• 文献标题:   Graphene Oxide. Origin of Acidity, Its Instability in Water, and a New Dynamic Structural Model
  • 文献类型:   Article
  • 作  者:   DIMIEV AM, ALEMANY LB, TOUR JM
  • 作者关键词:   graphene oxide, acidity, dynamic structural model, graphene interaction with water
  • 出版物名称:   ACS NANO
  • ISSN:   1936-0851 EI 1936-086X
  • 通讯作者地址:   Rice Univ
  • 被引频次:   299
  • DOI:   10.1021/nn3047378
  • 出版年:   2013

▎ 摘  要

The existing structural models of graphene oxide (GO) contradict each other and cannot adequately explain the acidity of its aqueous solutions. Inadequate understanding of chemical structure can lead to a misinterpretation of observed experimental phenomena. Understanding the chemistry and structure of GO should enable new functionalization protocols while explaining GO's limitations due to its water instability. Here we propose an unconventional view of GO chemistry and develop the corresponding "dynamic structural model" (DSM). In contrast to previously proposed models, the DSM considers GO as a system, constantly changing its chemical structure due to interaction with water. Using potentiometric titration, C-13 NMR, FTIR, UV-vis, X-ray photoelectron microscopy, thermogravimetric analysis, and scanning electron microscopy we show that GO does not contain any significant quantity of preexisting acidic functional groups, but gradually generates them through Interaction with water. The reaction with water results In C-C bond cleavage, formation of vinylogous carboxylic acids, and the generation of protons. An electrical double layer formed at the GO interface in aqueous solutions plays an important role In the observed GO chemistry. Prolonged exposure to water gradually degrades GO flakes converting them Into humic acid-like structures. The proposed DSM provides an explanation for the acidity of GO aqueous solutions and accounts for most of the known spectroscopic and experimental data.