Real-time spectroelectrochemical monitoring of the diazonium electrografting

Abstract

This work reports the first in-situ and real-time resolved spectroelectrochemical monitoring of a diazonium electrografting. Exploiting the 4-nitrobenzene diazonium salt reduction, we provide a spectral characterization of the adsorption kinetic...

Monitoring SEIRAS on a Graphitic Electrode for Surface-Sensitive Electrochemistry: Real-Time Electrografting

“…4-Amino-TEMPO is a stable aminoxyl radical-containing species (N–Ȯ) that exhibits a reversible electrochemical response and has been previously studied using infrared spectroscopy. , The electrooxidation of 4-amino-TEMPO allows the grafting of the molecule onto electrodes via amine bridging. − 4-NBD has been previously used as a probe to understand electrografting processes due to its clear spectral signal stemming from the nitro (NO 2 ) stretches and its redox behavior . The electroreduction of diazonium-containing species, such as 4-NBD, is a well-known process for functionalizing carbon electrodes and has been extensively studied both electrochemically ,− and spectroscopically. − …”

Operandosurface optical nanometrology reveals diazonium salts’ visible photografting mechanism

“…Pursuing such applications, however, requires a better understanding of the photochemically driven grafting process, insight into the reaction mechanism, and identifying its main controlling parameters. In spite of its popularity, quantitative studies of diazonium grafting kinetics are scarce, and the existing examples deal with electrochemical 30,31 or spontaneous grafting. 32,33 Since such grafting strategies strongly depend on the surface characteristics, their kinetics rather reveal the evolution of the surface properties and therefore does not generalize to the photografting situation.…”

When ionic liquids meet diazonium salts to generate thin layers of modified surfaces

“…However, recent electrochemical spectroscopy coupled with ultrafast voltammetry measurements evidenced the presence of diazenyl radical species intermediate, suggesting that the diazonium electroreduction occurs through a stepwise mechanism. [19,20] Thanks to these multiple modification strategies, we reached a point where almost any desired molecules moieties could be grafted with diazonium chemistry, either directly or through postfunctionalization. [21,22] Subsequently, particular efforts were made in the recent years to tune the geometry of these immobilized layers to finely modulate the properties of the modified surfaces.…”