Article Dans Une Revue ChemPhysChem Année : 2016

Perchlorination of Coronene Enhances its Propensity for Self-Assembly on Graphene

Résumé

Providing a quantitative understanding of the thermodynamics involved in molecular adsorption and self-assembly at a nanostructured carbon material is of fundamental importance and finds outstanding applications in the graphene era. Here, we study the effect of edge perchlorination of coronene, which is a prototypical polyaromatic hydrocarbon, on the binding affinity for the basal planes of graphite. First, by comparing the desorption barrier of hydrogenated versus perchlorinated coronene measured by temperature-programmed desorption, we quantify the enhancement of the strength of physisorption at the single-molecule level though chlorine substitution. Then, by a thermodynamic analysis of the corresponding monolayers based on force-field calculations and statistical mechanics, we show that perchlorination decreases the free energy of self-assembly, not only enthalpically (by enhancing the strength of surface binding), but also entropically (by decreasing the surface concentration). The functional advantage of a chemically modulated 2D self-assembly is demonstrated in the context of the molecule-assisted liquid-phase exfoliation of graphite into graphene.

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hal-04916592 , version 1 (28-01-2025)

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Simone Conti, Maria G. del Rosso, Artur Ciesielski, Jurgen Weippert, Artur Boettcher, et al.. Perchlorination of Coronene Enhances its Propensity for Self-Assembly on Graphene. ChemPhysChem, 2016, 17 (3), pp.352--357. ⟨10.1002/cphc.201501113⟩. ⟨hal-04916592⟩
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