Colorimetric Assay Conversion to Highly Sensitive Electrochemical Assay for Bimodal Detection of Arsenate Based on Cobalt Oxyhydroxide Nanozyme via Arsenate Absorption

This study reports a novel and convenient bimodal method for label-free and signal-off detection of arsenate in environmental samples. Cobalt oxyhydroxide (CoOOH) nanoflakes with facile preparation and intrinsic peroxidase-like activity as nanozyme can efficiently catalyze the conversion of chromogenic substrate such as 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) with the presence of H2O2 into green-colored oxidation products. CoOOH nanoflakes can specifically bind with arsenate via electrostatic attraction and As–O bond interaction, which gives rise to inhibition of the peroxidase-like activity of CoOOH. Thus, through arsenate specific inhibition of CoOOH nanozyme toward ABTS catalysis, a simple colorimetric method was developed for arsenate detection with a detection limit of 3.72 ppb. Based on the system of CoOOH nanozyme and ABTS substrate, this colorimetric method can be converted into an electrochemical sensor for arsenate assay by the utilization of CoOOH nanoflake-modified electrode. The electrochemical measurement can be realized by chronoamperometry, which showed more sensitive and a lower limit of detection as low as 56.1 ppt. The applicability of this bimodal method was demonstrated by measuring arsenate and total arsenic in different real samples such as natural waters and soil extracted solutions, and the results are of satisfactory accuracy as confirmed by inductively coupled plasma mass spectrometry analysis. The bimodal strategy offers obvious advantages including a label-free step, convenient operation, on-site assay, low cost, and high sensitivity, which is promising for reliable detection of arsenate and total arsenic in environmental samples.