Insight into the Multistate Emissive N, P-doped Carbon Nano-Onions: Emerging Visible-Light Absorption for Photocatalysis.

Carbon dots (CDs) have become one of the most emerging materials as an alternative solar light-induced photocatalyst in contrast to traditional metal-based systems. However, one of the major challenges is the lack of visible light absorption. Herein, we have fabricated unique N, P-co-doped CDs with a self-assembled onion-like layered structure by using a bottom-up facile synthesis technique from chitosan gel and phosphoric acid as molecular precursors. This typical layered structure of N, P-co-doped carbon nano onions (N, P-CNOs), with an average size of 25-50 nm, displays an enhanced visible light absorption. Detailed structural and elemental characterizations confirm the extensive aromatic domain with P-containing surface functionalities, while electrochemical study clarifies the lowering of band gaps as well as the creation of new electronic states in comparison to the pristine N-CDs. Furthermore, the intrinsic structural features are correlated with the underpinning photophysical processes by steady-state and time-resolved fluorescence spectroscopy. In addition, steady-state polarized emission and thermo-responsive PL properties have been carried out to unveil further the structure-property correlation of N, P-CNOs, and their comparative study with pristine N-CDs at the different excitation wavelengths. Finally, N, P-CNOs exhibit efficient visible-light-induced photocatalysis, and the detailed mechanistic study is carried out by trapping the photogenerated species in an aqueous medium. The prepared N, P-CNOs displayed an excellent visible-light photocatalytic performance over MB dye with a degradation efficiency of 75.8% within 120 min along with a degradation rate constant of ∼0.0109 min-1 . It is concluded that the easy to synthesize and low-cost N, P-CNOs with a unique morphology hold great potential for application in visible-light photocatalysis.