Near-infrared and visible dual emissive transparent nanopaper based on Yb(III)–carbon quantum dots grafted oxidized nanofibrillated cellulose for anti-counterfeiting applications
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We report a novel near-infrared (NIR) and visible dual emissive transparent Yb3+-nanopaper, which is produced from Yb3+-CQDs grafted oxidized nanofibrillated cellulose (Yb3+-CQDs-ONFC) using a press-controlled extrusion film-making method. The Yb3+-nanopaper exhibits excellent properties, including high transparency (90%), good flexibility, visible fluorescence and NIR phosphorescence. The morphology and chemical structures of Yb3+-nanopaper are investigated with SEM, TEM, XRD, XPS, ICP-OES and FT-IR spectroscopy. The experimental results show that the Yb3+-CQDs have been successfully grafted onto ONFC matrix, and the Yb3+-CQDs are well dispersed in nanopaper with strong visible-NIR dual emission under only one UV excitation. In the Yb3+-nanopaper, CQDs not only act as visible fluorescence “emitter” but also as “antenna” sensitizing Yb3+ ions with NIR characteristic luminescence. And the sensitization of the energy transfer pathway is mainly through singlet state (1LC). Furthermore, the surface passivation of Yb3+-CQDs with ONFC produces an enhanced NIR luminescence by eight times in intensity. Of importance here is that high level security codes of Yb3+-nanopaper can be achieved in three fashions including colour tuning from blue to yellow, NIR/visible spectra, and nanosecond/microsecond lifetime. In addition, aqueous solution of Yb3+-CQDs-ONFC being colourless and transparent can be applied as water-based security ink and spread on the currency note or filter paper, and the spread patterns on the filter paper are stable under water or moist environment.
KeywordsNIR-visible dual emission Yb(III) doped carbon quantum dots Oxidized nanofibrillated cellulose Water-based ink Transparent nanopaper
This work was supported by National Natural Science Foundation of China (31370578, 21703131), Doctoral Scientific Research Foundation of Shaanxi University of Science and Technology (2016BJ-40, BJ15-26). X.Z. thanks the supports from Hong Kong Research Grants Council (HKBU 22304115), Hong Kong Baptist University (FRG2/16-17/024, FRG1/15-16/052, RC-IRMS/16/17/02CHEM and RC-ICRS/1617/02C-CHEM).
- Divya V, Biju S, Varma RL, Reddy M (2010) Highly efficient visible light sensitized red emission from europium tris[1-(4-biphenoyl)-3-(2-fluoroyl)propanedione](1,10-phenanthroline) complex grafted on silica nanoparticles. J Mater Chem 20:5220–5227. https://doi.org/10.1039/C0JM00588F CrossRefGoogle Scholar
- Gao MX, Liu CF, Wu ZL, Zeng QL, Yang XX, Wu WB, Li YF, Huang CZ (2013) A surfactant-assisted redox hydrothermal route to prepare highly photoluminescent carbon quantum dots with aggregation-induced emission enhancement properties. Chem Commun 49:8015–8017. https://doi.org/10.1039/C3CC44624G CrossRefGoogle Scholar
- Guo J, Liu D, Filpponen I, Johansson L-S, Malho J-M, Quraishi S, Liebner F, Santos HA, Rojas OJ (2017) Photoluminescent hybrids of cellulose nanocrystals and carbon quantum dots as cytocompatible probes for in vitro bioimaging. Biomacromolecules 18:2045–2055. https://doi.org/10.1021/acs.biomac.7b00306 CrossRefGoogle Scholar
- Miao M, Zhao J, Feng X, Cao Y, Cao S, Zhao Y, Ge X, Sun L, Shi L, Fang J (2015) Fast fabrication of transparent and multi-luminescent TEMPO-oxidized nanofibrillated cellulose nanopaper functionalized with lanthanide complexes. J Mater Chem C 3:2511–2517. https://doi.org/10.1039/C4TC02622E CrossRefGoogle Scholar
- Raj DBA, Francis B, Reddy MLP, Butorac RR, Lynch VM, Cowley AH (2010) Highly luminescent poly(methyl methacrylate)-incorporated europium complex supported by a carbazole-based fluorinated β-diketonate ligand and a 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene oxide co-ligand. Inorg Chem 49:9055–9063. https://doi.org/10.1021/ic1015324 CrossRefGoogle Scholar
- Song N, Jiao D, Cui S, Hou X, Ding P, Shi L (2017) Highly anisotropic thermal conductivity of layer-by-layer assembled nanofibrillated cellulose/graphene nanosheets hybrid films for thermal management. ACS Appl Mater Interfaces 9:2924–2932. https://doi.org/10.1021/acsami.6b11979 CrossRefGoogle Scholar
- Zhao J, Wei Z, Feng X, Miao M, Sun L, Cao S, Shi L, Fang J (2014) Luminescent and transparent nanopaper based on rare-earth up-converting nanoparticle grafted nanofibrillated cellulose derived from garlic skin. ACS Appl Mater Interfaces 6:14945–14951. https://doi.org/10.1021/am5026352 CrossRefGoogle Scholar