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Polyoxometalate-based Rewritable Paper Hanjun Sun, Nan Gao, Jinsong Ren, and Xiaogang Qu Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/acs.chemmater.5b03711 • Publication Date (Web): 30 Oct 2015 Downloaded from http://pubs.acs.org on October 31, 2015
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Polyoxometalate-based Rewritable Paper Hanjun Sun,†,‡ Nan Gao, † Jinsong Ren, † and Xiaogang Qu†,* †Laboratory of Chemical Biology and State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022, China. ‡ University of the Chinese Academy of Sciences, Beijing, 100039, China.
ABSTRACT: Paper is of great importance for human society as writing materials but also bring enormously economical and environmental problems. Rewritable paper, which can be used repeatedly, is an alternative approach to solve these problems caused by both waste of paper and ink. Although several kinds of rewritable paper have been reported, the molecular degradation, short display time, high toxicity and expensive price of colour switching materials used in rewritable paper severely limit their practical applications. In consideration of the high stability, biocompatibility and commercial availability of keggin typed polyoxometalates(POM), herein, a new rewritable paper based on the reversible discoloration reactions of POM is designed. With a pen or a commercial desktop printer, H2O2-handwriting and H2O2-jet has been realized, respectively. After more than ten writing-erasing cycles, there is no observable colour fading on the rewritable paper. What’s more, the POM based rewritable paper (PRP) can keep handwritten and H2O2-jet printed characters and patterns to remain legible with high resolution at ambient conditions for more than three months. In considering that H2O2 and isopropanol are commonly used disinfectant, detergents and flavoring agent, while our daily UV disinfector can supply UV irradiation, the PRPs therefore show promising potential for use as a long-lasting rewritable paper.
Occupying a key position as a medium for daily communication, information dissemination and storage, paper is of great importance for human society.1-3 Although electronic media are becoming more and more popular, the average consumption of paper worldwide currently reaches 400 million tons per year and have been increased three times in the last three decades.1-3 Unfortunately, most of papers are used for only once reading before being discarded, and the papers and printing ink bring huge environmental problems including deforestation, solid waste and chemical pollution.4 Rewritable paper (RP), which can be used repeatedly, is an alternative approach that can solve the economical and environmental problems caused by both waste of paper and ink.5-13 Up to date, quiet progresses have been made in this area, light-responsive, pHresponsive and humidity-responsive color switching materials based RP have shown the potential in practical applications.5-13 However, some major challenges still existed:11, 13-16 Firstly, color switching stimuli often cause the molecular degradation of organic dyes; Secondly, many switchable materials can’t retain their color for a long time under ambient conditions, which is too short for reading and not suitable for information storage; Thirdly, the toxicity of switchable materials results in healthy problems in daily use; besides, synthesis routes of most switchable materials are complex, which would be time consuming and expensive. These issues remarkably limit their practical applications. Therefore, it is highly desired to develop RPs based on new materials and color switching mechanisms. Polyoxometalates (POMs) are a class of anionic metal oxide clusters of Mo, W, V and Nb. They have attracted great attentions due to their remarkable structural and electronic/magnetic properties, which promise their applications in the fields of catalysis and medicine during the last two decades.17,
18
One of the most interesting properties of POMs is that they keep their composition and structure during redox process; meanwhile, POMs which contain Mo or W can be switched to dark blue color when reduced, and will go back to the origin color when oxidized.19, 20 This reversible discoloration of POMs is similar with the color switching materials, which inspires us to explore their applications as display media in RPs (Figure 1A). In addition, compared with existing color switching materials, (i) the composition and structure of POMs are stable during the color switching;19, 20 (ii) both the oxidative and reduced state of POMs are stable and can retain their color for a long time under ambient conditions, which makes long time reading and information storage possible; (iii) the reaction conditions of color switching for POMs are simple and convenient, for example, H2O2 can oxidize the reduced POMs and the alcohol can reduce POMs under UV irradiation, which does not need catalyst; (iv) POMs have been used as drug agents and show biocompatibility;18, 21-30 (v) some POMs, such as keggin typed phosphomolybdic acid and phosphotungstic acid are commercially available which don’t need complex synthesis and have a relative lower price. Considering the above advantages of POMs, herein, we design a kind of RP based reversible discoloration of phosphomolybdic acid (H3PMo12O40) to address the existing limits of RPs. The information can be easily written by H2O2, erased by isopropanol under UV irradiation and retain for several months on POMs based RPs (PRPs). Moreover, using H2O2 as ink, we realized rewritable H2O2-jet printing on PRPs, which indicated the promising practical applications of the designed RP. In addition, H2O2 and isopropanol are widely used disinfectant and detergent31, 32 and our daily UV disinfector can supply UV irradiation, the PRPs therefore show promising potential for use as a long-lasting rewritable paper.
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and neat, which demonstrated the necessity of PEG in construction of PRPs (Figure S2).
Figure 1. (A) Structures of phosphomolybdic anion (PMo12O403-). (B) Illustrations of reversible color switching process of POMs. (C) Visible absorption spectra of POMs and reduced POMs (rPOMs) in mixtures of isopropanol and water (1:4). (D) A plot of the absorbance at 700 nm versus the number of cycles as the above solution of phosphomolybdic acid is cycled through oxidization and reduction.
Figure 2. Reversibility and repeatability of PRPs. (A) The reflective visible spectra of the prepared PRPs and the PRPs oxidized by H2O2, respectively. (B) A plot of reflectivities at 700 nm versus the number of cycles as the phosphomolybdic acid in the PRPs is cycled through oxidization (writing: H2O2 oxidize) and reduction (erasing: reducing POMs erase by isopropanol under UV irradiation). (C) Photographs for the prepared (left) and oxidative (right) PRPs, respectively. The size of PRPs is 20 mm by 20 mm.
Scheme 1. Schematic representations of the four-layer structure used to prepare the PRPs.
In our design, the oxidation and reduction of phosphomolybdic acid are the basic reactions which occurred in printing and erasing. The dark blue reduced POMs (rPOMs) are synthesized by photochemical method according to previous reports.33, 34 As shown in Figure 1B and Figure S1, after adding H2O2, the strong absorption band at ca. 700 nm of rPOMs disappeared and its dark blue color changed to light yellow within 3 min. When using isopropanol to reduce the POMs solution oxidized by H2O2, it came back to dark blue (Figure 1C and D). From the visible spectra, this process showed excellent reversibility and repeatability, which inspired us to construct POM based RP. The construction of PRPs was similar with that of previous report (Scheme 1).11 Polyethylene glycol (average Mn: 20000, PEG20000) was utilized not only to passivate efficiently the hydroxyl groups of paper but also possess excellent swellability and assisted the penetration of H2O2 molecules, consequently this increased the opportunity of triggering the redox reaction of POMs, which made the characters and patterns clearer on RP.11 For control, the PRPs without PEG20000 were also prepared. After writing characters, the H2O2 ink diffused rapidly on the surface of paper without PEG20000, resulting in the unclear written records; while for the PEG20000 passivated RP, the written characters were clear
Figure 3. Two productions of PRPs we design: (A) memos and (B) printing papers. (C) Hand writing on PRPs with a pen with H2O2 as ink.
The reversibility and repeatability is the most important property for RPs which the users concerns. Reflective visible spectroscopy was used to test the reversibility and repeatability of PRPs (Figure 2). The PRPs material exhibited strong absorption band in visible region with a low reflectivity (down to 10%), which almost didn’t reflect any visible light. After introduction of H2O2, the intensity of absorption band in visible region decreased with the oxidation of rPOMs in PRPs, especially in the region between 500-800 nm (Figure 2A). For studying the repeatability of PRPs, the reflectivity at 700 nm was also recorded after repetitive writing with H2O2 and erasing by isopropanol under UV irradiation, just slight decrease in reflective intensity was observed after 10 writing-erasing cycles (Figure 2B), and the reflective intensity of the back side of the paper was not significant enhanced after several time rewritings, which indicated that the POMs could be immobi-
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lized in the PRPs material, and proved the stability of PRPs (Figure S3).
Figure 4. (A) Repeatedly writing i) English characters; ii) Chinese characters and iii) numbers on the PRP memos. (B) Side-byside comparison of ink-jet prints with H2O2-jet prints. i) ink-jet prints printed by HP DeskJet 1011 printer with cartridges (HP 802, black); ii) H2O2-jet prints printed by the same printer with commercial HP 802 cartridges refilled with H2O2 (100~200 mM, 4 ml) on PRPs. (C) H2O2-jet printing complex patterns on the PRPs.
demonstrated the ability for information storage of PRPs than that of previous reports (Figure 5B).11, 13 Even some POMs have been used as drug agents and proved with low toxicity, in consideration of the importance of toxicity and safety issues of the rewritable materials, the cytotoxicity tests of phosphomolybdic acid we used in this work were carried out by using MTT assays. After 24 h incubation, MTT tests indicated that the POMs and rPOMs we used here were within low toxicity range (Figure S4), which indicated the safety of PRPs.29, 30 In summary, we have designed an effective and economic RPs based on the reversible discoloration reactions of POMs. The PRPs can keep handwritten and H2O2-jet printed letters and characters remain legible with high resolution at ambient conditions for more than three months, which is long enough for many practical applications involving temporary reading and even information storage. And after more than ten printing-erasing cycles, rewritable writings or printings have been realized without observable color fading, which exhibited high durability. The introduction of commercial POMs in PRs can overcome some problems of reported RPs, such as molecular degradation, short display time, high toxicity and expensive price caused by complex synthesis of reversible color switching materials. Since household UV disinfector can be used as UV light source and H2O2 and isopropanol are domestic disinfectant, detergents and flavoring agent, the designed PRPs show promising potential for use as a long-lasting rewritable paper.
ASSOCIATED CONTENT
Figure 5. (A) The reflective visible spectra of the PRPs. Black line: initial; Red line: after three months. (B) Comparison of the handwriting effects on PRPs. Left: initial; Right: after three months.
Considering the excellent performance of PRPs, we designed two productions: memos (6 cm × 2 cm) and A4 sized printing papers for daily use (Figure 3A and 3B). Using a pen with H2O2 (100~200 mM) as ink, English characters, Chinese characters and numbers could be handwritten on the memos repeatedly (Figure 3C and Figure 4A). Furthermore, taking advantages of current ink-jet printing techniques and priming H2O2 into the commercial cartridges, we realized H2O2-jet printing on PRPs by commercial ink-jet printers (Figure 4B). Besides the general characters and symbols, complex patterns could be printed on the PRPs as well (Figure 4C). Similar with memos, after erasing by isopropanol under UV irradiation, the memos and printing papers could be used repeatedly as well. More importantly, through a rough estimation, the per print of the PRP (based on a conservative 10 times reusage/sheet) just cost approximately one-fifth of the normal ink-jet printing (Table S1), thus this PRP showed potentially powerful market competitiveness. Furthermore, the retaining time of information is also very important for RPs. After three months, there was no obvious difference in the reflective visible spectra of PRPs (Figure 5A). And all the characters, numbers and patterns kept clear since they were written on the PRPs, which
Supporting Information. Experiment section; Response time of colour switching reaction of polyoxometalates; The effect of PEG20000 in PRPs; Stability of PRPs after 10 times’ rewritable cycles; Cytotoxicity studies of the POMs and rPOMs; H2O2-jet printing equipments; Cost Comparisons between H2O2-jet on PRPs and normal ink-jet; This material is available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION Corresponding Author * Address correspondence to Xiaogang Qu. Fax: (+86) 431-85262656 E-mail:
[email protected] Notes The authors declare no competing financial interests.
ACKNOWLEDGMENT This work was supported by 973 Project (2011CB936004, 2012CB720602), and NSFC (21210002, 21431007, 21533008).
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