Title

Thermodynamic Preference for Atom Adsorption on versus Intercalation into Multilayer Graphene

Publication Date

11-2-2020

Department

Ames Laboratory; Physics and Astronomy

Campus Units

Ames Laboratory, Physics and Astronomy

OSTI ID+

1727437

Report Number

IS-J 10371

DOI

10.1021/acs.jpclett.0c02887

Journal Title

The Journal of Physical Chemistry Letters

Volume Number

11

Issue Number

22

First Page

9725

Last Page

9730

Abstract

The thermodynamic preference of a foreign atom for adsorption on versus intercalation into a graphitic surface is of fundamental and widespread interest. From an exhaustive first-principles density functional theory investigation for 38 typical elements over the periodic table, we reveal a quasilinear correlation between the Shannon effective ionic radius and the chemical-potential difference for a single atom from adsorption to intercalation at multilayer graphene surfaces. A critical Shannon radius is found to be around 0.10 nm, below (above) which intercalation (adsorption) is more favorable for elements with ionic-like bonding after intercalation. Single atoms with van der Waals-biased bonding show some deviation from the linear relationship, while single atoms for the elements with covalent-like bonding do not favor intercalation relative to adsorption. An energy decomposition analysis indicates that the chemical-potential difference determining the thermodynamic preference of a foreign atom for adsorption versus intercalation results from the competition between the electronic and elastic strain effects.

DOE Contract Number(s)

AC02-07CH11358; AC02-05CH11231

Language

en

Publisher

Iowa State University Digital Repository, Ames IA (United States)

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