Substitutional Coinage Metals as Promising Defects for Adsorption and Detection of Gases on MoS₂ Monolayers: A...

Defective molybdenum disulfide (MoS₂) monolayers (MLs) modified with coinage metal atoms (Cu, Ag and Au) embedded in sulfur vacancies are studied at a dispersion-corrected density functional level. Atmospheric constituents (H₂, O₂ and N₂) and air pollutants (CO and NO), known as secondary greenhouse gases, are adsorbed on up to two atoms embedded into sulfur vacancies in MoS₂ MLs. The adsorption energies suggest that the NO (1.44 eV) and CO (1.24 eV) are chemisorbed more strongly than O₂ (1.07 eV) and N₂ (0.66 eV) on the ML with a cooper atom substituting for a sulfur atom. Therefore, the adsorption of N₂ and O₂ does not compete with NO or CO adsorption. Besides, NO adsorbed on embedded Cu creates a new level in the band gap. In addition, it was found that the CO molecule could directly react with the pre-adsorbed O₂ molecule on a Cu atom, forming the complex OOCO, via the Eley-Rideal reaction mechanism. The adsorption energies of CO, NO and O₂ on Au, Cu and Ag embedded into two sulfur vacancies were competitive. Charge transference occurs from the defective MoS₂ ML to the adsorbed molecules, oxidizing the later ones (NO, CO and O₂) since they act as acceptors. The total and projected density of states reveal that a MoS₂ ML modified with copper, gold and silver dimers could be used to design electronic or magnetic devices for sensing applications in the adsorption of NO, CO and O₂ molecules. Moreover, NO and O₂ molecules adsorbed on MoS₂-Au and MoS₂-Cu introduce a transition from metallic to half-metallic behavior for applications in spintronics. These modified monolayers are expected to exhibit chemiresistive behavior, meaning their electrical resistance changes in response to the presence of NO molecules. This property makes them suitable for detecting and measuring NO concentrations. Also, modified materials with half-metal behavior could be beneficial for spintronic devices, particularly those that require spin-polarized currents.