PNNL

Abstract

By means of the first-principles spin polarized density functional theory (DFT) calculations, we investigated structures and electronic properties of “external” nitrogen-containing groups (pyridine derivatives) modified graphene via single or double bonding mode. This study of single-bond pyridine derivatives modified graphene (SBPG) shows that the ortho-carbon is the most favorable adsorption site for pyridine derivatives on graphene, as confirmed by bader charge analysis. The external stability of pyridine derivatives on graphene by [2+2] cycloaddition is caused by the match between frontier orbitals of pyridine derivatives and those of graphene, which leading to the formation of stronger chemical bonds. Interestingly, electronic structure analysis reveals that the spin-up and spin-down parts DOS of SBPG clearly split, while it is not found for double-bonds pyridine derivatives modified graphene (DBPG). This work was supported by the 973 project (2013CB733501) and the National Natural Science Foundation of China ( 21101137, 21136001, 21176221, 21306169 and 91334013). D. Mei is supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.