An electrochemical bifunctional sensor for the detection of nitrite and hydrogen peroxide based on layer-by-layer multilayer films of cationic phthalocyanine cobalt(ii) and carbon nanotubes

Abstract

As vital biological mediators, the accurate detection of nitrite (NO₂⁻) and hydrogen peroxide (H₂O₂) is desirable for clinical monitoring and diagnosis. Herein, cationic 2,9,16,23-tetra[4-(N-methyl)pyridinyloxy]phthalocyanine cobalt(II) ([TMPyPcCo]⁴⁺) and acid-treated multiwalled carbon nanotubes (aCNTs) were alternately self-assembled on the glassy carbon electrode (GCE) by means of the electrostatic interaction, leading to a 3D loose and interconnected assembly of [TMPyPcCo/aCNTs]_n multilayer films. In the [TMPyPcCo/aCNTs]_n films, [TMPyPcCo]⁴⁺ is anchored onto the surface of aCNTs without any inert polymer binders, which is beneficial to expose more active sites for electrocatalysis. The effective combination of [TMPyPcCo]⁴⁺ and aCNTs brings many advantages in electrochemical detection, involving the fast oriented transmission of charges, permeable channels for ion adsorption and transport, and more sensing sites, thus the [TMPyPcCo/aCNTs]_n films display excellent electrochemical sensitivity towards both NO₂⁻ and H₂O₂. The responses of NO₂⁻ and H₂O₂ vary linearly with respect to the concentration from 5 µM to 30 mM and 10 µM to 9 mM. Furthermore, the superior cycling stability, reproducibility, and selectivity make [TMPyPcCo/aCNTs]_n films suitable for the real samples.