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Journal of

Electroanalytical
Chemistry
Journal of Electroanalytical Chemistry 589 (2006) 212–218
www.elsevier.com/locate/jelechem

Trends in reactivity of unsubstituted and substituted


cobalt-phthalocyanines for the electrocatalysis of glucose oxidation
Cristián Barrera a, Igor Zhukov b, Evelyn Villagra a, Fethi Bedioui c, Maritza A. Páez a,
Juan Costamagna a, José H. Zagal a,*
a
Facultad de Quı́mica y Biologı́a, Departamento de Quı́mica de los Materiales, Universidad de Santiago de Chile (USACH),
Casilla 40, Correo 33, Santiago, Chile
b
On leave from Department of Chemistry, Moscow State University, Moscow, Russian Federation
c
Laboratoire de Pharmacologie Chimique et Génétique, UMR CNRS 8151/U INSERM 640, Ecole Nationale Supérieure de Chimie de Paris,
11 rue Pierre et Marie Curie, 75231 Paris cedex 05, France

Received 7 December 2005; received in revised form 18 January 2006; accepted 10 February 2006
Available online 23 March 2006

Abstract

This study shows that cobalt macrocyclics, namely Co-phthalocyanine (CoPc), Co-hexadecafluorophthalocyanine (CoF16Pc), Co-
octaethylhexyloxyphthalocyanine (CoOEHPc), Co-tetraaminophthalocyanine (CoTAPc) and Co-tetrasulfophthalocyanine (CoTSPc),
strongly adsorbed on a graphite electrode surface, exhibit true electrocatalytic activity for the oxidation of glucose in alkaline solution.
The Tafel analysis of the electrochemical process occurring at these chemically modified electrodes, that become ‘‘molecular phthalocy-
anine electrodes’’, suggests that a first-one electron step is rate controlling with the symmetry of the energy barrier depending on the type
of substituents grafted on the macrocycle. The effect of substituents on the phthalocyanine ring on the catalytic activity was analyzed and
a non-linear correlation is found. The volcano-shaped plot obtained when comparing catalytic activities versus the Co(II)/(I) formal
potential indicates that a narrow window of Co(II)/(I) formal potentials exists for achieving maximum activity. In the particular case
of the present work, we find that the most active phthalocyanine is the unsubstituted CoPc.
Ó 2006 Elsevier B.V. All rights reserved.

Keywords: Cobalt phthalocyanine; Glucose oxidation; Electrocatalysis; Modified electrode

1. Introduction electrodes generally used consist of carbon paste, glassy


carbon, platinum, gold or nickel materials [1–7]. Also,
The oxidation of most carbohydrates, specially the one of the main drawbacks linked to these materials comes
reducing sugars is rather favorable from the thermody- from the need for multiple pulsed potential steps to achieve
namic point of view, so it can be expected that they can cleaning and activating sequences within the detection pro-
be easily detected electrochemically following liquid chro- cess. It is then interesting to find alternative electrode mate-
matography (LCEC). However, their electrochemical oxi- rials that present higher catalytic activity and more
dation is not easy, as it requires a large overpotential on practical operating procedures. The most promising
conventional electrodes that are commonly used in LCEC. approach for doing so is the use of chemically modified
Besides glucose oxidase-based biosensors that work only in electrodes (CMEs) containing selected redox species. Vari-
very specific conditions and do not apply for LCEC, the ous attempts have been made during the last recent years,
and CMEs made from nickel oxide [8,9], ruthenium oxide
or other metal oxide [10,11], copper oxide [12–15] and
*
Corresponding author. mixed valent Prussian blue [16] have been examined for
E-mail address: jzagal@lauca.usach.cl (J.H. Zagal). the oxidation of glucose.

0022-0728/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jelechem.2006.02.009

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