title: Electrocatalysis of 2,5-dimercapto-1,3,5-thiadiazole by 3,4-ethylenedioxy-substituted conducting polymers.
abstract: 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.
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, United States.
authors.forename: Gabriel G
authors.initials: GG
authors.lastname: Rodríguez-Calero
authors.forename: Michael A
authors.initials: MA
authors.lastname: Lowe
authors.forename: Stephen E
authors.initials: SE
authors.lastname: Burkhardt
authors.forename: Héctor D
authors.initials: HD
authors.lastname: Abruña
mesh_terms: D002384:Catalysis; D004563:Electrochemistry / Q000379:methods*; D005030:Ethylenes / Q000737:chemistry*; D008855:Microscopy, Electron, Scanning; D011108:Polymers / Q000737:chemistry*; D013830:Thiadiazoles / Q000737:chemistry*
chemical_list: C570413:2,5-dimercapto-1,3,5-thiadiazole; D005030:Ethylenes; D011108:Polymers; D013830:Thiadiazoles; C036216:ethylene