An ultrasensitive and highly selective nanomolar electrochemical sensor based on an electrocatalytic Peak Shift Analysis approach for copper trace detection in water.

Type Article
Date 2022-12
Language English
Author(s) Challier LylianORCID1, Forget AmélieORCID2, Bazin Charlène1, Tanniou Simon1, Le Doare Justine1, Davy Romain1, Bernard Hélène2, Tripier RaphaelORCID2, Laes-Huon AgatheORCID1, Le Poul Nicolas2
Affiliation(s) 1 : Laboratoire Détection Capteurs et Mesures, Unité Recherches et Développements Technologiques, Ifremer, Plouzané, France.
2 : Laboratoire CEMCA UMR CNRS 6521, Université de Bretagne Occidentale, 6 Avenue Victor le Gorgeu, C.S. 93837, 29238 Brest, France
Source Electrochimica Acta (0013-4686) (Elsevier BV), 2022-12 , Vol. 434 , P. 141298 (8p.)
DOI 10.1016/j.electacta.2022.141298
Keyword(s) Copper sensor, Modified graphite electrode, Electrolyte engineering, Hydrogen evolution reaction, Peak shift analysis
Abstract

Copper (Cu) sensing in the nanomolar range is an important challenge for marine water monitoring, especially with eco-friendly materials and reagents. For this purpose, electrochemical Cu(II) sensors appear as fully suitable because of their relatively high sensitivity, selectivity and adaptability for in situ measurements. So far, one of the usual electrochemical methods for Cu(II) sensing is adsorptive anodic stripping voltammetry (AdASV), since it offers a good selectivity, accumulation at open circuit potential and a reliable analytical response for concentrations above 10 nmol.L−1. Surprisingly, no work has ever addressed an electrocatalytic procedure to enhance the electrochemical copper sensing and allowed detection below 10 nM. Thus, we have developed an original two-step strategy based on the surface modification of pencil graphite electrodes (PGE) with p-aminobenzyl-C-functionalized cyclam, a strong chelating ligand for Cu(II), as well as the use of a simple reaction which can be electrocatalyzed by Cu such as HER (Hydrogen Evolution Reaction) to finally determine the accumulated amount of copper catalyst on the PGE. We show here that i) a well-defined diffusion-limited catalytic peak can be obtained from cyclic voltammetry (CV) experiments with Cu(II)-cyclam-modified PGE, ii) this HER peak potential is correlated to copper surface concentration, which can be sensed at the same time by adsorptive anodic stripping voltammetry and iii) peak shift analysis (SA) of the voltammetric curves is a more sensitive method than the commonly used stripping voltammetry to reveal copper accumulation at modified PGE. Indeed, the limit of detection (LOD) reached with this method is one order of magnitude lower compared to AdASV (LOD = 1.1 nM and 16 nM, respectively). These results illustrate the ability of electrocatalysis to be a relevant tool under certain conditions for metal trace detection through SA.

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Challier Lylian, Forget Amélie, Bazin Charlène, Tanniou Simon, Le Doare Justine, Davy Romain, Bernard Hélène, Tripier Raphael, Laes-Huon Agathe, Le Poul Nicolas (2022). An ultrasensitive and highly selective nanomolar electrochemical sensor based on an electrocatalytic Peak Shift Analysis approach for copper trace detection in water. Electrochimica Acta, 434, 141298 (8p.). Publisher's official version : https://doi.org/10.1016/j.electacta.2022.141298 , Open Access version : https://archimer.ifremer.fr/doc/00796/90831/