Mechanochemistry of phosphate esters confined between sliding iron surfaces

The molecular structure of lubricant additives controls not only their adsorption and dissociation behaviour at the nanoscale, but also their ability to reduce friction and wear at the macroscale. Here, we show using nonequilibrium molecular dynamics simulations with a reactive force field that tri(s-butyl)phosphate dissociates much faster than tri(n-butyl)phosphate when heated and compressed between sliding iron surfaces. For both molecules, dissociative chemisorption proceeds through cleavage of carbon−oxygen bonds. The dissociation rate increases exponentially with temperature and stress. When the rate−temperature−stress data are fitted with the Bell model, both molecules have similar activation energies and activation volumes and the higher reactivity of tri(s-butyl)phosphate is due to a larger pre-exponential factor. These observations are consistent with experiments using the antiwear additive zinc dialkyldithiophosphate. This study represents a crucial step towards the virtual screening of lubricant additives with different substituents to optimise tribological performance.

Catalytic Prebiotic Formation of Glycerol Phosphate Esters and an Estimation of Their Steady State Abundance under Plausible Early Earth Conditions

The emergence of biological phosphate esters of glycerol could have been a crucial step in the origin and evolution of life on the early Earth as glycerol phosphates today play a central role in biochemistry. We investigate here the formation of the glycerol phosphates by employing various rock samples, salts, and minerals as potential catalysts to aid the phosphorylation process. We report the synthesis of various phosphate esters of glycerol including glycerol-1-phosphate, glycerol-2-phosphate, cyclic glycerol-monophosphate as well as various diphosphate esters. Furthermore, the decomposition rates of glycerol phosphate under mild heating were also studied while keeping the pH constant. It was observed that glycerol phosphate starts decomposing quickly under mild heating conditions into inorganic orthophosphate and pyrophosphate, and a steady state concentration of ~0.5 M of glycerol phosphate may have been reasonable in ponds with abundant glycerol, phosphate, urea, and catalytic minerals.

Substituent Effects on the Thermal Decomposition of Phosphate Esters on Ferrous Surfaces

<p></p><p>Phosphate esters have a wide range of industrial applications, for example in tribology where they are used as vapour phase lubricants and antiwear additives. An atomic-level understanding of phosphate ester tribofilm formation mechanisms is required to improve their tribological performance. A process of particular interest is the thermal decomposition of phosphate esters on steel surfaces, since this initiates polyphosphate film formation. In this study, reactive force field (ReaxFF) molecular dynamics (MD) simulations are used to study the thermal decomposition of phosphate esters with different substituents on several ferrous surfaces. The ReaxFF parameterisation was validated for a representative system using density functional theory (DFT) calculations. During the MD simulations on Fe 3 O 4 (001) and α-Fe(110), chemisorption interactions between the phosphate esters and the surfaces occur even at room temperature, and the number of molecule-surface bonds increases as the temperature increases from 300 to 1000 K. Conversely, on hydroxylated, amorphous Fe 3 O 4 , most of the molecules are physisorbed and some desorption occurs at high temperature. Thermal decomposition rates were much higher on Fe 3 O 4 (001) and particularly α-Fe(110) compared to hydroxylated, amorphous Fe 3 O 4. This suggests that water passivates ferrous surfaces and inhibits phosphate ester chemisorption, decomposition, and ultimately polyphosphate film formation. For the alkyl phosphates, thermal decomposition proceeds mainly through CO and C-H cleavage on Fe 3 O 4 (001). Aryl phosphates show much higher thermal stability, and decomposition on Fe 3 O 4 (001) only occurs through P-O and C-H cleavage, which require very high temperature. The onset temperature for CO cleavage on Fe 3 O 4 (001) increases as: tertiary alkyl < secondary alkyl < primary linear alkyl ≈ primary branched alkyl < aryl. This order is consistent with experimental observations for the thermal stability of antiwear additives with similar substituents. The simulation results clarify a range of surface and substituent effects on the thermal decomposition of phosphate esters on steel that should be helpful for the design of new molecules with improved tribological performance.<br></p><p></p>

DBU and TU Synergistically Induced Ring-Opening Polymerization of Phosphate Esters: A Mechanism Study

Biocompatible and biodegradable polyphosphoesters derived from ring-opening polymerization (ROP) of phosphate ester have drawn increasing attention because of their potential applications in clinical and therapeutic fields. The related knowledge of...