Chemical reactivity of Lithium doped monolayer and bilayer graphene

GRAFENO

BIBLIOGRAFIA NACIONAL QUIMICA

2011

Herein, we perform a comparative investigation on the reactivity of pristine and lithium doped monolayer and bilayer graphene. To study the addition of free radicals and 1,3 dipolar cycloadditions, we employed periodic DFT calculations. In all cases lithium increases the reactivity, even though the effect is weaker for the 1,3 dipolar cycloaddition as compared with that exhibited by free radicals. The effect of lithium doping is local and decreases as the functional group is attached far from the lithium atom. The increased reactivity can be explained by analyzing the band structure at the Fermi level. Lithium doped graphene is metallic thus showing an increased reactivity toward free radicals as observed for metallic nanotubes. However, the metallic character of lithium doped graphene is lost when free radicals like OH, SH, H, F, and CH3 are attached; the Fermi level is raised and a gap is opened. The reactivity of bilayer graphene was almost unaffected by the lithium doping. Therefore, to enhance the reactivity of graphene it is crucial to use the monolayer form. Also, it is important to eliminate defects to decrease lithium diffusion to the other side of the sheet because Li atoms can remove the functional groups attached to graphene, forming compounds like LiOH, LiF, etc. Finally, for comparative purposes, we performed M06-2X and MP2 calculations for the addition of free radicals to lithium doped benzene. The results showed similar trends to those observed for graphene. This work demonstrates that lithium doping can dramatically increase the reactivity of graphene to such an extent that chemical groups that do not react with graphene become bonded when lithium is underneath. Thus, lithium doping can open new avenues for investigating the chemistry of the rather unreactive sp2 framework of graphene.

Journal of Physical Chemistry C v.115, no 27, 2011. -- p. 13392-13398

American Chemical Society

2011

 

Información sobre Derechos de Autor

(Por favor lea este aviso antes de abrir los documentos u objetos)

La legislación uruguaya protege el derecho de autor sobre toda creación literaria, científica o artística, tanto en lo que tiene que ver con sus derechos morales, como en lo referente a los derechos patrimoniales con sujeción a lo establecido por el derecho común y las siguientes leyes

(LEY 9.739 DE 17 DE DICIEMBRE DE 1937 SOBRE PROPIEDAD LITERARIA Y ARTISTICA CON LAS MODIFICACIONES INTRODUCIDAS POR LA LEY DE DERECHO DE AUTOR Y DERECHOS CONEXOS No. 17.616 DE 10 DE ENERO DE 2003, LEY 17.805 DE 26 DE AGOSTO DE 2004, LEY 18.046 DE 24 DE OCTUBRE DE 2006 LEY 18.046 DE 24 DE OCTUBRE DE 2006)

ADVERTENCIA - La consulta de este documento queda condicionada a la aceptación de las siguientes condiciones de uso: Este documento es únicamente para usos privados enmarcados en actividades de investigación y docencia. No se autoriza su reproducción con fines de lucro. Esta reserva de derechos afecta tanto los datos del documento como a sus contenidos. En la utilización o cita de partes debe indicarse el nombre de la persona autora.

PDF

Inglés

Artículo

dx.doi.org/10.1021/jp203547b