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The adsorption of CO, NO, and O2 molecules onto Cu, Ag, and Au atoms placed in the S vacancies of a WS2 monolayer was elucidated within dispersion-corrected density functional theory. The binding energies computed for embedded defects into S vacancies were 2.99 (AuS), 2.44 (AgS), 3.32 eV (CuS), 3.23 (Au2S2), 2.55 (Ag2S2), and 3.48 eV/atom (Cu2S2), respectively. The calculated diffusion energy barriers from an S vacancy to a nearby site for Cu, Ag, and Au were 2.29, 2.18, and 2.16 eV, respectively. Thus, the substitutional atoms remained firmly fixed at temperatures above 700 K. Similarly, the adsorption energies showed that nitric oxide and carbon oxide molecules exhibited stronger chemisorption than O2 molecules on any of the metal atoms (Au, Cu, or Ag) placed in the S vacancies of the WS2 monolayer. Therefore, the adsorption of O2 did not compete with NO or CO adsorption and did not displace them. The density of states showed that a WS2 monolayer modified with a Cu, Au, or Ag atom could be used to design sensing devices, based on electronic or magnetic properties, for atmospheric pollutants. More interestingly, the adsorption of CO changed only the electronic properties of the MoS2-AuS monolayer, which could be used for sensing applications. In contrast, the O2 molecule was chemisorbed more strongly than CO or NO on Au2S2, Cu2S2, or Ag2S2 placed into di-S vacancies. Thus, if the experimental system is exposed to air, the low quantities of O2 molecules present should result in the oxidation of the metallic atoms. Furthermore, the O2 molecules adsorbed on WS2-Au2S2 and WS2-CuS introduced a half-metallic behavior, making the system suitable for applications in spintronics. [ABSTRACT FROM AUTHOR]

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 Au2S2, Cu2S2 and Ag2S2 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-Au2s2 and MoS2-Cu2s2 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. [ABSTRACT FROM AUTHOR]