Engineering Electron-Rich Sites on CoSe Nanosheets for the Enhanced Electroanalysis of As(III): A Study on the Electronic Structure via X-ray Absorption Fine Structure Spectroscopy and Density Functional Theory Calculation.

Vacancy and doping engineering are promising pathways to improve the electrocatalytic ability of nanomaterials for detecting heavy metal ions. However, the effects of the electronic structure and the local coordination on the catalytic performance are still ambiguous. Herein, cubic selenium vacancy-rich CoSe (c-CoSe) and P-doped orthorhombic CoSe (o-CoSe|P) were designed via vacancy and doping engineering. An o-CoSe|P-modified glass carbon electrode (o-CoSe|P/GCE) acquired a high sensitivity of 1.11 μA ppb toward As(III), which is about 40 times higher than that of c-CoSe, outperforming most of the reported nanomaterial-modified glass carbon electrodes. Besides, o-CoSe|P/GCE displayed good selectivity toward As(III) compared with other divalent heavy metal cations, which also exhibited excellent stability, repeatability, and practicality. X-ray absorption fine structure spectroscopy and density functional theory calculation demonstrate that electrons transferred from Co and Se to P sites through Co-P and Se-P bonds in o-CoSe|P. P sites obtained plentiful electrons to form active centers, which also had a strong orbital coupling with As(III). In the detection process, As(III) was bonded with P and reduced by the electron-rich sites in o-CoSe|P, thus acquiring a reinforced electrochemical sensitivity. This work provides an in-depth understanding of the influence of the intrinsic physicochemical properties of sensitive materials on the behavior of electroanalysis, thus offering a direct guideline for creating active sites on sensing interfaces.