Abstract
AbstractThe electrochemical grafting of the “in-situ” prepared diazopyridinium salt have permitted the attachment of pyridine moieties onto platinum and glassy carbon surfaces. The modification of the electrode surfaces is observed by a redox probe. The ability of the film for the complexation of copper (II) ions is demonstrated by square wave voltammetry. After 45 min accumulation of copper (II) ions onto the grafted electrode surfaces, the electrode signal obtained by square wave voltammetry measurement served to discriminate the adsorbed heavy metal ions. Such measurements showed that the grafted pyridine has the ability to display complexing behavior toward some heavy metal ions. DFT calculations support a strong binding of the pyridine moieties onto the Pt surface. The most favorable complexation mode of copper (II) ions as suggested from DFT is the bidentate complex. This strategy is vital in constructing a wide range of different electrochemical sensors.
Highlights
Electrochemical reduction of aryldiazonium salts, at quite low electrode potential, has permitted the modification of the electrode surface with aryl moieties [1] which may serve as physical barriers or platforms for further modifications [2-4] or are used in molecular electronics and bio sensing [5,6]
A strong feature that makes this method appealing for surface modification reactions is the remarkable stability of the nanocomposite structure generated after the attachment of aryl moieties on the electrode surface
We have performed the calculation of the Bond Dissociation Energy (BDE) [13,15] of the grafted pyridine moiety onto the 9 atom Pt cluster [19] and the effect of the second bonded moiety
Summary
Electrochemical reduction of aryldiazonium salts, at quite low electrode potential, has permitted the modification of the electrode surface with aryl moieties [1] which may serve as physical barriers or platforms for further modifications. The covalently grafted 2D pyridinic layers onto the Pt and GC (Glassy Carbon) surface, issued from their corresponding diazonium salts, were explored for the complexation of the copper (II) ions. This is the first study to our knowledge that uses the theoretical calculation to evaluate the binding energy of the grafted pyridinic layer, and the interaction (adsorption energy) of the copper (II) ions with this grafted layer. Electrochemical modification of platinum and glassy carbon surfaces with pyridine layers and their use... 723
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