Ochs, O., Martsinovich, N. orcid.org/0000-0001-9226-8175, Heckl, W.M. et al. (1 more author) (2020) Quantifying the ultraslow desorption kinetics of 2,6-naphthalenedicarboxylic acid monolayers at liquid–solid interfaces. The Journal of Physical Chemistry Letters, 11 (17). pp. 7320-7326. ISSN 1948-7185
Abstract
Kinetic effects in monolayer self-assembly at liquid–solid interfaces are not well explored but can provide unique insights. We use variable-temperature scanning tunneling microscopy (STM) to quantify the desorption kinetics of 2,6-naphthalenedicarboxylic acid (NDA) monolayers at nonanoic acid–graphite interfaces. Quantitative tracking of the decline of molecular coverages by STM between 57.5 and 65.0 °C unveiled single-exponential decays over the course of days. An Arrhenius plot of rate constants derived from fits results in a surprisingly high energy barrier of 208 kJ mol–1 that strongly contrasts with the desorption energy of 16.4 kJ mol–1 with respect to solution as determined from a Born–Haber cycle. This vast discrepancy indicates a high-energy transition state. Expanding these studies to further systems is the key to pinpointing the molecular origin of the remarkably large NDA desorption barrier.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2020 American Chemical Society. This is an author-produced version of a paper subsequently published in Journal of Physical Chemistry Letters. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 03 Sep 2020 10:39 |
Last Modified: | 11 Aug 2021 00:38 |
Status: | Published |
Publisher: | American Chemical Society (ACS) |
Refereed: | Yes |
Identification Number: | 10.1021/acs.jpclett.0c01882 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:165100 |