Electrocatalytic Reduction of Molecular Oxygen Using a Poly(terthiophene carboxylic acid) Appended by 1,5-Diaminonaphthalene Copper Complex

Abstract

The conducting polymer electrochemically obtained from a newly synthesized 5,2′:5′,2″ -terthiophene- 3′ -carboxylic acid monomer was modified with 1,5-diaminonaphthalene by covalent bonding, and the modified electrode was complexed with copper ions. All modifications were characterized by Fourier transform infrared spectroscopy (FTIR), electron spectroscopy for chemical analysis (ESCA), and cyclic voltammetry (CV) techniques. The electrode modified with copper ions caused a positive shift in the peak potential for oxygen reduction to 0.30 V when compared to the absence of copper in the modified electrode. An ESCA study indicates the participation of Cu(I) species in the process of catalytic reduction of oxygen. The kinetics for oxygen reduction was studied by rotating ring-disk voltammetry. The results reveal 3.6 electrons participating in the reduction of oxygen with about 75% conversion to water in an aqueous medium of 0.1 M KNO3. The kinetic study also indicates the presence of an inner sphere mechanism between copper and oxygen during the latter’s reduction. The calculated rate constant from the kinetic study on the electrocatalytic reduction of oxygen was found to be higher when compared to other copper complexes adsorbed on the carbon electrode surface. This modified electrode was also tested for the estimation of oxygen content in an aqueous solution. © 2002 The Electrochemical Society. All rights reserved.

1,10-phenanthroline metal complex covalently bonding to poly- (pyrrole-3-carboxylic acid)-coated carbon: An efficient electrocatalyst for oxygen reduction

“…Compared with the results of other research group [16,[34][35][36] shown in Table 1, our results are more competitive and satisfactory in terms of ORR activities. In this case, both of the two catalysts, especially the CuPPyPhen/C catalyst are good candidates for nonnoble metal ORR catalysts with excellent performances among the reported catalysts of the same kind up to date.…”

Biomimetic Copper Complex Containing Polymer Modified Electrode for Electrocatalytic Reduction of Oxygen

“…Moreover, while removing the oxygen atmosphere by purging argon, the current of copper(II) peak of the modified electrode is returned back to its original position and this result indicates that the oxygen binds with the copper ion reversibly. The ORR takes place in the same region of similar reported copper complex-polymer modified electrodes, -0.05 to -0.2 V [33]. …”

“…Several research groups have investigated the electrocatalytic performance of copper complexes with different ligands; (a) Cu(II) complex of 4,7-diphenyll,l0-phenanthroline disulfonate adsorbed on graphite electrodes [26][27] (b) Cu(II) hexaazamacrocyclic complex on glassy carbon electrode [28] (c) copper(II)-2,4,6-tris(2-pyridyl)-1,3,5-triazine complex adsorbed on a graphite electrode [29] (d) copper(II)-tris(3-aminopropyl)amine and imidazole complex on pyrolytic graphite electrode [30], (e) substituted-1,10-phenonthroline-copper complexes on graphite [31] and edge-plane graphite electrodes [32]. The copper complex, 1,5-diaminonaphthalene copper was attached to the conducting polymer poly-terthiophene carboxylic acid, which further deposited on GCE and studied ORR [33]. Gewirth et al reported a very high ORR activity for a synthetic copper based electrocatalyst, copper complex of 3,5-diamino-1,2,4-triazole supported on carbon black [34].…”

Chiral Recognition of Proline Enantiomers by the Catalytic Oxygen Reduction and Formation of Cu(II)‐Polymer Complex Crystals

“…Thus, to overcome the above problems, a simple and rapid method that used a conducting poly (terthiophenecarboxylic acid) (pTTC) electrode has been developed for the chiral recognition of proline enantiomers. The polymer, pTTC was obtained from a novel monomer [21] that has applications as a DNA biosensor and as an oxygen sensor [22,23]. A glassy carbon surface coated with pTTC was modified with copper ions and then covered with Nafion.…”

“…The response of the lproline-Cu(II) complex modified electrode to the oxygen reduction reaction was 30 % larger than that of the d-proline-Cu complex. After this, the peak current became constant for both of the enantiomers due to the saturation of O 2 in the sodium acetate solution [23].…”