Waterborne fluorescent dual anti-counterfeiting ink based on Yb/Er-carbon quantum dots grafted with dialdehyde nano-fibrillated cellulose
Graphical abstract
Synopsis
A simple way to fabricate novel and simple method to prepare the waterborne fluorescent dual anti-counterfeiting ink based on Yb and Er doped CQDs/DANFC composites, which provides a reference for its anti-counterfeiting application in printing and packaging industry.
Introduction
In the information age, data security is particularly important in economic and military fields as well as in our daily lives (Cui, Hegde, Phang, Lee, & Ling, 2014). To ensure the safety and integrity of important information (such as banknotes, documents, certificates, brands, etc.), anti-counterfeit technology is increasingly demanded as they can produce sensitive and stable responses in special forms (Yoon et al., 2013). In recent years, several types of anti-counterfeiting mechanisms have been developed, such as marking (Hu, Chen, Tang, Hu, & Zhou, 2012; Hu, Zhong, Chen, & Chen, 2014), bar code (Yang et al., 2017), thermal imaging, and fluorescence detection (Jiang et al., 2016; Liang et al., 2019; Nair, Abhilash, & Surendran, 2019; Yin et al., 2019). Among them, fluorescent ink has emerged as candidates with high potentials, since other materials either suffer from preparation complexity, low stability, or a lack of multiple anti-counterfeiting capabilities (Bu et al., 2019; Chen, Hu et al., 2019, Chen, Xie et al., 2019; Kumar, Singh, & Gupta, 2016; Ma et al., 2019; Qu, Wang, Lu, Liu, & Wang, 2012; Song, Lin et al., 2016; Shahla, Davood, Omid, & Masoud, 2020; Xu, Zhang et al., 2019, Xu, Lei et al., 2019). Anti-counterfeiting fluorescent ink has the advantages of simple preparation, convenient use, and remarkable effect, so it is widely used in many aspects of life. Generally, traditional luminescent materials including rare earth metals (Cuevas et al., 2019; Zhang et al., 2018), CdS (Tang et al., 2016), ZnS (Prasad & Karthikeyan, 2019), CdTe (Jiang, Zhu, Yao, Fu, & Guan, 2012), photochromic compounds (Yang, Ho, & Chan, 2019), are controlled by monochromic radiation under ultraviolet (UV) and near infrared (NIR) light excitation. However, the photocontrol of such compounds is still very challenging, because the fluorescent substances usually have unfavorable features such as inflexible adjustability, single color emission, and low color purity. Compared with traditional luminescent materials, the new luminescent materials can be smartly controlled by excitable wavelengths and have multiple emission modes exhibiting improved photophysical properties, facile tunability, and excellent compatibility, which are considered to be effective ways for anti-counterfeiting (Chen, Xie et al., 2019; Yao, Tian, & Wu, 2019; Zhang et al., 2018).
In recent years, carbon quantum dots (CQDs), as a new comer of 0 D dimension carbon nanomaterials (Esteves da Silva & Gonçalves, 2011; Jing, Zhao, Sun, Zhong, & Peng, 2019; Sun et al., 2006; Wang et al., 2018), have excellent physiochemical properties, such as high optical stability (Kelarakis, 2015), low-toxicity (Jiang et al., 2016), super conductivity (Zhao et al., 2019), good biocompatibility (Guo et al., 2017), simple preparation, and high quantum yield. CQDs are widely used in fluorescence anti-counterfeiting, bioimaging (Demir et al., 2018), drug delivery (Feng, Ai, An, Yang, & Zhao, 2016), photocatalysis (Xu, Bao, Zhou, Zeng, & Hu, 2016), sensor probes (Ma et al., 2019), supercapacitors (Zhao et al., 2019), and so on. These excellent physiochemical properties make CQDs a promising material in many technological areas (Li et al., 2018; You, Zhang, Liu, & Lei, 2016). However, the poor production yield (Jing et al., 2019), and single luminescence behavior (Zhu et al., 2013) have limited their practical applications. Many studies have shown that doping heteroatoms into CQDs is an effective way to increase quantum yield and improve the fluorescence properties of CQDs for specific applications (Zhao et al., 2019). Yang et al. prepared La-doped CQDs (La-CQDs) through microwave pyrolysis, and the quantum yield and fluorescence lifetime are greatly improved (Yang et al., 2018). Similarly, Zhao et al. described Yb3+-doped CQDs though one step hydrothermal method, achieving the effect of NIR and visible dual emission (Zhang et al., 2018). The feasibility of anti-counterfeiting performance is normally controlled by UV and NIR double excitation via blending some rare earth elements such as Yb3+ and Er3+ with CQDs (Gayathri, Ghosh, Sudhakara, & Viswanath, 2015; Xue et al., 2018). Er3+ ion has a specific UCPL performance because of its large stokes shift and line-shaped emission in the near infrared region. Therefore, it is interesting to dope Er3+ into CQDs to give them more complex luminescence behavior. Meanwhile, it is necessary to embed the use of sensitizers to luminescence of Er3+ ions as it can generate energy transfer between the sensitizer and the activator to produce efficient fluorescence emission. Yb3+ ion is a good choice to introduce the sensitizer because its absorption cross section near 980 nm which can well match the energy difference of Er3+, and resulting in higher probability of transferring energy to enhance UCPL (Shi et al., 2018; Wei, Zhang, Liu, Han, & Yuan, 2017; Zhang et al., 2018). However, the relationships between the CQDs/substrate interface photon energy transfer have not been systemically studied, and the mechanism of UV and NIR double excitation by CQDs based composites still needs to be further studied.
Nanofibrillated cellulose (NFC), a rod-like cellulosic fiber with a diameter of tens of nanometers and a length of several microns, has aroused much interest due to its larger specific surface area, special rheological properties, a large number of hydroxyl groups, higher mechanical modulus, etc. (Cao et al., 2019; Deepa et al., 2015; Khalil et al., 2014; Oksman et al., 2016; Qi, Cheng, Ye, Zhu, & Aparicio, 2019; Trache, Hussin, Haafiz, & Thakur, 2017). More importantly, we found that NFC has a similar rheological properties and thixotropic properties with conventional waterborne ink (Cao et al., 2019; Qi et al., 2019). When a shear force is applied to the solution, the viscosity drops rapidly to a lower level, but the viscosity would return to the original level once the shear force removed, which is completely consistent with the pseudoplastic fluid (Quraishi, Plappert, Grießer, Gindl-Altmutter, & Liebner, 2019; Wang & Fu, 2019). Considering the advantages of CQDs and NFC, the interface barrier can be eliminated, and the nanoscaled mixtures with intimate contacts can be fabricated. In addition, we expected to improve the accessible area between CQDs and NFC interface and then form a channel for photon energy transfer. And also, to construct the system of anti-counterfeiting waterborne ink by adding NFC for the improvement of the overall rheological properties.
In this paper, the waterborne fluorescent dual anti-counterfeiting ink based on UV and NIR double excitation mechanism was successfully prepared. CQDs were doped with rare earth elements Yb and Er, and successfully grafted onto NFC by reductive amination reaction. Then, NFC was added into waterborne ink because of its special rheological properties. Thixotropy and curing properties of waterborne ink were measured. The results showed that NFC, as a carrier of CQDs can be added to waterborne ink, which is of great significance in improving the rheological properties of ink.
Section snippets
Materials and chemicals
The cellulose sample (pine pulp, DP = 1000) was supplied by Hubei Chemical Fiber Co., Ltd. (Hubei, China). Commercial endoglucanase (Banzyme 2900) was purchased from UPM-kymmene Co., Ltd (Jiangsu, China). Ytterbium chloride hexahydrate (YbCl3·6H2O, purity ≥ 99.99 %) and erbium chloride hexahydrate (ErCl3·6H2O, purity ≥ 99.9 %) were purchased from Shanghai Sheeny Metal Material Co. Ltd. (Shanghai, China). 2-picolineborane (C6H10NB, purity ≥ 95 %) and polyvinyl alcohol 1799 [PVA-1799, alcoholysis
Morphology and structural characteristics
The fabrication of Yb/Er-CQDs-DANFC was shown in Scheme 1. Firstly, the double rare-doped CQDs (Yb/Er-CQDs) with amino groups (proved by FTIR, Fig. 2f) with the average size of 3.42 nm (Fig. 1f) were first synthesized through hydrothermal method using CA, EDA, YbCl3, and ErCl3 as raw materials, respectively. The amide bonds were prepared by dehydration condensation reaction between carboxyl group and amino group of CA, and the coordinate bonds were generated under the attraction of positive and
Conclusions
The research developed and investigated the performance of an Er and Yb doped CQDs, which is a NFC supported CQDs capable of both traditional photoluminescence and up-conversion luminescence. In view of their desirable photoluminescence behavior, we combined the Yb/Er-CQDs-DANFC composites with NFC suspensions to prepared waterborne ink, which emits 450 nm blue fluorescence under 370 nm excitation, while doped quantum dots emit 550 nm green fluorescence under 980 nm near infrared radiation,
CRediT authorship contribution statement
Pengfei Li: Methodology, Conceptualization, Formal analysis, Data curation, Software, Writing - original draft, Writing - review & editing. Jinsong Zeng: Investigation, Data curation, Funding acquisition, Project administration, Supervision. Bin Wang: Methodology, Validation, Writing - review & editing, Investigation. Zheng Cheng: Writing - review & editing, Software. Jun Xu: Writing - review & editing, Visualization, Validation, Investigation. Wenhua Gao: Writing - review & editing. Kefu Chen:
Declaration of Competing Interest
There are no conflicts to declare.
Acknowledgements
This research was financially supported by National Key R&D Program of China (2017YFB0307902), Guangdong provincial science & technology plan projects (Number: 2015B020241001), the National Natural Science Foundation of China (No. 31600471), China Postdoctoral Science Foundation (2019TQ0100), the Fundamental Research Funds for the Central Universities (2019MS085 and 2017YFB0307902), and State Key Laboratory of Pulp and Paper Engineering (201833).
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