Stability and Formation Mechanisms of Carbonyl- and Hydroxyl-Decorated Holes in Graphene Oxide

被引:124
作者
Bagri, A. [1 ]
Grantab, R. [1 ]
Medhekar, N. V. [1 ]
Shenoy, V. B. [1 ]
机构
[1] Brown Univ, Div Engn, Providence, RI 02906 USA
基金
美国国家科学基金会;
关键词
REACTIVE FORCE-FIELD; TOTAL-ENERGY CALCULATIONS; WAVE BASIS-SET; GRAPHITE OXIDE; MOLECULAR-DYNAMICS; THIN-FILMS; SHEETS; TRANSPARENT; OXIDATION; REAXFF;
D O I
10.1021/jp908801c
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
By use of molecular dynamics simulations, we have studied the evolution of epoxy and hydroxyl functional groups on graphene oxide (GO) during high-temperature thermal reduction. We find that the reduced GO sheets are characterized by a large number of stable holelike defects formed by breaking of C-C bonds in the basal plane. These defects are always decorated by the carbonyl (C=O) groups and are formed due to the strain in the basal plane created by epoxy and hydroxyl functional groups that are located close to each other. With very few exceptions, the carbonyl groups that are observed in Raman spectroscopy and other experimental studies are generally attributed to the C=O terminations of the edges. However, our study using first-principles calculations and a reactive force field approach clearly shows that the formation of carbonyl groups within the graphene basal plane is energetically favorable compared to other well-known functional groups such as epoxies and ethers. We have identified the specific reaction mechanisms that lead to the formation of these holes starting from particular initial configurations of epoxy and hydroxyl functional groups. These configurations can be readily found on GO sheets with random distribution of epoxy and hydroxyl groups and do not require an ordered arrangement of any particular functional groups.
引用
收藏
页码:12053 / 12061
页数:9
相关论文
共 42 条
[1]   Materials science - Oxygen breaks into carbon world [J].
Ajayan, PM ;
Yakobson, BI .
NATURE, 2006, 441 (7095) :818-819
[2]  
BAGRI A, UNPUB
[3]   MOLECULAR-DYNAMICS WITH COUPLING TO AN EXTERNAL BATH [J].
BERENDSEN, HJC ;
POSTMA, JPM ;
VANGUNSTEREN, WF ;
DINOLA, A ;
HAAK, JR .
JOURNAL OF CHEMICAL PHYSICS, 1984, 81 (08) :3684-3690
[4]   Electronic confinement and coherence in patterned epitaxial graphene [J].
Berger, Claire ;
Song, Zhimin ;
Li, Xuebin ;
Wu, Xiaosong ;
Brown, Nate ;
Naud, Cecile ;
Mayou, Didier ;
Li, Tianbo ;
Hass, Joanna ;
Marchenkov, Atexei N. ;
Conrad, Edward H. ;
First, Phillip N. ;
de Heer, Wait A. .
SCIENCE, 2006, 312 (5777) :1191-1196
[5]   Organic and molecular magnets [J].
Blundell, SJ ;
Pratt, FL .
JOURNAL OF PHYSICS-CONDENSED MATTER, 2004, 16 (24) :R771-R828
[6]   Modeling of graphite oxide [J].
Boukhvalov, D. W. ;
Katsnelson, M. I. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (32) :10697-10701
[7]   Impermeable atomic membranes from graphene sheets [J].
Bunch, J. Scott ;
Verbridge, Scott S. ;
Alden, Jonathan S. ;
van der Zande, Arend M. ;
Parpia, Jeevak M. ;
Craighead, Harold G. ;
McEuen, Paul L. .
NANO LETTERS, 2008, 8 (08) :2458-2462
[8]   Electromechanical resonators from graphene sheets [J].
Bunch, J. Scott ;
van der Zande, Arend M. ;
Verbridge, Scott S. ;
Frank, Ian W. ;
Tanenbaum, David M. ;
Parpia, Jeevak M. ;
Craighead, Harold G. ;
McEuen, Paul L. .
SCIENCE, 2007, 315 (5811) :490-493
[9]   Synthesis and solid-state NMR structural characterization of 13C-labeled graphite oxide [J].
Cai, Weiwei ;
Piner, Richard D. ;
Stadermann, Frank J. ;
Park, Sungjin ;
Shaibat, Medhat A. ;
Ishii, Yoshitaka ;
Yang, Dongxing ;
Velamakanni, Aruna ;
An, Sung Jin ;
Stoller, Meryl ;
An, Jinho ;
Chen, Dongmin ;
Ruoff, Rodney S. .
SCIENCE, 2008, 321 (5897) :1815-1817
[10]   Printed graphene circuits [J].
Chen, Jian-Hao ;
Ishigami, Masa ;
Jang, Chaun ;
Hines, Daniel R. ;
Fuhrer, Michael S. ;
Williams, Ellen D. .
ADVANCED MATERIALS, 2007, 19 (21) :3623-3627