Oxygenated deuterium-activated luminescent color-changing metal-organic framework material, and preparation method and application thereof

Abstract

The present application relates to a kind of deuterium oxide activated luminescent color-changing metal organic framework material and its preparation method and application, belong to optical anti-counterfeiting technical field.The deuterium oxide activated luminescent color-changing metal organic framework material is composed of lanthanide ion and organic ligand;The lanthanide ion is Tb 3+ And Sm 3+ Two ions are combined with any one of Gd 3+ , Y 3+ , Lu 3+ And La 3+ When the luminescent color-changing metal organic framework material is dispersed in H2O and D2O, under the irradiation of ultraviolet light of 254nm excitation wavelength, two different luminescent colors are shown.Remove ultraviolet lamp, after solvent volatilization, no trace can be seen under daylight lamp.Again, after different solvents are added, color is shown again.This luminescent color-changing metal organic framework material can be used for information transmission and reproduction.

Description

Technical Field

[0001] This invention belongs to the field of optical anti-counterfeiting technology, and specifically relates to a deuterium oxide-activated luminescent color-changing metal-organic framework material, its preparation method, and its application. Background Technology

[0002] Traditional product packaging technologies, such as watermarks, stamps, and digital signature standards, are gradually being phased out due to their ease of replication. Fluorescent printed patterns, with their adjustable and designable emission characteristics, can provide a high level of security, effectively protecting valuable documents. However, traditional luminescent materials, such as dye molecules and quantum dots, while capable of producing multicolor emission, are limited in their practical application in the field of anti-counterfeiting due to their susceptibility to photobleaching and significant contamination problems.

[0003] Trivalent lanthanides are widely used in the construction of multimode emission platforms due to their unique 4f electron orbital structure and abundant energy levels. For example, Tb 3+ and Sm 3+ Lanthanide-doped fluorescent materials have been widely used in the development of green and red downconversion luminescent materials. Among the many modes of luminescence, lanthanide-doped fluorescent materials, lanthanide metal-organic frameworks (Ln-MOFs) have attracted much attention due to their unique framework structure, tunable pores, and high stability. The organic ligands of Ln-MOFs typically exhibit strong absorption in the ultraviolet region, thus enabling energy transfer and achieving efficient downconversion luminescence of lanthanide ions. Color changes can be achieved by adjusting the proportion of dopant ions. However, anti-counterfeiting measures for Ln-MOFs generally require external forces, such as high temperatures or pH levels, which severely hinders their development in anti-counterfeiting applications. The porous structure of Ln-MOFs allows for sufficient contact between rare earth ions and the solvent. By utilizing energy transfer between rare earth elements and the vibrational frequency fixed by the solvent, the emission color of Ln-MOFs can be altered, thereby achieving an anti-counterfeiting effect. Summary of the Invention

[0004] In response to the increasingly serious problem of counterfeiting, the present invention aims to design a lanthanide metal-organic framework optical anti-counterfeiting material. This lanthanide metal-organic framework optical anti-counterfeiting material is dispersed in H₂O or D₂O solvent, and displays information in different colors under ultraviolet light. After the ultraviolet light is removed and the solvent evaporates, no trace remains, thus meeting advanced anti-counterfeiting requirements.

[0005] To achieve the above-mentioned objectives, the technical solution adopted by this invention is: a deuterium oxide-activated luminescent color-changing metal-organic framework material, composed of lanthanide ions and organic ligands; wherein the lanthanide ions are Tb 3+ and Sm 3+ Two ions and Gd 3+ Y 3+ Lu 3+ and La3+ Any combination of the following; in mole ratio, Tb 3+ Sm 3+ Gd 3 Or Y 3+ Or Lu 3+ Or La 3+ = (0.4-0.45): (0.1-0.05): 0.5.

[0006] Furthermore, the organic ligand is selected from one of pyromellitic acid, terephthalic acid, isophthalic acid, and 2-aminoterephthalic acid.

[0007] A method for preparing a deuterium oxide-activated luminescent color-changing metal-organic framework material includes the following steps:

[0008] 1) Add lanthanide chloride and organic ligand to an organic solvent, sonicate to dissolve, then add sodium acetate and continue sonication to obtain a suspension; the lanthanide ion is Tb 3+ and Sm 3+ Two ions and Gd 3+ Y 3+ Lu 3+ and La 3+ Any combination of the following;

[0009] 2) Place the suspension in a reaction vessel with a polytetrafluoroethylene liner, and put it into a drying oven for hydrothermal reaction to obtain the precursor;

[0010] 3) The precursor was washed sequentially with N,N-dimethylformamide, anhydrous ethanol and deionized water to obtain a precipitate.

[0011] 4) After activating the obtained precipitate in methanol, wash it again with methanol and deionized water in sequence, dry it, grind it, and obtain the target product.

[0012] Further, in step 1), the organic solvent is N,N-dimethylformamide.

[0013] Furthermore, in step 1), the molar ratio is nitrate or chloride of lanthanide ions: organic ligand: N,N-dimethylformamide: sodium acetate = 1:0.5:(1.0-1.5):0.5.

[0014] Furthermore, in step 2), the hydrothermal reaction is carried out at a temperature of 120℃-160℃ for a duration of 12h-48h.

[0015] Furthermore, in step 4), the activation time is 6h-48h.

[0016] This invention provides the application of a deuterium oxide-activated luminescent color-changing metal-organic framework material as an anti-counterfeiting material in optical anti-counterfeiting.

[0017] Furthermore, the information recorded by the deuterium oxide-activated luminescent color-changing metal-organic framework material is displayed in different colors in H2O and D2O.

[0018] Furthermore, the deuterium oxide-activated luminescent color-changing metal-organic framework material displays green or yellow in H2O and yellow or orange in D2O.

[0019] The design principle of this invention is: the cause of color change is related to Tb. 3+ To Sm 3+ The energy difference and the coupling effect of solvent vibrations are related. Tb 3+ To Sm 3+ The energy difference matches the characteristic vibrational frequency of the deuterated hydroxyl group in D₂O, thereby reducing nonradiative transitions during energy transfer. This leads to increased Tb in heavy water. 3+ To Sm 3+ The energy transfer efficiency is higher in water than in sm, thus enhancing the Sm 3 + The red light component ultimately triggers the color-changing phenomenon, enabling the encryption and transmission of information.

[0020] The beneficial effects of this invention are:

[0021] 1. The deuterium oxide activated luminescent color-changing metal-organic framework material provided by this invention has a simple preparation method, inexpensive raw materials, stable optical properties, and can work in high temperature and high humidity environments, meeting the needs of advanced anti-counterfeiting.

[0022] 2. The deuterium oxide-activated luminescent color-changing metal-organic framework material provided by this invention can realize the encryption and transmission of information.

[0023] 3. The deuterium oxide-activated luminescent color-changing metal-organic framework material provided by this invention allows the information to be clearly seen on paper under ultraviolet light. After the ultraviolet light is removed and the solvent evaporates, no trace is visible on the paper. Upon re-addition of solvent, the information becomes clearly visible again under ultraviolet light. Attached Figure Description

[0024] Figure 1 For Tb 0.4 / Sm 0.1 @Gd 0.5 -An anti-counterfeiting diagram of MOFs.

[0025] Figure 2 For Tb 0.45 / Sm 0.05 @Gd 0.5 -An anti-counterfeiting diagram of MOFs. Detailed Implementation

[0026] Example 1: Deuterium oxide activated luminescent color-changing metal-organic framework material Tb 0.4 / Sm 0.1 @Gd 0.5 -MOFs

[0027] In this embodiment, the deuterium oxide-activated luminescent color-changing metal-organic framework material is composed of lanthanide ions (Tb). 3+ 、Sm 3+ and Gd 3+ Composed of organic ligands phenyltricarboxylic acid; Tb 3+ Sm 3+ Gd 3 = 0.4:0.1:0.5; Chemical formula composition: Tb 0.4 / Sm 0.1 @Gd 0.5 -MOFs.

[0028] I. Preparation method is as follows

[0029] Terbium chloride (0.1494 g, 0.4 mol), samarium chloride (0.0365 g, 0.1 mol), gadolinium chloride (0.1361 g, 0.5 mol), and trimesic acid (0.1051 g, 0.5 mol) were placed in a beaker. Then, N,N-dimethylformamide (100 mL, 1.3 mol) was added to the beaker, and the mixture was sonicated for 30 min to obtain a clear solution. Then, sodium acetate (0.1361 g, 0.5 mol) was added, and the mixture was sonicated for another 30 min to obtain a white suspension.

[0030] The obtained white suspension was placed into a 100 mL polytetrafluoroethylene-lined reaction vessel, which was then placed in a forced-air drying oven and subjected to hydrothermal reaction at 120 °C for 24 h. After the reaction was completed, the reaction vessel was allowed to stand for 24 h to obtain the precursor.

[0031] The obtained precursor was washed three times by centrifugation at 5000 r / min with N,N-dimethylformamide, anhydrous ethanol and deionized water to obtain a white precipitate.

[0032] The resulting white precipitate was activated in 50 mL of methanol, then washed three times successively with methanol and deionized water, dried at 60 °C for 24 h, and ground to obtain the target product, white powder Tb. 0.4 / Sm 0.1 @Gd 0.5 -MOFs.

[0033] II. Anti-counterfeiting applications

[0034] Tb 0.4 / Sm0.1 @Gd 0.5 - MOFs are dispersed in H2O to make luminescent ink, which is then used to draw a tree pattern on non-fluorescent white paper with a brush.

[0035] like Figure 1 As shown, the pattern shows no trace under sunlight, but under ultraviolet light, the green tree pattern is clearly visible. After removing the ultraviolet light, the paper is observed under sunlight, and still no trace is visible; this is the first layer of anti-counterfeiting. Next, a drop of heavy water is added to the pattern; under ultraviolet light, the tree clearly turns yellow. After removing the ultraviolet light, the paper is observed under sunlight, and still no trace is visible; this is the second layer of anti-counterfeiting.

[0036] Example 2: Deuterium oxide activated luminescent color-changing metal-organic framework material Tb 0.45 / Sm 0.05 @Gd 0.5 -MOFs

[0037] In this embodiment, the deuterium oxide-activated luminescent color-changing metal-organic framework material is composed of lanthanide ions (Tb). 3+ 、Sm 3+ and Gd 3+ Composed of organic ligands phenyltricarboxylic acid; Tb 3+ Sm 3+ Gd 3 = 0.45:0.05:0.5; Chemical formula composition: Tb 0.45 / Sm 0.05 @Gd 0.5 -MOFs.

[0038] I. Preparation method is as follows

[0039] Terbium chloride (0.1680 g, 0.45 mol), samarium chloride (0.0182 g, 0.05 mol), gadolinium chloride (0.1361 g, 0.5 mol), and trimesic acid (0.1051 g, 0.5 mol) were placed in a beaker. Then, N,N-dimethylformamide (100 mL, 1.3 mol) was added to the beaker, and the mixture was sonicated for 30 min to obtain a clear solution. Then, sodium acetate (0.1361 g, 0.5 mol) was added, and the mixture was sonicated for another 30 min to obtain a white suspension.

[0040] The obtained white suspension was placed into a 100 mL polytetrafluoroethylene-lined reaction vessel, which was then placed in a forced-air drying oven and subjected to hydrothermal reaction at 120 °C for 24 h. After the reaction was completed, the reaction vessel was allowed to stand for 24 h to obtain the precursor.

[0041] The obtained precursor was washed three times by centrifugation at 5000 r / min with N,N-dimethylformamide, anhydrous ethanol and deionized water to obtain a white precipitate.

[0042] The resulting white precipitate was activated in 50 mL of methanol, then washed three times successively with methanol and deionized water, dried at 60 °C for 24 h, and ground to obtain the target product, white powder Tb. 0.45 / Sm 0.05 @Gd 0.5 -MOFs.

[0043] II. Anti-counterfeiting applications

[0044] Tb 0.45 / Sm 0.05 @Gd 0.5 - MOFs are dispersed in H2O to make luminescent ink, which is then used to draw a tree pattern on non-fluorescent white paper with a brush.

[0045] like Figure 2 As shown, the pattern shows no trace under sunlight, but under ultraviolet light, the yellow tree pattern is clearly visible. After removing the ultraviolet light, the paper is observed under sunlight, and still no trace is visible; this is the first layer of anti-counterfeiting. Next, a drop of heavy water is added to the pattern; under ultraviolet light, the tree clearly turns orange. After removing the ultraviolet light, the paper is observed under sunlight, and still no trace is visible; this is the second layer of anti-counterfeiting.

[0046] Example 3: Deuterium oxide activated luminescent color-changing metal-organic framework material Tb 0.4 / Sm 0.1 @Y 0.5 -MOFs

[0047] The preparation method is the same as in Example 1, except that gadolinium chloride is replaced with yttrium chloride (0.1516 g, 0.5 mol), while all other conditions remain unchanged, to obtain the target product Tb. 0.4 / Sm 0.1 @Y 0.5 -MOFs.

[0048] Dispersing it in H2O and D2O to prepare luminescent ink still provides anti-counterfeiting protection.

[0049] Example 4: Deuterium oxide activated luminescent color-changing metal-organic framework material Tb 0.4 / Sm 0.1 @Lu 0.5 -MOFs

[0050] The preparation method is the same as in Example 1, except that gadolinium chloride is replaced with lutetium chloride (0.1947 g, 0.5 mol), while all other conditions remain unchanged, to obtain the target product Tb.0.4 / Sm 0.1 @Lu 0.5 -MOFs.

[0051] Dispersing it in H2O and D2O to prepare luminescent ink still provides anti-counterfeiting protection.

[0052] Example 5: Deuterium oxide activated luminescent color-changing metal-organic framework material Tb 0.4 / Sm 0.1 @La 0.5 -MOFs

[0053] The preparation method was the same as in Example 1, except that gadolinium chloride was replaced with lanthanum chloride (0.1336 g, 0.5 mol), while all other conditions remained unchanged, to obtain the target product Tb. 0.4 / Sm 0.1 @La 0.5 -MOFs.

[0054] Dispersing it in H2O and D2O to prepare luminescent ink still provides anti-counterfeiting protection.

[0055] Example 6: Deuterium oxide activated luminescent color-changing metal-organic framework material Tb 0.45 / Sm 0.05 @Y 0.5 -MOFs

[0056] The preparation method is the same as in Example 2, except that gadolinium chloride is replaced with yttrium chloride (0.1516 g, 0.5 mol), while all other conditions remain unchanged, to obtain the target product Tb. 0.45 / Sm 0.05 @Y 0.5 -MOFs.

[0057] Dispersing it in H2O and D2O to prepare luminescent ink still provides anti-counterfeiting protection.

[0058] Example 7: Deuterium oxide activated luminescent color-changing metal-organic framework material Tb 0.45 / Sm 0.05 @Lu 0.5 -MOFs

[0059] The preparation method is the same as in Example 2, except that gadolinium chloride is replaced with lutetium chloride (0.1947 g, 0.5 mol), while all other conditions remain unchanged, to obtain the target product Tb. 0.45 / Sm 0.05 @Lu 0.5 -MOFs.

[0060] Dispersing it in H2O and D2O to prepare luminescent ink still provides anti-counterfeiting protection.

[0061] Example 8: Deuterium oxide activated luminescent color-changing metal-organic framework material Tb 0.45 / Sm 0.05 @La 0.5 -MOFs

[0062] The preparation method is the same as in Example 2, except that gadolinium chloride is replaced with lanthanum chloride (0.1336 g, 0.5 mol), while all other conditions remain unchanged, to obtain the target product Tb. 0.45 / Sm 0.05 @La 0.5 -MOFs.

[0063] Dispersing it in H2O and D2O to prepare luminescent ink still provides anti-counterfeiting protection.

Claims

1. The application of a deuterium oxide-activated luminescent color-changing metal-organic framework material as an anti-counterfeiting material in optical anti-counterfeiting, characterized in that, The deuterium oxide-activated luminescent color-changing metal-organic framework material exhibits green or yellow in H₂O and yellow or orange in D₂O; the deuterium oxide-activated luminescent color-changing metal-organic framework material is composed of lanthanide ions and organic ligands; the lanthanide ions are Tb 3+ and Sm 3+ Two ions and Gd 3+ Y 3+ Lu 3+ and La 3+ Any combination of the following; in mole ratio, Tb 3+ Sm 3+ Gd 3 Or Y 3+ Or Lu 3+ Or La 3+ = (0.4-0.45): (0.1-0.05): 0.5; The organic ligand is selected from one of pyromellitic acid, terephthalic acid, isophthalic acid and 2-aminoterephthalic acid.

2. The application according to claim 1, characterized in that, The preparation method of the deuterium oxide-activated luminescent color-changing metal-organic framework material includes the following steps: 1) Add the chloride salt and organic ligand of lanthanide ions to an organic solvent, dissolve by sonication, add sodium acetate, and continue sonication to obtain a suspension; the lanthanide ions are Tb 3+ and Sm 3+ Two ions and Gd 3+ Y 3+ Lu 3+ and La 3+ Any combination of the following; 2) Place the suspension in a reaction vessel with a polytetrafluoroethylene liner, and put it into a drying oven for hydrothermal reaction to obtain the precursor; 3) The precursor was washed sequentially with N,N-dimethylformamide, anhydrous ethanol and deionized water to obtain a precipitate; 4) After activating the obtained precipitate in methanol, wash it again with methanol and deionized water in sequence, dry it, grind it, and obtain the target product.

3. The application according to claim 2, characterized in that, In step 1), the organic solvent is N,N-dimethylformamide.

4. The application according to claim 3, characterized in that, In step 1), the molar ratio is lanthanide chloride : organic ligand : N,N-dimethylformamide : sodium acetate = 1 : 0.5 : (1.0-1.5) : 0.

5.

5. The application according to claim 2, characterized in that, In step 2), the hydrothermal reaction is carried out at a temperature of 120℃-160℃ for a duration of 12h-48h.

6. The application according to claim 2, characterized in that, In step 4), the activation time is 6h-48h.

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