RESUMO
We recently reported a new molecular heterocyclic friction modifier (FM) that exhibits excellent friction and wear reduction in the boundary lubrication regime. This paper explores the mechanisms by which friction reduction occurs with heterocyclic alkyl-cyclen FM molecules. We find that these chelating molecules adsorb onto (oxidized) steel surfaces far more tenaciously than conventional FMs such as simple alkylamines. Molecular dynamics simulations argue that the surface coverage of our heterocyclic FM molecules remains close to 100% even at 200 °C. This thermal stability allows the FMs to firmly anchor to the surface, allowing the hydrocarbon chains of the molecules to interact and trap base oil lubricant molecules. This results in thicker boundary film thickness compared with conventional FMs, as shown by optical interferometry measurements.
RESUMO
Developing homogeneous catalysts that convert CS2 and COS pollutants into environmentally benign products is important for both fundamental catalytic research and applied environmental science. Here we report a series of air-stable dimeric Pd complexes that mediate the facile hydrolytic cleavage of both CS2 carbon-sulfur bonds at 25 °C to produce CO2 and trimeric Pd complexes. Oxidation of the trimeric complexes with HNO3 regenerates the dimeric starting complexes with the release of SO2 and NO2. Isotopic labelling confirms that the carbon and oxygen atoms of CO2 originate from CS2 and H2O, respectively, and reaction intermediates were observed by gas-phase and electrospray ionization mass spectrometry, as well as by Fourier transform infrared spectroscopy. We also propose a plausible mechanistic scenario based on the experimentally observed intermediates. The mechanism involves intramolecular attack by a nucleophilic Pd-OH moiety on the carbon atom of coordinated µ-OCS2, which on deprotonation cleaves one C-S bond and simultaneously forms a C-O bond. Coupled C-S cleavage and CO2 release to yield [(bpy)3Pd3(µ3-S)2](NO3)2 (bpy, 2,2'-bipyridine) provides the thermodynamic driving force for the reaction.
