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N- versus p-doping of graphite: What drives its wet-chemical exfoliation?


We have performed the syntheses of a novel pyrene-porphyrazine conjugate (ZnPzPy) and a reference porphyrazine (ZnPz) to promote the wet-chemical exfoliation of graphite based on the synergetic use of ultrasonication, centrifugation, and doping. ZnPzPy features, on one hand, a hydrophobic pyrene to anchor to the basal plane of graphene, and, on the other hand, an amphoteric porphyrazine to either p- or n-dope graphene. To this end, we have characterized the individual building blocks, that is, ZnPzPy and exfoliated graphite, and the resulting electron donor-acceptor nanohybrid, that is, ZnPzPy / nanographene (ZnPzPy-NG), by means of an arsenal of microscopies and spectroscopies. From a full-fledged characterization we conclude that ZnPzPy facilitates the exfoliation of graphite affording suspensions featuring 9.5% of single- or few-layered ZnPzPy-NG with a mean average size of 200 ± 140 nm. Importantly, a notable shift of charge density from nanographene to ZnPzPy in the ground state of ZnPzPy-NG corroborates the preference of exfoliated graphite to undergo p-doping rather than n-doping. As an immediate consequence, a full charge separation leads in the excited state to a 750 ± 150 ps lived charge separated state.

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Publication details

The article was received on 12 May 2017, accepted on 10 Jul 2017 and first published on 11 Jul 2017

Article type: Paper
DOI: 10.1039/C7NR03379F
Citation: Nanoscale, 2017, Accepted Manuscript
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    N- versus p-doping of graphite: What drives its wet-chemical exfoliation?

    B. Wang, V. Engelhardt, A. Roth, R. Faust and D. M. Guldi, Nanoscale, 2017, Accepted Manuscript , DOI: 10.1039/C7NR03379F

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