Surface Sensitive Photoluminescence of Carbon Nanodots: Coupling between the Carbonyl Group and π‑Electron System

The functional groups and π-electron system of carbon dots (C-dots) were carefully controlled by several innovative chemical methods, without any changes in size, to unravel the relationship between the surface structure and photoluminescence (PL). The results of experiments and theoretical calculations reveal that the PL of C-dots is related to the surface state. The energy gap is determined by the coupling of the π-electron system and carbonyl group, and the quantum yield (QY) is dependent on the carbonyl group. The carbonyl group is the main factor increasing the ratio of nonradiation to radiation recombination, thereby leading to the low QY of C-dots. This work provides a strategy for effectively tuning the structure of C-dots, giving rise to the tunable PL emission wavelength and highly desirable QY, which enables us to further unravel the PL mechanism.