Ultra-Sensitive and Selective Detection of Arsenic(III) via Electroanalysis over Cobalt Single-Atom Catalysts

Abstract

Achieving highly sensitive and selective detection of trace-level As(III) and clarifying the underlying mechanism is still a intractable problem. The electroanalysis of As(III) relies on the electrocatalytic ability of the sensing interface. Herein, we first adopt single-atom catalysts as the electrocatalyst in As(III) detection. Cobalt single-atoms anchored on nitrogen-doped carbon material (Co SAC) were found to have an extraordinary sensitivity of 11.44 μA ppb^-1 with excellent stability and repeatability, which so far is the highest among non-noble metal nanomaterials. Co SAC also exhibited a superior selectivity toward As(III) compared with some bivalent heavy metal ions (HMIs). Combining X-ray absorption spectroscopy (XAFS), density functional theory (DFT) calculation, and reaction kinetics simulation, we demonstrated that Co single atoms stabilized in N₂C₂ support serve as active sites to catalyze H₃AsO₃ reduction via the formation of Co-O hybridization bond, leading to a lower energy barrier, promoting the breakage of As-O bonds. Importantly, the first electron transfer is the rate-limiting step of arsenic reduction and is found to be more favorable on Co-SAC both thermodynamically and kinetically. This work not only expands the potential applicaiton of single-atom catalysts in the detection and treatment of As(III), but also provides atomic-level catalytic insights into HMIs sensing interfaces.