Mechanochemical Association Reaction of Interfacial Molecules Driven by Shear

Arash Khajeh, Xin He, Jejoon Yeon, Seong Kim, Ashlie Martini

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Shear-driven chemical reaction mechanisms are poorly understood because the relevant reactions are often hidden between two solid surfaces moving in relative motion. Here, this phenomenon is explored by characterizing shear-induced polymerization reactions that occur during vapor phase lubrication of α-pinene between sliding hydroxylated and dehydroxylated silica surfaces, complemented by reactive molecular dynamics simulations. The results suggest that oxidative chemisorption of the α-pinene molecules at reactive surface sites, which transfers oxygen atoms from the surface to the adsorbate molecule, is the critical activation step. Such activation takes place more readily on the dehydroxylated surface. During this activation, the most strained part of the α-pinene molecules undergoes a partial distortion from its equilibrium geometry, which appears to be related to the critical activation volume for mechanical activation. Once α-pinene molecules are activated, association reactions occur between the newly attached oxygen and one of the carbon atoms in another molecule, forming ether bonds. These findings have general implications for mechanochemistry because they reveal that shear-driven reactions may occur through reaction pathways very different from their thermally induced counterparts and specifically the critical role of molecular distortion in such reactions.

Original languageEnglish (US)
Pages (from-to)5971-5977
Number of pages7
JournalLangmuir
Volume34
Issue number21
DOIs
StatePublished - May 29 2018

Fingerprint

association reactions
Chemical activation
Association reactions
activation
shear
Molecules
molecules
vapor phase lubrication
Oxygen
Atoms
Adsorbates
Chemisorption
solid surfaces
Silicon Dioxide
Ether
chemisorption
Lubrication
sliding
Molecular dynamics
Chemical reactions

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry

Cite this

Khajeh, Arash ; He, Xin ; Yeon, Jejoon ; Kim, Seong ; Martini, Ashlie. / Mechanochemical Association Reaction of Interfacial Molecules Driven by Shear. In: Langmuir. 2018 ; Vol. 34, No. 21. pp. 5971-5977.
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Mechanochemical Association Reaction of Interfacial Molecules Driven by Shear. / Khajeh, Arash; He, Xin; Yeon, Jejoon; Kim, Seong; Martini, Ashlie.

In: Langmuir, Vol. 34, No. 21, 29.05.2018, p. 5971-5977.

Research output: Contribution to journalArticle

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