Interactions Balancing Competition and Cooperation between Covalent–Organic Framework Additives and PEG Base Oil toward Advanced Lubrication

Severe competition between nanolubricant additives and polar lubricating oil molecules for the formation of lubricant films has been hindering the progress of green and advanced lubricants. In this work, based on the tautomerism of cyanuric acid molecule (trione and triol configurations), two kinds of triazine-based covalent-organic frameworks (COFs), that is, Ton-COFs and Tol-COFs, were synthesized as additives of the polar PEG 400 oil, realizing compromise between them by providing delicate interactions. The triazine matrix bonding with intense polar groups in the framework of additives offers more powerful interactions to competitively form the adsorbed lubricant film on the surface of the metal substrate over PEG 400 oil and also bolts PEG 400 oil molecules by the hydrogen bonding inside the pore of the framework to cooperatively bear against the load. Molecular quantum chemical calculations further confirm that Ton-COFs can produce a more intense interaction with Fe atoms in the form of coordination and ions···π than Tol-COFs, far beyond PEG 400, and the cross-sectional profile of the worn surface definitely exhibits a protective lubricant film only composed of Ton-COFs. Consequently, at the low concentration of 0.3 wt %, the excellent friction reduction (41.2%) and antiwear property (97.4%) are achieved for the Ton-COFs compared to pure PEG 400 oil; moreover, 28.6% and 79.0% for Tol-COFs at the essential concentration of 0.7 wt % are achieved. This finding provides a novel insight from molecules to materials into guiding the development of additives for advanced lubricants.