Photoluminescence quenching of thermally treated waste-derived carbon dots for selective metal ion sensing.

In the present study, carbon-dots (CDs) were derived from the thermal oxidation of an agricultural waste, bitter tea residue, to obtain different sp2/sp3 ratios and electronic structures for metal sensing. The CDs obtained from calcination at 700 °C exhibited the highest photoluminescence (PL) quantum yield (QY) of 11.8% among all the samples treated at different temperatures. These CDs had a high degree of graphitization, which resulted in a strong π-π* electron transition, and hence in a high QY. The strong photoluminescence of the CDs could be used to sense the metal ions Ag+, Sr2+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+, and Sn2+ by monitoring their PL intensity at an excitation wavelength of 320 nm. The metals inhibited the PL intensity in the order Ag+ > Fe2+, Fe3+, Ni2+ > Sr2+, Co2+, Cu2+, Sn2+, which demonstrated that the CDs exhibited high metal ion detection capability and selectivity. The detection of Fe3+ using CDs was performed in the range of 10-100 ppm with a LOD (limit of detection) value of 0.380 ppm. Theoretical calculations demonstrated that Ag+, Sr2+, and Sn2+ induced charge transfer excitation and that Fe2+ and Ni2+ induced d-d transitions via complexation with the sp2 clusters. The charge transfer excitation and d-d transitions hindered the π-π* transition of the sp2 clusters, leading to a quenching effect. On the other hand, Li+, Na+, and K+ ions did not alter the π-π* transition of the sp2 clusters, resulting in a negligible quenching effect. In summary, the oxidation level and electronic structure of CDs derived from bitter tea residue could be tailored, and the CDs were shown to be a facile, sustainable, and eco-friendly material for metal sensing.