Characterization of the Deposition of Organic Molecules at the Surface of Gold by the Electrochemical Reduction of Aryldiazonium Cations

• Published in: Langmuir 2005-07, Vol.21 (15), p.6855-6865
• Main Authors: Laforgue, Alexis, Addou, Tania, Bélanger, Daniel
• Format: Article
• Language: English
• Subjects: Chemistry; Exact sciences and technology; General and physical chemistry
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/la047369c

The deposition of 4-X phenyl groups (X = NO2, COOH, N−(C2H5)2) on polycrystalline gold electrode was achieved by the electrochemical reduction of the corresponding 4-substituted phenyldiazonium tetrafluoroborate salts in anhydrous acetonitrile media. The electrochemical quartz crystal microbalance measurements evidenced a two-step deposition process:  the first one is the deposition of close to a monolayer and the second one is the relatively slower growth of multilayers. In this second region, the deposition is less efficient than for the first one. The electrochemical behavior of the resulting modified gold electrode was investigated in the presence of an electroactive redox probe and these results, together with the electrochemical quartz crystal microbalance data, demonstrated significant differences in reactivity and in deposition efficiency between the diazonium salts. The characterization of the modified electrodes by cyclic voltammetry and electrochemical impedance spectroscopy, as well as X-ray photoelectron spectroscopy measurements, showed that the formation of multilayers is possible and that a significant fraction of the deposited material remained at the electrode surface, even following ultrasonic treatment. The X-ray photoelectron spectroscopy data indicate that the existence of Au−C and Au−NN−C linkages (where C represents a carbon atom of the phenyl group) is uncertain. Nonetheless, the deposition of the aryl groups by electrochemical reduction of diazonium cations yielded a film that adheres well to the gold surface and the deposited organic film hindered gold oxides formation in acidic medium.