Surface Functionalization of WS₂ Nanosheets with Alkyl Chains for Enhancement of Dispersion Stability and...

Tungsten disulfide (WS₂) exhibits intriguing tribological properties and has been explored as an excellent lubricious material in thin-film and solid lubricants. However, the poor dispersibility of WS₂ has been a major challenge for its utilization in liquid lubricant applications. Herein, a top-down integrated approach is presented to synthesize oxygenated WS₂ (WS₂-O) nanosheets via strong acid-mediated oxidation and ultrasound-assisted exfoliation. The ultrathin sheets of WS₂-O, comprising 4-7 molecular lamellae, exhibit oxygen/hydroxyl functionalities. The organosilanes having variable surface-active leaving groups (chloro and ethoxy) are covalently grafted, targeting the hydroxyl/oxygen functionalities on the surface of WS₂-O nanosheets. The grafting of organosilanes is governed by the reactivity of chloro and ethoxy leaving groups. The DFT calculations further support the covalent interaction between the WS₂-O nanosheets and organosilanes. The alkyl chain-functionalized WS₂-O nanosheets displayed excellent dispersibility in mineral lube base oil. A minute dose of chemically functionalized-WS₂ (0.2 mg.mL^-1) notably enhanced the tribological properties of mineral lube oil by reducing the friction coefficient (52%) and wear volume (79%) for a steel tribopair. Raman analysis of worn surfaces revealed WS₂-derived lubricious thin film formation. The improved tribological properties are attributed to ultralow thickness, stable dispersion, and low shear strength of chemically functionalized WS₂ nanosheets, along with protective thin film formation over the contact interfaces of a steel tribopair. The present work opens a new avenue toward exploiting low-dimensional nanosheets for minimizing energy losses due to high friction.