Simple Full-Spectrum Heterogeneous Photocatalyst for Photo-induced Atom Transfer Radical Polymerization (ATRP) under UV/vis/NIR and its Application for the Preparation of Dual Mode Curing Injectable Photoluminescence Hydrogel

The utilizing light with broadband range has attracted lots of research interest for the photo induced reversible-deactivation radical polymerization (RDRP). However, it is still a challenge for a single catalyst to simultaneously respond to various lights with highly varied wavelengths. Here, we proposed a simple strategy for the preparation of a heterogeneous photocatalyst suitable for photo induced atom transfer radical polymerization (photoATRP) under full spectrum (from UV/vis light to NIR), by combining pyridine nitrogen doped carbon dots (N-CDs) and upconversion nanoparticles (UCNPs). In the presence of these robust UCNP@SiO2@N-CDs composite particles, the photoATRP could be carried on under the different irradiations of UV, blue, green, red, white, and 980 nm NIR light, with a low loading of part per million concentrations of the CuBr2/L catalyst. Moreover, the excellent solvent and aqueous compatibility allow UCNP@SiO2@N-CDs to be capable for photoATRP in both organic solvents and aqueous media, providing well-defined hydrophobic and hydrophilic polymers with low dispersity and excellent chain-end fidelity. In addition, the photoATRP with 980 nm NIR exhibited excellent penetrations through visible-light-proof barriers. The system could be used for the preparation of an injectable hydrogel that had dual curing and photoluminescence modes. Owing to the "living" characteristics of polymer chains achieved through ATRP, the hydrogel was capable to be easily repaired by using monomer as the binder.