Volume 241, 2023

Shear-activated chemisorption and association of cyclic organic molecules

Abstract

Mechanochemical activation has created new opportunities for applications such as solvent-free chemical synthesis, polymer processing, and lubrication. However, mechanistic understanding of these processes is still limited because the mechanochemical response of a system is a complex function of many variables, including the direction of applied stress and the chemical features of the reactants in non-equilibrium conditions. Here, we studied shear-activated reactions of simple cyclic organic molecules to isolate the effect of chemical structure on reaction yield and pathway. Reactive molecular dynamics simulations were used to model methylcyclopentane, cyclohexane, and cyclohexene subject to pressure and shear stress between silica surfaces. Cyclohexene was found to be more susceptible to mechanochemical activation of oxidative chemisorption and subsequent oligomerization reactions than either methylcyclopentane or cyclohexane. The oligomerization trend was consistent with shear-driven polymerization yield measured in ball-on-flat sliding experiments. Analysis of the simulations showed the distribution of carbon atom sites at which oxidative chemisorption occurred and identified the double bond in cyclohexene as being the origin of its shear susceptibility. Lastly, the most common reaction pathways for association were identified, providing insight into how the chemical structures of the precursor molecules determined their response to mechanochemical activation.

Graphical abstract: Shear-activated chemisorption and association of cyclic organic molecules

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
01 Mey 2022
Accepted
23 Jun 2022
First published
23 Jun 2022

Faraday Discuss., 2023,241, 194-205

Author version available

Shear-activated chemisorption and association of cyclic organic molecules

F. H. Bhuiyan, Y. Li, S. H. Kim and A. Martini, Faraday Discuss., 2023, 241, 194 DOI: 10.1039/D2FD00086E

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