Post-synthetic regulation of the fluorescence of CDs: insights into the fluorescence mechanism

Abstract

Exploring the origin of emission is fundamental in the field of carbon dots (CDs). Due to the lack of suitable in situ probing techniques, it is necessary to explore effective alternative methods that can accurately reflect the relationship between the emission and the composition of the functional groups of CDs. Herein, we propose a new method of post-synthetic treatment of CDs by photo-oxidation to investigate the origin of emission for CDs. After the addition of a photo-oxidant into pre-prepared CDs under UV irradiation, the fluorescence of CDs can be regulated from the original orange emission to the final green emission due to the damage of original functional groups and the formation of new functional groups on CDs during the post-treatment process. The abundant dynamic information about the functional groups and emissions of CDs during the visible and ready-to-monitor post-treatment process makes it possible to quantitatively analyze the origin of the emission of CDs. Our results suggest that the emission sub-peaks at 560 nm and 600 nm relate to the CD surface-state-associated –NH₃⁺ groups, while the emission sub-peak at 537 nm or 494 nm is associated with the CD surface-state-associated –OH groups or the CD surface-state-associated carbonyl groups (CO). Under UV irradiation, the CD surface-state-associated –NH₃⁺ groups can be continuously converted into the CD surface-state-associated –OH groups and the CD surface-state-associated carbonyl groups (CO), leading to the changed emission color of CDs.