Mechanistic Insights on Functionalization of Graphene with Ozone.

Autor: Vahdat MT; Laboratory of Advanced Separations (LAS), École Polytechnique Fédérale de Lausanne (EPFL), Sion CH-1950, Switzerland.; Theory and Simulation of Materials (THEOS) and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), EPFL, Lausanne CH-1015, Switzerland., Li S; Laboratory of Advanced Separations (LAS), École Polytechnique Fédérale de Lausanne (EPFL), Sion CH-1950, Switzerland., Huang S; Laboratory of Advanced Separations (LAS), École Polytechnique Fédérale de Lausanne (EPFL), Sion CH-1950, Switzerland., Bondaz L; Laboratory of Advanced Separations (LAS), École Polytechnique Fédérale de Lausanne (EPFL), Sion CH-1950, Switzerland., Bonnet N; Theory and Simulation of Materials (THEOS) and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), EPFL, Lausanne CH-1015, Switzerland., Hsu KJ; Laboratory of Advanced Separations (LAS), École Polytechnique Fédérale de Lausanne (EPFL), Sion CH-1950, Switzerland., Marzari N; Theory and Simulation of Materials (THEOS) and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), EPFL, Lausanne CH-1015, Switzerland., Agrawal KV; Laboratory of Advanced Separations (LAS), École Polytechnique Fédérale de Lausanne (EPFL), Sion CH-1950, Switzerland.
Jazyk: angličtina
Zdroj: The journal of physical chemistry. C, Nanomaterials and interfaces [J Phys Chem C Nanomater Interfaces] 2023 Nov 07; Vol. 127 (45), pp. 22015-22022. Date of Electronic Publication: 2023 Nov 07 (Print Publication: 2023).
DOI: 10.1021/acs.jpcc.3c03994
Abstrakt: The exposure of graphene to O 3 results in functionalization of its lattice with epoxy, even at room temperature. This reaction is of fundamental interest for precise lattice patterning, however, is not well understood. Herein, using van der Waals density functional theory (vdW-DFT) incorporating spin-polarized calculations, we find that O 3 strongly physisorbs on graphene with a binding energy of -0.46 eV. It configures in a tilted position with the two terminal O atoms centered above the neighboring graphene honeycombs. A dissociative chemisorption follows by surpassing an energy barrier of 0.75 eV and grafting an epoxy group on graphene reducing the energy of the system by 0.14 eV from the physisorbed state. Subsequent O 3 chemisorption is preferred on the same honeycomb, yielding two epoxy groups separated by a single C-C bridge. We show that capturing the onset of spin in oxygen during chemisorption is crucial. We verify this finding with experiments where an exponential increase in the density of epoxy groups as a function of reaction temperature yields an energy barrier of 0.66 eV, in agreement with the DFT prediction. These insights will help efforts to obtain precise patterning of the graphene lattice.
Competing Interests: The authors declare no competing financial interest.
(© 2023 The Authors. Published by American Chemical Society.)
Databáze: MEDLINE
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