Electrocatalytic Activity of Cobalt Phthalocyanines Revisited: Effect of the Number of Oxygen Atoms and Conjugation to Carbon Nanomaterials

The synthesis and characterization of tetrakis[4(4-acetlyphenoxy)phthalocyanato] cobalt (II) ( 1 ) are presented. Complex 1 together with the reported tetrakis dimethyl 5-(phenoxy)-isophthalatephthalocyaninato] cobalt (II) ( 2 ) are conjugated to carbon-based nanomaterials: graphene quantum dots (GQDs) and single-walled carbon nanotubes (SWCNTs) via π-π stacking, taking advantage of the π electrons on the graphitic structure of the nanomaterial as well as on the aromatic rings of the Co phthalocyanines (CoPcs). The electrocatalytic behaviour of the CoPcs, GQDs, SWCNTs and their respective conjugates towards the electrochemical oxidation of catechol was studied. The electrocatalytic probes were drop-dried onto the electrode surface of the glassy carbon electrode (GCE). The electrochemical oxidation of catechol was studied using cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry. Complex 2 when linked to GQDs gave the lowest oxidation peak potentials of 0.33 V. Low catechol detection limits (LOD) of 0.057 µM was obtained for complex 2 with SWCNT. Thus, complex 2 containing more oxygen atoms outperformed complex 1 with less oxygen atoms. The CoPcs on their own showed moderate electrocatalytic behaviour, hence showing the importance of conjugating them to the carbon nanomaterials. SWCNT-based electrodes performed better than GQDs, and an improvement in the LoDs, sensitivity and the catalytic rate was observed upon conjugation. Graphical Abstract