N, S/P co-doped hemicellulose-based carbon dots with tunable fluorescence for anti-counterfeiting

Based on the status quo of high energy consumption and low utilization of nonfibrous components in traditional pulp and paper industry, a sustainable and facile approach was proceeded to realize the high-value utilization of hemicelluloses from papermaking waste liquor. The hemicellulose waste produced by ethanol precipitation in pre-hydrolysis liquor (PHL), was directly used to fabricate carbon dots (CDs) via a hydrothermal method. The hydrothermal carbonization and heteroatoms doping contributed to the sp2 conjugated domains and surface defect states of CDs, thus creating the bright blue (N-CDs), deep cyan (N/S-CDs), and light cyan (N/P-CDs) fluorescence under UV radiation. The XPS analysis and density functional theory (DFT) calculations demonstrated that the large sp2 conjugated system and the synergistic effect of CO, N-(C)3, CS, and PO groups promoted the narrow of band gap and the red-shift of fluorescence emission. Importantly, the prepared CDs grew in situ on cotton fibers, showed excellent fluorescent performance. The obtained CDs could be also utilized to prepare anti-counterfeiting film and ink due to their excellent optical features, verifying the great potential application as security material. The feasible strategy of the high-value conversion of biomass waste opens a window of opportunity for the practical anti-counterfeiting utilizations.