Conti S, Del Rosso MG, Ciesielski A, Weippert J, Boettcher A, Shin Y, Melinte G, Ersen O, Casiraghi C, Feng X, Muellen K, Kappes MM, Samori P, Cecchini M (2016)
Publication Type: Journal article
Publication year: 2016
Book Volume: 17
Pages Range: 352-357
Journal Issue: 3
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.
APA:
Conti, S., Del Rosso, M.G., Ciesielski, A., Weippert, J., Boettcher, A., Shin, Y.,... Cecchini, M. (2016). Perchlorination of Coronene Enhances its Propensity for Self-Assembly on Graphene. ChemPhysChem, 17(3), 352-357. https://doi.org/10.1002/cphc.201501113
MLA:
Conti, Simone, et al. "Perchlorination of Coronene Enhances its Propensity for Self-Assembly on Graphene." ChemPhysChem 17.3 (2016): 352-357.
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