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Li and Na Adsorption on Graphene and Graphene Oxide Examined by Density Functional Theory, Quantum Theory of Atoms in Molecules, and Electron Localization Function
Adsorption of Li and Na on pristine and defective graphene and graphene oxide (GO) is studied using density functional theory (DFT) structural and electronic calculations, quantum theory of atoms in molecules (QTAIM), and electron localization function (ELF) analyses. DFT calculations show that Li a...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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MDPI
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6412830/ https://www.ncbi.nlm.nih.gov/pubmed/30791506 http://dx.doi.org/10.3390/molecules24040754 |
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author | Dimakis, Nicholas Salas, Isaiah Gonzalez, Luis Vadodaria, Om Ruiz, Korinna Bhatti, Muhammad I. |
author_facet | Dimakis, Nicholas Salas, Isaiah Gonzalez, Luis Vadodaria, Om Ruiz, Korinna Bhatti, Muhammad I. |
author_sort | Dimakis, Nicholas |
collection | PubMed |
description | Adsorption of Li and Na on pristine and defective graphene and graphene oxide (GO) is studied using density functional theory (DFT) structural and electronic calculations, quantum theory of atoms in molecules (QTAIM), and electron localization function (ELF) analyses. DFT calculations show that Li and Na adsorptions on pristine graphene are not stable at all metal coverages examined here. However, the presence of defects on graphene support stabilizes both Li and Na adsorptions. Increased Li and Na coverages cause metal nucleation and weaken adsorption. Defective graphene is associated with the presence of band gaps and, thus, Li and Na adsorptions can be used to tune these gaps. Electronic calculations show that Li– and Na–graphene interactions are Coulombic: as Li and Na coverages increase, the metal valences partially hybridize with the graphene bands and weaken metal–graphene support interactions. However, for Li adsorption on single vacancy graphene, QTAIM, ELF, and overlap populations calculations show that the Li-C bond has some covalent character. The Li and Na adsorptions on GO are significantly stronger than on graphene and strengthen upon increased coverages. This is due to Li and Na forming bonds with both carbon and oxygen GO atoms. QTAIM and ELF are used to analyze the metal–C and metal–metal bonds (when metal nucleation is present). The Li and Na clusters may contain both covalent and metallic intra metal–metal bonds: This effect is related to the adsorption support selection. ELF bifurcation diagrams show individual metal–C and metal–metal interactions, as Li and Na are adsorbed on graphene and GO, at the metal coverages examined here. |
format | Online Article Text |
id | pubmed-6412830 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-64128302019-04-09 Li and Na Adsorption on Graphene and Graphene Oxide Examined by Density Functional Theory, Quantum Theory of Atoms in Molecules, and Electron Localization Function Dimakis, Nicholas Salas, Isaiah Gonzalez, Luis Vadodaria, Om Ruiz, Korinna Bhatti, Muhammad I. Molecules Article Adsorption of Li and Na on pristine and defective graphene and graphene oxide (GO) is studied using density functional theory (DFT) structural and electronic calculations, quantum theory of atoms in molecules (QTAIM), and electron localization function (ELF) analyses. DFT calculations show that Li and Na adsorptions on pristine graphene are not stable at all metal coverages examined here. However, the presence of defects on graphene support stabilizes both Li and Na adsorptions. Increased Li and Na coverages cause metal nucleation and weaken adsorption. Defective graphene is associated with the presence of band gaps and, thus, Li and Na adsorptions can be used to tune these gaps. Electronic calculations show that Li– and Na–graphene interactions are Coulombic: as Li and Na coverages increase, the metal valences partially hybridize with the graphene bands and weaken metal–graphene support interactions. However, for Li adsorption on single vacancy graphene, QTAIM, ELF, and overlap populations calculations show that the Li-C bond has some covalent character. The Li and Na adsorptions on GO are significantly stronger than on graphene and strengthen upon increased coverages. This is due to Li and Na forming bonds with both carbon and oxygen GO atoms. QTAIM and ELF are used to analyze the metal–C and metal–metal bonds (when metal nucleation is present). The Li and Na clusters may contain both covalent and metallic intra metal–metal bonds: This effect is related to the adsorption support selection. ELF bifurcation diagrams show individual metal–C and metal–metal interactions, as Li and Na are adsorbed on graphene and GO, at the metal coverages examined here. MDPI 2019-02-19 /pmc/articles/PMC6412830/ /pubmed/30791506 http://dx.doi.org/10.3390/molecules24040754 Text en © 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Dimakis, Nicholas Salas, Isaiah Gonzalez, Luis Vadodaria, Om Ruiz, Korinna Bhatti, Muhammad I. Li and Na Adsorption on Graphene and Graphene Oxide Examined by Density Functional Theory, Quantum Theory of Atoms in Molecules, and Electron Localization Function |
title | Li and Na Adsorption on Graphene and Graphene Oxide Examined by Density Functional Theory, Quantum Theory of Atoms in Molecules, and Electron Localization Function |
title_full | Li and Na Adsorption on Graphene and Graphene Oxide Examined by Density Functional Theory, Quantum Theory of Atoms in Molecules, and Electron Localization Function |
title_fullStr | Li and Na Adsorption on Graphene and Graphene Oxide Examined by Density Functional Theory, Quantum Theory of Atoms in Molecules, and Electron Localization Function |
title_full_unstemmed | Li and Na Adsorption on Graphene and Graphene Oxide Examined by Density Functional Theory, Quantum Theory of Atoms in Molecules, and Electron Localization Function |
title_short | Li and Na Adsorption on Graphene and Graphene Oxide Examined by Density Functional Theory, Quantum Theory of Atoms in Molecules, and Electron Localization Function |
title_sort | li and na adsorption on graphene and graphene oxide examined by density functional theory, quantum theory of atoms in molecules, and electron localization function |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6412830/ https://www.ncbi.nlm.nih.gov/pubmed/30791506 http://dx.doi.org/10.3390/molecules24040754 |
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