Enhanced Reactivity in Janus Transition Metal Dichalcogenide Quantum Dots: Charge-Density Asymmetry and Hydrodesulfurization Potential

Abstract: Quantum dots (QDs) are nanoscale materials that exhibit unique electronic and optical properties due to quantum confinement effects, making them highly relevant for applications in catalysis, optoelectronics, and energy conversion. While transition metal dichalcogenide (TMD) QDs have been extensively studied in their pristine forms, Janus-type TMD QDs -- featuring compositional asymmetry across their atomic layers -- offer an additional degree of tunability through charge-density gradients and curvature effects, yet remain comparatively unexplored. In this work, we investigate the electronic and structural properties of Janus TMD QDs composed of molybdenum (Mo) or tungsten (W) in combination with chalcogen elements (S, Se, Te) and oxygen, exploring three distinct structural classes: pristine, non-oxidized Janus, and oxidized Janus phases. Using first-principles calculations, including static DFT and ab initio molecular dynamics (AIMD) simulations, we analyze curvature evolution, electrostatic potential isosurfaces, charge-density asymmetry, and surface formation energies to assess size- and composition-dependent stability. Our findings reveal that oxidation induces significant curvature and charge localization, particularly in W-based systems, enhancing their potential as catalysts for hydrodesulfurization reactions. Additionally, we identify size- and geometry-dependent stability trends, with larger and beta-type QDs exhibiting superior thermodynamic and thermal robustness. These results provide a comprehensive theoretical foundation for the design and synthesis of structurally tunable Janus QDs with tailored properties for catalytic and electronic applications.