Sulfur Species in Graphene Oxide

被引:203
作者
Eigler, Siegfried [1 ,2 ,3 ,4 ]
Dotzer, Christoph [1 ,2 ,3 ,4 ]
Hof, Ferdinand [1 ,2 ,3 ,4 ]
Bauer, Walter [1 ,2 ,3 ,4 ]
Hirsch, Andreas [1 ,2 ,3 ,4 ]
机构
[1] Univ Erlangen Nurnberg, Dept Chem & Pharm, D-91054 Erlangen, Germany
[2] Univ Erlangen Nurnberg, Inst Adv Mat & Proc ZMP, D-91054 Erlangen, Germany
[3] Univ Erlangen Nurnberg, Dept Chem & Pharm, D-90762 Furth, Germany
[4] Univ Erlangen Nurnberg, Inst Adv Mat & Proc ZMP, D-90762 Furth, Germany
基金
欧洲研究理事会;
关键词
graphene oxide; IR spectroscopy; organosulfate; sulfur; thermogravimetry; REDUCTION; DIOXIDE; WATER;
D O I
10.1002/chem.201300387
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The structure of graphene oxide (GO) is of crucial importance for its chemical functionalization. However, the sulfur content present in GO prepared by Hummers' method has only been addressed by a few authors so far. It has been reported that hydrolysis of sulfur species takes place and that stable sulfonic groups are present in graphite oxide. In this manuscript, in contrast to earlier reports, sulfate species are identified that are covalently bound to GO and still present after extensive aqueous work-up. Additionally, we exclude the possibility that sulfonic groups are present in GO as major species after aqueous work up. Our results are based on bulk characterization of graphene oxide by thermogravimetry and subsequent analysis of the decomposition products using mass spectroscopy and infrared spectroscopy. Up to now, the combustion temperature between 200 and 300 degrees C remained almost unaddressed. In a temperature dependant experiment we reveal two main decomposition steps that differ in temperature and that are closely related to the sulfur species in GO. While the decomposition, between 200 and 300 degrees C, is related to the degradation of organosulfate, the other one, between 700 and 800 degrees C, is assigned to the pyrolysis of inorganic sulfate. Furthermore, organosulfate is to some extent responsible for the reactivity of GO. Therefore, the structural model of GO was extended by adding organosulfate in addition to epoxy and hydroxyl groups, which are predominantly covalently bound above and below the carbon skeleton. Furthermore, the identification of organosulfate groups beneath epoxy groups makes new molecular architectures feasible and can be used to explain the properties of GO in various applications.
引用
收藏
页码:9490 / 9496
页数:7
相关论文
共 35 条
[1]  
Bagri A, 2010, NAT CHEM, V2, P581, DOI [10.1038/nchem.686, 10.1038/NCHEM.686]
[2]   On the interaction of sodium dodecyl sulfate with oligomers of poly(ethylene glycol) in aqueous solution [J].
Bernazzani, L ;
Borsacchi, S ;
Catalano, D ;
Gianni, P ;
Mollica, V ;
Vitelli, M ;
Asaro, F ;
Feruglio, L .
JOURNAL OF PHYSICAL CHEMISTRY B, 2004, 108 (26) :8960-8969
[3]  
Brodie B., 1855, ANN CHIM PHYS, V45, P351
[4]  
Burger A, 2000, J PHARM SCI-US, V89, P457, DOI 10.1002/(SICI)1520-6017(200004)89:4<457::AID-JPS3>3.0.CO
[5]  
2-G
[6]   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
[7]   Chemical Reduction of Graphene Oxide to Graphene by Sulfur-Containing Compounds [J].
Chen, Wufeng ;
Yan, Lifeng ;
Bangal, P. R. .
JOURNAL OF PHYSICAL CHEMISTRY C, 2010, 114 (47) :19885-19890
[8]  
Cooper Daniel R., 2012, ISRN Condensed Matter Physics, DOI 10.5402/2012/501686
[9]   Pristine Graphite Oxide [J].
Dimiev, Ayrat ;
Kosynkin, Dmitry V. ;
Alemany, Lawrence B. ;
Chaguine, Pavel ;
Tour, James M. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (05) :2815-2822
[10]   Graphene Oxide. Origin of Acidity, Its Instability in Water, and a New Dynamic Structural Model [J].
Dimiev, Ayrat M. ;
Alemany, Lawrence B. ;
Tour, James M. .
ACS NANO, 2013, 7 (01) :576-588