期刊
JOURNAL OF MOLECULAR MODELING
卷 23, 期 2, 页码 -出版社
SPRINGER
DOI: 10.1007/s00894-017-3214-2
关键词
Non covalent interactions; Polymer graphene nanocomposites; NCI analysis; Functionalized polymer building blocks
类别
资金
- SOLVAY, S.A.
- COST Materials, Physical and Nanosciences (MPNS) Action MP0901: Designing Novel Materials for Nanodevices-From Theory to Practice (NanoTP)
- Fund for Scientific Research, Flanders [FWO-12F4416N]
- Free University of Brussels (VUB)
Understanding the interaction between graphene and polymers is of essential interest when designing novel nanocomposites with reinforced mechanical and electrical properties. In this computational study, the interaction of pristine graphene (PG) and graphene oxide (GO) with a series of functional groups, representative of the functionalised buildings blocks occurring in different polymers, and attached to aliphatic and aromatic chains, is analyzed using dispersioncorrected semi-empirical methods (PM6-D3H4X) and density functional theory calculations with empirical dispersion corrections. Functional groups include alkyl, hydroxyl, aldehyde, carboxyl, amino and nitro groups, and the binding energies of these groups with graphene derivatives (PG and GO) are determined. Nitro-and carbonyl groups display stronger interactions in both aliphatic and aromatic chains. The importance of dispersion-type and non-covalent interactions (NCI) in general, which typically, double the interaction energies, is revealed. The results are interpreted in an extensive NCI analysis in order to characterize the different types of NCI, providing a better understanding of the nature of the interaction (p-p stacking, CH-p bonding, H-bonding and lone pair-p interaction) at stake. In order to highlight the influence of polymer structure/conformation on top of that of their functional groups, the binding of three polymers, polyethylene (PE), polystyrene (PS) and polyvinylidene fluoride (PVDF), on pristine graphene is also investigated. Our calculations indicate that, although all polymers exhibit evident attractive interactions with the graphene sheet, the overall interaction is strongly influenced by the specific polymer structure. Thus, three main conformations of PVDF (the so-called alpha, beta and gamma, epsilon conformations) are analyzed and we find that, although the a-conformer with a trans-gauche-trans-gauche (TGTG') conformation is the lowest energy conformer, the beta-conformation of PVDF with the hydrogen atoms facing the graphene (BFup) has the strongest interaction with the graphene surface among the polymers under consideration. Taken together, our computational approach sheds light on the character and importance of non-covalent graphene-polymer functional group interactions combined with the structural/conformational properties of the polymer, which are at stake in the design of novel nanocomposites with reinforced mechanical and electrical properties.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据