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

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI: https://doi.org/10.1039/c8cp02903b · OSTI ID:1468180
 [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

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.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of Newcastle, Callaghan, NSW (Australia)
Sponsoring Organization:
USDOE; ORNL Laboratory Directed Research and Development (LDRD) Program; Australian Research Council
Grant/Contract Number:
AC05-00OR22725; LE170100032
OSTI ID:
1468180
Alternate ID(s):
OSTI ID: 1460896
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Vol. 20, Issue 30; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

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Figures / Tables (9)