Determination of subnanomolar levels of mercury (II) by using a graphite paste electrode modified with MWCNTs and Hg(II)-imprinted polymer nanoparticles.

Mercury ion-imprinted polymer nanoparticles (Hg-IP-NPs) were synthesized via precipitation polymerization by using itaconic acid as a functional monomer. A carbon paste electrode was impregnated with the synthesized Hg-IP-NPs and MWCNTs to obtain a highly sensitive and selective electrode for determination of Hg(II). Mercury ion is first accumulated on the electrode surface via an open circuit procedure. After reduction of Hg(II) ions to its metallic form at a negative pre-potential, square wave anodic stripping voltammetry was applied to generate the electrochemical signal. The high affinity of the Hg-IP-NPs for Hg(II) was substantiated by comparing of the signals of electrodes with imprinted and non-imprinted polymer. The beneficial effect of MWCNTs on the voltammetric signal is also demonstrated. Under the optimized conditions and at a typical working potential of +0.05 V (vs. Ag/AgCl), the electrode has a linear response in the 0.1-20 nmol L-1 Hg(II) concentration range and a 29 pM detection limit. The electrochemical sensitivity is as high as 1441 A·M-1·cm-2 which is among the best values known. The electrode was applied to the determination of Hg(II) in water samples. Graphical abstract Schematic representation of the sensor electrode modified with mercury-imprinted polymer nanoparticles, and the recognition and voltammetric determination steps.