Self-Limited Grafting of Sub-Monolayers via Diels-Alder Reaction on Glassy Carbon Electrodes: An Electrochemical Insight.

The grafting of molecular monolayers is critical for the functionalization of surfaces. In molecular electrochemistry, the surface modification of electrodes and the way molecules are attached to the electrode surface are highly critical to electron transfers and electrochemical reactions. In this paper, sub-monolayers were covalently grafted onto glassy carbon (GC) electrodes via Diels-Alder cycloaddition with two soluble dienophiles, that is, propargyl bromide and ethynyl ferrocene. Such an approach is clean (no by-product, no catalyst/additive) and occurs under mild conditions by heating at 50 °C in toluene for few hours. The as-modified electrodes were thoroughly characterized by FTIR, XPS, and cyclic voltammetry using both millimetric GC electrodes and ultra-microelectrodes. Cyclic voltammetry gave access to surface coverage and clearly evidenced the covalent grafting of sub-monolayers. The grafting of functional sub-monolayers via Diels-Alder cycloaddition could be easily extended to various functionalities and carbons to prepare electrochemical sensors or electrocatalytic surfaces.

Plasmonic mode interferences and Fano resonances in Metal-Insulator-Metal nanostructured interface.

Metal-insulator-metal systems exhibit a rich underlying physics leading to a high degree of tunability of their spectral properties. We performed a systematic study on a metal-insulator-nanostructured metal system with a thin 6 nm dielectric spacer and showed how the nanoparticle sizes and excitation conditions lead to the tunability and coupling/decoupling of localized and delocalized plasmonic modes. We also experimentally evidenced a tunable Fano resonance in a broad spectral window 600 to 800 nm resulting from the interference of gap modes with white light broad band transmitted waves at the interface playing the role of the continuum. By varying the incident illumination angle shifts in the resonances give the possibility to couple or decouple the localized and delocalized modes and to induce a strong change of the asymmetric Fano profile. All these results were confirmed with a crossed comparison between experimental and theoretical measurements, confirming the nature of different modes. The high degree of control and tunability of this plasmonically rich system paves the way for designing and engineering of similar systems with numerous applications. In particular, sensing measurements were performed and a figure of merit of 3.8 was recorded ranking this sensor among the highest sensitive in this wavelength range.