a wide range of microenvironments surrounding molecular electrocatalysts at electrode interfaces and the positioning of electrocatalysts at specific distances from the electrode surface for optimal functionality.

Talk to us

Join us for a 30 min session where you can share your feedback and ask us any queries you have

Schedule a call

Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.