Adaptive Lubrication and Antiwear Enabled by Synergy Between Friction‐Induced In Situ Tribo‐Click Reaction and Gel Confinement of Reaction Products

ABSTRACT Friction and wear cause massive energy dissipation and mechanical failure, driving the demand for advanced lubrication. Here, we report a facile gel‐confined in situ tribo‐click platform triggered by interfacial friction. Azide and alkyne precursors are incorporated into supramolecular gel lubricants; reciprocal sliding on copper releases catalytic Cu(I) ions to initiate on‐site Cu(I)‐catalyzed azide‐alkyne cycloaddition (CuAAC) reactions, producing lubricious triazole adducts. The 3D supramolecular network physically traps base oil and tribo‐products via molecular confinement and anchoring, facilitating dense, durable tribofilms. This system exhibits intrinsic adaptive behavior: harsher frictional stimuli accelerate tribo‐click conversion and yield more lubricating species. Through systematic characterization, we show that, unlike conventional liquid‐oil systems, the gel network suppresses product diffusion and leaching, drastically improving tribofilm thickness and long‐term stability. By synergizing tribocatalytic click chemistry with the spatial confinement of low‐molecular‐weight gelators (LMWGs), this work establishes a high‐performance self‐adaptive lubrication paradigm in friction control.