An ultrasensitive and highly selective nanomolar electrochemical sensor based on an electrocatalytic peak shift analysis approach for copper trace detection in water

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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.