(Photo)electrocatalysis of molecular oxygen reduction by S-doped graphene decorated with a star-shaped oligothiophene.

Heteroatom-doped graphene-based materials attract great interest as non-metal electrocatalysts for the oxygen reduction reaction (ORR). In this work, a straightforward approach was described to prepare nanoensembles of star-shaped oligothiophene 1 supramolecularly immobilized on sulfur-doped graphene sheets (SG). The 1/SG ensemble was comprehensively characterized by Raman and IR spectroscopy and morphologically imaged by HR-TEM, while the loading of 1 onto SG was estimated by TGA under an inert atmosphere. Based on detailed electrochemical and electrocatalytic assays, 1/SG was proved to be a highly efficient and stable electrocatalyst toward the ORR. The high catalytic activity of 1/SG was attributed to the (a) presence of chemical defects, induced by the insertion of electron rich sulfur within the lattice of SG, (b) existence of structural defects, due to the generation of vacancies along the carbon lattice in SG, and (c) high and homogeneous coverage of the SG surface by the sulfur-rich star-shaped oligothiophene 1. In addition, the optical properties of 1/SG were screened by UV-Vis and steady-state and time-resolved PL and the development of strong photoinduced intra-ensemble electronic interactions within the ensemble was revealed. Exploiting the latter, by photoirradiating 1/SG, a significantly improved photoelectrocatalytic activity towards the ORR was observed.