Heating-free synthesis of red emissive carbon dots through separated processes of polymerization and carbonization

Abstract

Polymerization and carbonization are believed as two basic processes for the bottom-up synthesis of carbon dots (CDs). Since these two processes usually occur simultaneously due to the high reaction temperature and fast reaction rate, it is still a challenge to separate and control these two processes. In the present work, we reported a new room temperature method, which achieved the separated and controlled polymerization and carbonization processes. The polymerization process is realized by dissolving o-phenylenediamine (OPD) in ethanol at room temperature, and finally obtained polymer dots (PDs) without any lattice with a sphere size of 29.6 nm. The carbonization process begins in a manual way by adding concentrated sulfuric acid. After carbonization, CDs (noted as CPDs in this work) with a size of 3.6 nm and a clear lattice can be obtained. Importantly, the separated polymerization and carbonization make us possible to adjust the composition or interactions of intermediate products during the synthesis process. As a prototype, we added acetic acid (AA) additives into OPD precursors during the polymerization stage. Due to the crosslink enhanced emission (CEE) effect via hydrogen bonds which are produced by the amide groups from AA reaction products with H in the -NH₃⁺ or aromatic ring, the resulted CPDs show improved PLQY from an initial 6.87% (without AA) to 16.47%. The current work realized the separated and controllable polymerization and carbonization processes, opening up the door for tuning the composition and interactions of intermediate products before carbonization.

Keywords: Carbonization; Fluorescence regulation; Heating-free synthesis; Red emissive carbon dots; Separation processes of polymerization.