Electrocatalysis of 2,5-Dimercapto-1,3,5-thiadiazole by 3,4-Ethylenedioxy-Substituted Conducting Polymers

• Published in: Langmuir 2011-11, Vol.27 (22), p.13904-13909
• Main Authors: Rodríguez-Calero, Gabriel G, Lowe, Michael A, Burkhardt, Stephen E, Abruña, Héctor D
• Format: Article
• Language: English
• Subjects: Catalysis; Chemistry; Electrochemistry; Electrochemistry - methods; Electrochemistry: Charge Transfer, Electrocatalysis, Kinetics, Bioelectrochemistry; Ethylenes - chemistry; Exact sciences and technology; General and physical chemistry; Kinetics and mechanism of reactions; Microscopy, Electron, Scanning; Polymers - chemistry; Thiadiazoles - chemistry
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/la202706s

The electronic properties of electropolymerized films of the 3,4-ethylenedioxy-substituted conducting polymers (CP) poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3,4-ethylenedioxypyrrole) (PEDOP) and poly(3,4-ethylenedioxyselenophene) (PEDOS) have been investigated, along with their electrocatalytic activity toward 2,5-dimercapto-1,3,4-thiadiazole (DMcT). For the electropolymerized films, the conductivity onset potential was most negative for PEDOP (−1.50 V), followed by PEDOS (−1.35 V) and with PEDOT possessing the most positive onset (−1.15 V). The heterogeneous charge transfer rate constant for DMcT in solution at polymer-film-modified glassy carbon electrodes (GCEs) was studied. It was found that compared to PEDOP, both PEDOS and PEDOT performed better as electrocatalysts, with PEDOS having a heterogeneous charge transfer rate constant of 1.8 × 10–3 cm/s. The film morphology of the electropolymerized films was investigated via SEM, and some film characteristics could be correlated with electrocatalytic activity. The potential use of CP/DMcT composites for lithium ion batteries (LIBs) is discussed.