Abstract
<jats:p>MXenes are promising candidates for solid lubrica tion applications due to their two-dimensional struc ture and weak interlayer bonding. However, their widespread practical implementation as solid lubri cants is currently hampered by degradation (e.g., oxidation, structural-breakdown), poor adherence or environmental sensitivity. This study demon strates that molecular termination engineering via silanization enables a transition to long-term en dured lubrication in HF-free synthesized Ti3C2Tx MXene. Specifically, mercapto-functionalized MX ene achieved an outstanding performance, sustaining stable coefficient of friction (COF: 0.15) for 133,000 sliding cycles (>72 hours) with negligible wear, sur passing previously reported MXene-based lubricants. Comprehensive characterization, and density functional theory (DFT) calculations, reveals that this superior performance originates from silane-mediated anchoring, which facilitates the tribochemical forma tion of a robust multicomponent tribolayer consisting of sp2-carbon, silane fragments, TiO2, and degraded MXene fragments. This mechanism contrasts with the commonly assumed lamellar easy-shear behavior, highlighting instead the dominant role of tribochem istry in governing friction as MXene flakes slide over the formed tribolayer. The resulting interfacial archi tecture suppresses materials loss and maintains a per sistent low-shear interface. These findings establish termination engineering as a powerful strategy for achieving persistent macroscopic low-friction, in two dimensional materials, while simultaneously opening new pathways for the design of ultra-durable solid lu bricants and functional interfaces beyond tribology.</jats:p>