High Selectivity and Sensitivity in Chemiresistive Sensing of Co(II) Ions with Liquid-Phase Exfoliated Functionalized MoS2: A Supramolecular Approach

Abstract

Chemical sensing of water contamination by heavy metal ions is key as it represents a most severe environmental problem. Liquid-phase exfoli-ated two-dimensional (2D) transition metal dichalcogenides (TMDs) are suitable candidates for chemical sensing thanks to their high surface-to-volume ratio, sensitivity, unique electrical characteristics, and scalability. However, TMDs lack selectivity due to nonspecific analyte-nanosheet interactions. To overcome this drawback, defect engineering enables controlled functionalization of 2D TMDs. Here, ultrasensitive and selec-tive sensors of cobalt(II) ions via the covalent functionalization of defect-rich MoS2 flakes with a specific receptor, 2,2′:6′,2′′-terpyridine-4′-thiol is developed. A continuous network is assembled by healing of MoS2 sulfur vacancies in a tailored microfluidic approach, enabling high control over the assembly of thin and large hybrid films. The Co2+ cations compl-exation represents a powerful gauge for low concentrations of cationic species which can be best monitored in a chemiresisitive ion sensor, featuring a 1 pm limit of detection, sensing in a broad concentration range (1 pm- 1 μm) and sensitivity as high as 0.308 ± 0.010 lg([Co2+])-1 com-bined with a high selectivity towards Co2+ over K+, Ca2+, Mn2+, Cu2+, Cr3+, and Fe3+ cations. This supramolecular approach based on highly specific recognition can be adapted for sensing other analytes through specific ad-hoc receptors.