Amino group positions dependent morphology and coverage of electropolymerized metallophthalocyanine (M = Ni and Co) films on electrode surfaces

Arumugam , Sivanesan & Abraham John, S. (2008) Amino group positions dependent morphology and coverage of electropolymerized metallophthalocyanine (M = Ni and Co) films on electrode surfaces. Electrochimica Acta, 53(22), pp. 6629-6635.

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Abstract

Electropolymerized films of teraaminometallophthalocyanines (MTAPc; M = Ni and Co) with amino groups at α- (4α-MTAPc) and β- (4β-MTAPc) positions were prepared on glassy carbon (GC) and indium tin oxide (ITO) electrodes. It was found that the electropolymerization growth rate of 4α-MTAPc was less than that of 4β-MTAPc prepared under identical conditions. Further, the surface coverage of the polymerized 4β-MTAPc film was greater than that of 4α-MTAPc polymerized film. Atomic force microscopy (AFM), X-ray diffraction (XRD) and UV–visible spectroscopic studies were carried out for the polymerized films of 4α-NiIITAPc (p-4α-NiIITAPc) and 4β-NiIITAPc (p-4β-NiIITAPc) alone because both Ni(II) and Co(II) polymerized films show similar trend in electropolymerization and surface coverage values. AFM images show that p-4α-NiIITAPc film contains islands and the thickness of this film was nearly three times less than that of p-4β-NiIITAPc. XRD patterns for the two polymerized films reveal that p-4β-NiIITAPc film was relatively more crystalline than p-4α-NiIITAPc film. Further, the compactness of these films was scrutinized from their barrier properties toward [Fe(CN)6]3−/4− redox couple. The differences in the polymerization growth rate of 4α-MTAPc and 4β-MTAPc, and the thicknesses of the resultant polymerized films suggest that unlike 4β-MTAPc one or two amino groups might have not involved in electropolymerization in the case of 4α-MTAPc. Further, the influence of surface coverage on the electrocatalytic properties of the polymerized films was studied by taking p-4β-CoIITAPc and p-4α-CoIITAPc films as examples. The electrocatalytic oxygen reduction current was almost same at both the electrodes suggesting that only the surface species were involved in the electrocatalytic reduction of oxygen.

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ID Code: 78426
Item Type: Journal Article
Refereed: Yes
Keywords: Tetraaminometallophthalocyanine, Electropolymerization, AFM, XRD, Oxygen reduction
DOI: 10.1016/j.electacta.2008.04.052
ISSN: 0013-4686
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 2008 Elsevier Ltd.
Deposited On: 09 Nov 2014 23:33
Last Modified: 11 Nov 2014 23:38

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