Effect of Methyl Groups on Formation of Ordered or Layered Graphitic Materials from Aromatic Molecules

Jana, Asmita; Kearney, Logan T.; Naskar, Amit K.; Grossman, Jeffrey C.; Ferralis, Nicola

doi:10.1002/smll.202302985

Title: Effect of Methyl Groups on Formation of Ordered or Layered Graphitic Materials from Aromatic Molecules

Journal Article · 24 June 2023 · Small

DOI: https://doi.org/10.1002/smll.202302985 · OSTI ID:1986354

^[1]; Kearney, Logan T. ^[2];

^[2]; Grossman, Jeffrey C. ^[1];

^[1]

Department of Materials Science and Engineering Massachusetts Institute of Technology Cambridge MA 02139 USA
Carbon and Composites Group Chemical Sciences Division Oak Ridge National Laboratory Oak Ridge TN 37831 USA

Abstract Developing functionally complex carbon materials from small aromatic molecules requires an understanding of how the chemistry and structure of its constituent molecules evolve and crosslink, to achieve a tailorable set of functional properties. Here, molecular dynamics (MD) simulations are used to isolate the effect of methyl groups on condensation reactions during the oxidative process and evaluate the impact on elastic modulus by considering three monodisperse pyrene‐based systems with increasing methyl group fraction. A parameter to quantify the reaction progression is designed by computing the number of new covalent bonds formed. Utilizing the previously developed MD framework, it is found that increasing methylation leads to an almost doubling of bond formation, a larger fraction of the new bonds oriented in the direction of tensile stress, and a higher basal plane alignment of the precursor molecules along the direction of tensile stress, resulting in enhanced tensile modulus. Additionally, via experiments, it is demonstrated that precursors with a higher fraction of methyl groups result in a higher alignment of molecules. Moreover, increased methylation results in the lower spread of single molecule alignment which may lead to smaller variations in tensile modulus and more consistent properties in carbon materials derived from methyl‐rich precursors.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 1986354

Journal Information:: Small, Journal Name: Small Journal Issue: 43 Vol. 19; ISSN 1613-6810

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
alignment
carbon fibers
crosslinking
elastic properties
graphitic carbon
methyl groups
pyrene

Title: Effect of Methyl Groups on Formation of Ordered or Layered Graphitic Materials from Aromatic Molecules

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