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A computational study on the role of noncovalent interactions in the stability of polymer/graphene nanocomposites

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Abstract

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 dispersion-corrected 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 (π–π stacking, CH–π bonding, H-bonding and lone pair–π 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 α, β and γ, ε conformations) are analyzed and we find that, although the α-conformer with a trans-gauche-trans-gauche (TGTG’) conformation is the lowest energy conformer, the β-conformation of PVDF with the hydrogen atoms facing the graphene (“F-up”) 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.

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Acknowledgements

The authors would like to acknowledge the financial support of SOLVAY, S.A. In addition, the authors acknowledge support from the COST Materials, Physical and Nanosciences (MPNS) Action MP0901: “Designing Novel Materials for Nanodevices—From Theory to Practice (NanoTP)”. M. A. thanks the Fund for Scientific Research , Flanders (FWO-12F4416N), for a postdoctoral fellowship, and the Free University of Brussels (VUB) for financial support.

The authors, and in particular P.G. and F.D.P., want to dedicate this contribution to their colleague Henri Chermette to whom this special issue is dedicated. Henri has been a very fine colleague, almost a friend, for so many years, a true companion in the search for what Density Functional Theory can really contribute to chemistry. That the recently developed and completetely density based NCI method may help chemists in the design of nanocomposites may be an illustration where the Density has led us, and will lead us.

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Authors and Affiliations

  1. Research Group General Chemistry (ALGC) Pleinlaan 2, Vrije Universiteit Brussel (VUB), 1050, Brussels, Belgium

    S. Güryel, M. Alonso, B. Hajgató, G. Van Lier, P. Geerlings & F. De Proft

  2. SOLVAY S.A., Innovation Center, Ransbeekstraat 310, 1120, Brussels, Belgium

    Y. Dauphin

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  1. S. Güryel
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  2. M. Alonso
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Correspondence to P. Geerlings.

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This paper belongs to Topical Collection Festschrift in Honor of Henry Chermette

Appendix

Appendix

Fig. 12
figure 12

NCI analysis of H-nitro with GO and PG. The gradient isosurfaces (s = 0.5 a.u.) are colored on a BGR scale according to the sign (λ2)ρ over the range −0.02 to 0.02 a.u.

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Güryel, S., Alonso, M., Hajgató, B. et al. A computational study on the role of noncovalent interactions in the stability of polymer/graphene nanocomposites. J Mol Model 23, 43 (2017). https://doi.org/10.1007/s00894-017-3214-2

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