Design of Carbon Dots for Metal-free Photoredox Catalysis

The photoreduction potential of a set of four different carbon dots (CDs) was investigated. The CDs were synthesized by using two different preparation methods - hydrothermal and pyrolytic - and two sets of reagents - neat citric acid and citric acid doped with diethylenetriamine. The hydrothermal syntheses yielded amorphous CDs, which were either nondoped (a-CDs) or nitrogen-doped (a-N-CDs), whereas the pyrolytic treatment afforded graphitic CDs, either non-doped (g-CDs) or nitrogen-doped (g-N-CDs). The morphology, structure, and optical properties of four different types of CDs revealed significant differences depending on the synthetic pathway. The photocatalytic activities of the CDs were investigated as such, that is, in the absence of any other redox mediators, on the model photoreduction reaction of methyl viologen. The observed photocatalytic reaction rates: a-N-CDs >= g-CDs > a-CDs >= g-N-CDs were correlated with the presence/absence of fluorophores, to the graphitic core, and to quenching interactions between the two. The results indicate that nitrogen doping reverses the photoredox reactivity between amorphous and graphitic CDs and that amorphous N-doped CDs are the most photoredox active, a yet unknown fact that demonstrates the tunable potential of CDs for ad hoc applications.