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Title: Inducing regioselective chemical reactivity in graphene with alkali metal intercalation

Abstract

First principles calculations demonstrate that alkali metal atoms, intercalated between metal substrates and adsorbed graphene monolayers, induce localised regions of increased reactivity. The extent of this localisation is proportional to the size of the alkali atom and the strength of the graphene–substrate interaction. Thus, larger alkali atoms are more effective (e.g. K > Na > Li), as are stronger-interacting substrates (e.g. Ni > Cu). Despite the electropositivity of these alkali metal adsorbates, analysis of charge transfer between the alkali metal, the substrate and the adsorbed graphene layer indicates that charge transfer does not give rise to the observed regioselective reactivity. Instead, the increased reactivity induced in the graphene structure is shown to arise from the geometrical distortion of the graphene layer imposed by the intercalated adsorbed atom. Finally, we show that this strategy can be used with arbitrary adsorbates and substrate defects, provided such structures are stable, towards controlling the mesoscale patterning and chemical functionalisation of graphene structures.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Newcastle, Callaghan, NSW (Australia). Newcastle Inst. for Energy and Resources
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Computational Sciences and Engineering Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Newcastle, Callaghan, NSW (Australia)
Sponsoring Org.:
USDOE; ORNL Laboratory Directed Research and Development (LDRD) Program; Australian Research Council
OSTI Identifier:
1468180
Alternate Identifier(s):
OSTI ID: 1460896
Grant/Contract Number:  
AC05-00OR22725; LE170100032
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 20; Journal Issue: 30; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Mitchell, Izaac, Irle, Stephan, and Page, Alister J. Inducing regioselective chemical reactivity in graphene with alkali metal intercalation. United States: N. p., 2018. Web. doi:10.1039/c8cp02903b.
Mitchell, Izaac, Irle, Stephan, & Page, Alister J. Inducing regioselective chemical reactivity in graphene with alkali metal intercalation. United States. doi:10.1039/c8cp02903b.
Mitchell, Izaac, Irle, Stephan, and Page, Alister J. Tue . "Inducing regioselective chemical reactivity in graphene with alkali metal intercalation". United States. doi:10.1039/c8cp02903b. https://www.osti.gov/servlets/purl/1468180.
@article{osti_1468180,
title = {Inducing regioselective chemical reactivity in graphene with alkali metal intercalation},
author = {Mitchell, Izaac and Irle, Stephan and Page, Alister J.},
abstractNote = {First principles calculations demonstrate that alkali metal atoms, intercalated between metal substrates and adsorbed graphene monolayers, induce localised regions of increased reactivity. The extent of this localisation is proportional to the size of the alkali atom and the strength of the graphene–substrate interaction. Thus, larger alkali atoms are more effective (e.g. K > Na > Li), as are stronger-interacting substrates (e.g. Ni > Cu). Despite the electropositivity of these alkali metal adsorbates, analysis of charge transfer between the alkali metal, the substrate and the adsorbed graphene layer indicates that charge transfer does not give rise to the observed regioselective reactivity. Instead, the increased reactivity induced in the graphene structure is shown to arise from the geometrical distortion of the graphene layer imposed by the intercalated adsorbed atom. Finally, we show that this strategy can be used with arbitrary adsorbates and substrate defects, provided such structures are stable, towards controlling the mesoscale patterning and chemical functionalisation of graphene structures.},
doi = {10.1039/c8cp02903b},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 30,
volume = 20,
place = {United States},
year = {2018},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Figure 1 Figure 1: Schematic representation of epoxidation of adsorbed graphene monolayers. The blue sphere represents the position of the alkali metal atom, which is either below a (a) hexagon (b) carbon atom or (c) carbon-carbon bond in the graphene sheet. Red bonds are those which are epoxidated.

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Works referenced in this record:

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.