Stability of Substituted Phenyl Groups Electrochemically Grafted at Carbon Electrode Surface

Abstract

The electrochemical reduction of an aryl diazonium tetrafluoroborate salt, dissolved in acetonitrile, at a carbon electrode surface allowed the grafting of aryl groups with the formation of a carbon-carbon bond. Groups such as 4-carboxyphenyl, 4-nitrophenyl, 4-diethylaniline (DEA), and 4-bromophenyl were grafted at a glassy carbon electrode surface. The stability of these grafted groups, present at the glassy carbon electrode surface, was studied at various electrode potentials in aqueous media. In appropriate experimental conditions, the as-grafted groups severely inhibit the cyclic voltammetry response of selected redox probes. Thus, the reappearance and/or increase of an electrochemical response, after polarization, was taken as an indication that a modification of the grafted layer occurred. Our results demonstrated that polarization at very positive (ca. 1.8 V) and negative (ca. -2 V) potentials is needed to observe an electrochemical response. Electrochemical impedance and X-ray photoelectron spectroscopies were also used to investigate the stability of the grafted layers. The impedance data usually tracks fairly well the cyclic voltammetry results, although the former appears to be more sensitive to changes that are occurring upon polarization of the modified electrode. Interestingly, the XPS data indicate clearly that the grafted layer is not always completely removed at the extreme positive and negative potentials investigated. A mechanism was proposed to explain the transformation occurring during polarization of the modified electrode and involves desorption of the substituted aryl groups during the concomitant hydrogen, oxygen, or chlorine evolution and finally leaving close to a covalently bonded monolayer of the grafted species at the electrode surface.

Electronic Structure of Methoxy-, Bromo-, and Nitrobenzene Grafted onto Si(111)

“…This adventitious nitrogen signal was also observed by other groups. 6,7,17,18 Generally, our findings from XPS are similar to those of refs 6 and 7 where grafting also occurred on Si(111). For the methoxybenzene process, the C1s intensity was much less, indicating a considerably smaller adsorbate layer thickness.…”

Covalent modification of graphitic carbon substrates by non-electrochemical methods

“…For systems studied in detail, the attached coatings have been shown to be largely unaffected by elevated temperatures [10,11] and extended sonication in aggressive solvents [10,11,12,13]. In electrochemical investigations, grafted layers have also been shown to withstand cycling over a wide potential range [14,15,16].…”

Chemically Modified Carbon Nanotubes: Derivatization and Their Applications

“…The C -C bond formed in this strategy is significantly stronger than the gold -thiol bond and they can withstand temperature upto 700 K without being lost from the surface [18]. It is quite stable over wide potential window in the range 2.6 -5.6 V depending on the substituents on the para position [19]. In contrast to the enhanced stability, formation of these layers on electrode surfaces are less controlled than for the alkane-thiol system.…”