CN113024570A - Spiropyran-loaded metal-organic framework photochromic material and preparation method thereof - Google Patents

Spiropyran-loaded metal-organic framework photochromic material and preparation method thereof Download PDF

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CN113024570A
CN113024570A CN202110300954.4A CN202110300954A CN113024570A CN 113024570 A CN113024570 A CN 113024570A CN 202110300954 A CN202110300954 A CN 202110300954A CN 113024570 A CN113024570 A CN 113024570A
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spiropyran
photochromic material
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mof
organic framework
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杨玉慧
李宇晴
陈义龙
何哲
王朝晖
何钧照
江国华
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Zhejiang University of Technology ZJUT
Zhejiang Sci Tech University ZSTU
Zhejiang University of Science and Technology ZUST
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    • C07—ORGANIC CHEMISTRY
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    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
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    • C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
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Abstract

The invention discloses a spiropyran-loaded metal-organic framework photochromic material and a preparation method thereof, belonging to the technical field of organic solid photochromic materials. The method loads the spiropyran in a lanthanide metal-organic frame in a liquid-assisted grinding or solvent adsorption mode to prepare the photochromic material, and the photochromic material can accurately read and hide recorded information only by alternately using ultraviolet light and visible light irradiation within a very short time, so that double anti-counterfeiting is realized, and meanwhile, the photochromic material has very high fatigue resistance and is an attractive next-generation intelligent information anti-counterfeiting protection material.

Description

Spiropyran-loaded metal-organic framework photochromic material and preparation method thereof
Technical Field
The invention relates to the technical field of organic solid photochromic materials, in particular to a spiropyran-loaded metal-organic framework photochromic material and a preparation method thereof.
Background
Photoluminescent materials have received much attention because of their excellent properties in storage, information recording and protection, information security, and the like.
However, the practical application of the static luminescent output material in the aspect of information anti-counterfeiting has certain disadvantages, because the information recorded therein is directly exposed to visible light or near infrared light and ultraviolet light, and the information can not be hidden under the excitation of light. The development of a novel luminescent material with a dual-emission function can well solve the problem, the material can change the internal structure thereof through the excitation of light, thereby realizing the change of luminous output, enabling the information written therein to be subjected to visible and invisible conversion, improving the safety of the information, and being considered as an ideal material for preventing the information from being tampered and plagiarized. Typically, the information written therein is hidden and only visible when needed, thus providing unforgeable protection for the information.
In recent years, the development of anti-counterfeiting materials has attracted a great deal of attention in order to prevent the adverse effects on economy and information security of more and more counterfeit products on the market. However, the conventional method has an insignificant effect, and some luminescent materials rely on continuous addition of reactants for their luminescent output, which causes environmental pollution on one hand, and on the other hand, some reactions are irreversible, and the luminescent output after change cannot be recovered after external light excitation, so that information is exposed to the outside and the expected anti-counterfeit effect cannot be achieved. In contrast, a material with double color-changing performance is a candidate material with great potential, and under alternate illumination, reversible visible and invisible conversion of multiple information modes can be realized, and recorded information can be accurately hidden and read, so that the aim of double anti-counterfeiting is fulfilled, and the material is an attractive next-generation intelligent information anti-counterfeiting protection material.
Disclosure of Invention
The invention aims to provide a spiropyran-loaded metal-organic framework photochromic material and a preparation method thereof, which are used for solving the problems in the prior art, so that the photochromic material can realize reversible visible and invisible conversion of multiple information modes only under the alternate irradiation of ultraviolet light and visible light, and the aim of double anti-counterfeiting is fulfilled.
In order to achieve the purpose, the invention provides the following scheme:
one of the purposes of the invention is to provide a photochromic material, which is a spiropyran-loaded lanthanide metal-organic framework photochromic material.
Further, the lanthanide metal is one of europium, terbium, cerium or dysprosium.
Further, the ligand of the lanthanide metal-organic framework is terephthalic acid.
Another object of the present invention is to provide a method for preparing the above photochromic material, comprising the following steps:
the spiropyran is loaded in a lanthanide metal-organic framework by means of liquid-assisted grinding or solvent adsorption.
Further, when a liquid-assisted grinding mode is adopted, the preparation method comprises the following steps:
and (3) grinding the lanthanide metal-organic framework and the spiropyran in the presence of toluene, and drying after grinding to obtain the photochromic material.
Further, the mass ratio of the lanthanide metal-organic framework to the spiropyran is 1-2: 1.
Further, the grinding time is 30min-1h, and the temperature of the drying treatment is room temperature.
Further, when a solvent adsorption mode is adopted, the preparation method comprises the following steps:
(1) preparing a spiropyran toluene solution with the concentration of 0.1-0.3 mol/L;
(2) mixing the lanthanide metal-organic framework and the spiropyran toluene solution, standing at room temperature, and drying to remove the solvent after standing to obtain the photochromic material.
Further, the mass-to-volume ratio of the lanthanide metal-organic framework to the spiropyran toluene solution is 200 mg: 0.4-1.2 mL.
The invention also aims to provide an application of the photochromic material in information anti-counterfeiting.
Lanthanide ions have the characteristics of linear emission spectrum, high color purity, long fluorescence life and the like, and are selected to be used as metal ions for assembly, the emission spectrum of the metal ions is overlapped with the absorption spectrum of cyanine (MC) after ring opening of the spiropyran, the distance between donor ions and acceptor cyanine (MC) is proper, energy transfer from the lanthanide ions of the donor to the acceptor (MC) can occur after ultraviolet irradiation, and the photochromic performance of the spiropyran can be greatly improved.
The open and closed ring isomerization of the photo-induced molecular spiropyran modulates the process of photochromic energy transfer between the spiropyran acceptor and the lanthanide donor, respectively, resulting in a reversible fluorescence switch of the lanthanide luminescence center in the Ln-MOF host. The photoresponsive host-guest system can realize reversible visible and invisible conversion of multiple information modes only under the alternate irradiation of ultraviolet light and visible light.
The invention discloses the following technical effects:
the invention utilizes the regular and stable holes of lanthanide series metal-organic framework material ((Ln-MOF) to load organic photochromic molecules in a host-guest doping mode3+) The energy transfer process between the fluorescent material and the spiropyran realizes the conversion of the fluorescence color of the material; on the other hand, the spiropyran molecules can have enough space in a solid state to carry out ring-opening-ring-closing reaction by virtue of the protection effect of the framework material, so that the stability and the fatigue resistance of the spiropyran molecules are improved.
The open and closed ring isomerization of the photo-induced molecular spiropyran modulates the process of photochromic energy transfer between the spiropyran acceptor and the lanthanide donor, respectively, resulting in a reversible fluorescence switch of the lanthanide luminescence center in the Ln-MOF host. The photoresponsive host-guest system can realize reversible visible and invisible conversion of multiple information modes only under the alternate irradiation of ultraviolet light and visible light.
The system of the invention can accurately read and hide the recorded information only by alternately irradiating with ultraviolet light and visible light within a very short time, thereby realizing the double anti-counterfeiting purpose, simultaneously having very high fatigue resistance and being an attractive next-generation intelligent information anti-counterfeiting protection material.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a graph showing the UV absorption spectrum of a sample SP @ Eu-MOF-2 powder in example 2 of the present invention;
FIG. 2 is a graph showing the UV absorption spectrum of a sample SP @ Eu-MOF-2 thin film in example 2 of the present invention;
FIG. 3 is a graph showing the cycle of 50 recoveries of SP @ Eu-MOF-2 film samples in example 2 of the present invention by 365nm UV light irradiation;
FIG. 4 is a fluorescence emission spectrum of a sample of SP @ Eu-MOF-5 powder prepared in example 5 of the present invention before and after UV irradiation.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The structure of the ligand phthalic acid in the lanthanide series metal-organic framework (Ln-MOF) is as follows:
Figure BDA0002986251630000051
the spiropyran has the structure:
Figure BDA0002986251630000052
example 1
(1) Preparation of europium-based Metal-organic frameworks (Eu-MOF)
Terephthalic acid (300mg, 1.8mmol) and europium nitrate hexahydrate (1.608g, 3.6mmol) are added into a 250mL reaction bottle at room temperature, then N, N-dimethylformamide (180mL), absolute ethyl alcohol (12mL) and deionized water (16.2mL) are added into the reaction bottle, the reaction bottle is heated at 80 ℃ for 48 hours, after the reaction is finished, the reaction bottle is slowly cooled to room temperature at the speed of 10 ℃ per hour, the reaction bottle is repeatedly washed with N, N-dimethylformamide for three times, and the white solid powder is obtained by centrifugal drying. I.e. a europium-based metal-organic framework (Eu-MOF).
(2) Spiropyran (SP-CH)3) Supported Eu-MOF (liquid assisted grinding)
Eu-MOF (50mg) and SP-CH3(25mg) in a ratio of 2:1, placing the mixture into an agate mortar, adding 0.2mL of toluene solution into the agate mortar, grinding until the solvent is volatilized, then adding 0.2mL of toluene solution, continuing grinding, continuously repeating the steps, grinding for 30 minutes, finally washing with toluene for three times, and drying at room temperature. Obtaining a sample SP @ Eu-MOF-1.
Example 2
(1) Preparation of europium-based Metal-organic frameworks (Eu-MOF)
The preparation method is the same as example 1.
(2) Spiropyran (SP-CH)3) Supported Eu-MOF
The preparation method is the same as example 1, except that the grinding time is 1 hour, and a sample SP @ Eu-MOF-2 is obtained.
In the embodiment, the spiropyran molecules are loaded into a framework material in a liquid-assisted grinding mode, a loaded SP @ Eu-MOF-2 solid powder sample is brown, and the color of the sample is changed from brown to purple after the sample is irradiated for 20s by ultraviolet light with the wavelength of 365 nm; after standing for 15min under visible light, the color is completely changed from purple to brown, and the good color change is still realized after 50 times of repeated circulation.
FIG. 1 is a graph of solid ultraviolet absorption before and after ultraviolet light irradiation of a SP @ Eu-MOF-2 powder sample, with the ordinate being ultraviolet absorption intensity and the abscissa being wavelength of ultraviolet scanning; as can be seen from FIG. 1, when the sample was irradiated with UV light having a wavelength of 365nm, the position of the absorption peak was clearly red-shifted and the peak was gradually increased, which indicates that the ring-opening reaction of the spiropyran molecules in the frame was able to occur by UV light irradiation.
The preparation method comprises the following steps of (1) doping SP @ Eu-MOF-2 solid sample powder and Polydimethylsiloxane (PDMS) in a proportion of 0.2%, putting the mixture into a mold, drying the mixture in a vacuum drying oven for 1 hour, heating the mixture to 80 ℃, cooling the mixture to room temperature after a film is solidified, and further verifying the application effect of SP @ Eu-MOF-2 in the anti-counterfeiting label: after the cured film sample is irradiated for 20s by ultraviolet light with the wavelength of 365nm, the color is changed from transparent color to purple, the response time is quicker compared with that of other films, the color-changed sample is heated for 15min at 80 ℃ and completely reverts to transparent color, and the film sample still has better color change after being repeatedly cycled for 50 times.
FIG. 2 is a graph of the solid UV absorption spectrum before and after UV irradiation of a film made by mixing solid sample powder with transparent Polydimethylsiloxane (PDMS) in a ratio of 0.2%, the ordinate is UV absorption intensity, and the abscissa is the wavelength of UV scanning; as can be seen from FIG. 2, the film sample has an absorption peak at 550nm, and the peak value of the absorption peak is significantly increased when the film is irradiated by ultraviolet light with a wavelength of 365nm, which indicates that the spiropyran molecules can undergo a ring-opening reaction in the frame by the irradiation of the ultraviolet light, and the Polydimethylsiloxane (PDMS) does not affect the performance of the sample.
FIG. 3 is a cycle chart of 50 times of recovery of a film sample after being irradiated by ultraviolet light with a wavelength of 365nm, and it can be seen that the sample has good luminescence property and stable cycle property.
This example successfully loaded spiropyran molecules into the Eu-MOF framework by a liquid-assisted milling process, on the one hand by europium ions (Eu)3+) The process of transferring energy to the cyanine (MC) part realizes the change of the fluorescence color of the material, realizes the double fluorescence switch of the material through the alternate irradiation of ultraviolet light and visible light, and achieves the double anti-counterfeiting purpose; on the other hand, the spiropyran molecules can have enough space in a solid state to carry out ring-opening-ring-closing reaction by virtue of the protection effect of the framework material, so that the stability and the fatigue resistance of the spiropyran molecules are improved. Through the mixing of the solid sample and PDMS, the fast response under ultraviolet light can be realized, and the fatigue resistance of the sample is improved.
Example 3
(1) Preparation of europium-based Metal-organic frameworks (Eu-MOF)
The preparation method is the same as example 1.
(2) Spiropyran (SP-CH)3) Supported Eu-MOF
The preparation method was the same as example 1, except that Eu-MOF (50mg) and SP-CH3(50mg) 1: 1 to obtain a sample SP @ Eu-MOF-3.
Example 4
(1) Preparation of europium-based Metal-organic frameworks (Eu-MOF)
The preparation method is the same as example 1.
(2) Spiropyran (SP-CH)3) Supported Eu-MOF
The preparation method was the same as example 1, except that Eu-MOF (50mg) and SP-CH3(50mg) 1: 1, and grinding for 1h to obtain a sample SP @ Eu-MOF-4.
Example 5
(1) Preparation of europium-based Metal-organic frameworks (Eu-MOF)
The preparation method is the same as example 1.
(2) Spiropyran (SP-CH)3) Supported Eu-MOF (solvent adsorption method)
Weighing SP-CH3(32mg) was placed in a glass bottle, and toluene (1mL) was further added to prepare a spiropyran solution having a concentration of 0.1 mol/L. Eu-MOF (200mg) was weighed into a 10mL glass bottle, a spiropyran solution (0.4mL) was weighed into the glass bottle, left to stand under visible light at room temperature for 4 hours, then dried to remove the solvent, finally washed three times with toluene and dried at room temperature. Obtaining a sample SP @ Eu-MOF-5.
In the embodiment, the spiropyran molecules are loaded into the frame material in a solvent adsorption mode, the loaded solid powder sample is brown, and the color of the sample begins to change from brown to purple after the sample is irradiated for 20 seconds by ultraviolet light with the wavelength of 365 nm; after standing for 15min under visible light, the color is completely changed from purple to brown, and the good color change is still realized after 50 times of repeated circulation.
The solid sample powder and Polydimethylsiloxane (PDMS) are doped into a mold according to the proportion of 0.2%, the mixture is dried for 1 hour in a vacuum drying oven, the temperature is 80 ℃, after the film is solidified, the mixture is cooled to room temperature, the color of the solidified sample begins to change from transparent color to purple after being irradiated by ultraviolet light with the wavelength of 365nm for 20 seconds, the color-changed sample is heated for 15min at the temperature of 80 ℃ and completely reverts to transparent color, and the sample still has good color change after being repeatedly cycled for 50 times.
FIG. 4 is a fluorescence emission spectrum of SP @ Eu-MOF-5 powder before and after ultraviolet light irradiation, wherein the ordinate is fluorescence intensity and the abscissa is fluorescence scanning wavelength; as can be seen from FIG. 4, there is an emission peak of europium ion at 620nm and an emission peak of spiropyran at 650 nm; after the ultraviolet irradiation with the wavelength of 365nm, the emission peak intensity of europium ions at 620nm is obviously reduced, and the emission peak intensity of spiropyran at 650nm is increased and has obvious red shift, which shows that after the ultraviolet irradiation, europium ions in an Eu-MOF framework can transfer energy to spiropyran molecules, so that the luminous performance of the spiropyran molecules is obviously improved.
In this example, the spiropyran molecules are successfully loaded into the Eu-MOF framework by a solvent adsorption method, and on the one hand, europium ions (Eu) are utilized3+) The process of transferring energy to the cyanine (MC) part realizes the change of the fluorescence color of the material, realizes the double fluorescence switch of the material through the alternate irradiation of ultraviolet light and visible light, and achieves the double anti-counterfeiting purpose; on the other hand, the spiropyran molecules can have enough space in a solid state to carry out ring-opening-ring-closing reaction by virtue of the protection effect of the framework material, so that the stability and the fatigue resistance of the spiropyran molecules are improved. Through the mixing of the solid sample and PDMS, the fast response under ultraviolet light can be realized, and the fatigue resistance of the sample is improved.
Example 6
(1) Preparation of europium-based Metal-organic frameworks (Eu-MOF)
The preparation method is the same as example 1.
(2) Spiropyran (SP-CH)3) Supported Eu-MOF
The preparation method is the same as example 5, except that the spiropyran solution is added in two times, and 0.4mL of the spiropyran solution is added each time, so as to obtain a sample SP @ Eu-MOF-6.
Example 7
(1) Preparation of europium-based Metal-organic frameworks (Eu-MOF)
The preparation method is the same as example 1.
(2) Spiropyran (SP-CH)3) Supported Eu-MOF
The preparation method is the same as that of example 5, except that 0.4mL of the spiropyran solution is added in three times, and 0.4mL of the spiropyran solution is added each time, so as to obtain a sample SP @ Eu-MOF-7.
Example 8
(1) Preparation of europium-based Metal-organic frameworks (Eu-MOF)
The preparation method is the same as example 1.
(2) Spiropyran (SP-CH)3) Supported Eu-MOF
The preparation method is the same as example 5, except that 1.2mL of the spiropyran solution is added at a time to obtain a sample SP @ Eu-MOF-8.
Example 9
(1) Preparation of a terbium-based Metal-organic framework (Tb-MOF)
At room temperature, terephthalic acid (300mg, 1.8mmol) and terbium nitrate hexahydrate (1.608g, 3.6mmol) are added into a 250mL reaction bottle, N-dimethylformamide (180mL), absolute ethyl alcohol (12mL) and deionized water (16.2mL) are added into the reaction bottle, the reaction bottle is heated at 80 ℃ for 48 hours, after the reaction is finished, the reaction bottle is slowly cooled to room temperature at the speed of 10 ℃ per hour, the reaction bottle is repeatedly washed with the N, N-dimethylformamide for three times, and the white solid powder, namely terbium-based metal-organic framework (Tb-MOF), is obtained through centrifugal drying.
(2) Spiropyran (SP-CH)3) Supported Tb-MOF (liquid auxiliary grinding)
Tb-MOF (50mg) and SP-CH3(25mg) in a ratio of 2:1, placing the mixture into an agate mortar, adding 0.2mL of toluene solution into the agate mortar, grinding until the solvent is volatilized, then adding 0.2mL of toluene solution, continuing grinding, continuously repeating the steps, grinding for 1 hour, finally washing with toluene for three times, and drying at room temperature. Obtaining a sample SP @ Tb-MOF-2.
The loaded solid powder sample is brown, and the color of the sample begins to change from brown to purple after the sample is irradiated by ultraviolet light with the wavelength of 365nm for 20 s; after standing for 15min under visible light, the color changed from purple to brown completely.
The solid sample powder and Polydimethylsiloxane (PDMS) are doped into a mold according to the proportion of 0.2%, the mixture is dried for 1 hour in a vacuum drying oven, the temperature is 80 ℃, after the film is solidified, the mixture is cooled to room temperature, the color of the solidified sample begins to change from transparent color to purple after being irradiated by ultraviolet light with the wavelength of 365nm for 20 seconds, the color-changed sample is heated for 15min at the temperature of 80 ℃ and completely reverts to transparent color, and the sample still has good color change after being repeatedly cycled for 50 times.
Example 10
(1) Preparation of a terbium-based Metal-organic framework (Tb-MOF)
The preparation method is the same as example 3.
(2) Spiropyran (SP-CH)3) Supported Tb-MOF (solvent adsorption)
Weighing SP-CH3(32mg) was placed in a glass bottle, and toluene (1mL) was further added to prepare a spiropyran solution having a concentration of 0.1 mol/L. Tb-MOF (200mg) was weighed into a 10mL glass vial, then the spiropyran solution (0.4mL) was weighed into a glass vial, allowed to stand at room temperature for 4 hours, then placed in a vacuum oven for drying to remove the solvent, and finally washed three times with toluene and dried at room temperature. Obtaining a sample SP @ Tb-MOF-5.
The loaded solid powder sample is brown, and the color of the sample begins to change from brown to purple after the sample is irradiated by ultraviolet light with the wavelength of 365nm for 20 s; after standing for 15min under visible light, the color is completely changed from purple to brown, and the good color change is still realized after 50 times of repeated circulation.
The solid sample powder and Polydimethylsiloxane (PDMS) are doped into a mold according to the proportion of 0.2%, the mixture is dried for 1 hour in a vacuum drying oven, the temperature is 80 ℃, after the film is solidified, the mixture is cooled to room temperature, the color of the solidified sample begins to change from transparent color to purple after being irradiated by ultraviolet light with the wavelength of 365nm for 20 seconds, the color-changed sample is heated for 15min at the temperature of 80 ℃ and completely reverts to transparent color, and the sample still has good color change after being repeatedly cycled for 50 times.
Example 11
(1) Preparation of cerium-based Metal-organic frameworks (Ce-MOF)
At room temperature, adding terephthalic acid (300mg, 1.8mmol) and cerous nitrate hexahydrate (1.608g, 3.6mmol) into a 250mL reaction bottle, adding N, N-dimethylformamide (180mL), absolute ethyl alcohol (12mL) and deionized water (16.2mL) into the reaction bottle, heating at 80 ℃ for 48 hours, slowly cooling to room temperature at the speed of 10 ℃ per hour after the reaction is finished, repeatedly washing with N, N-dimethylformamide for three times, and centrifugally drying to obtain white solid powder, namely the cerium-based metal-organic framework (Ce-MOF) preparation.
(2) Spiropyran (SP-CH)3) Supported Ce-MOF (liquid assisted grinding)
Ce-MOF (50mg) and SP-CH3(25mg) in a ratio of 2:1, placing the mixture into an agate mortar, adding 0.2mL of toluene solution into the agate mortar, grinding until the solvent is volatilized, then adding 0.2mL of toluene solution, continuing grinding, continuously repeating the steps, grinding for 1 hour, finally washing with toluene for three times, and drying at room temperature. Obtaining a sample SP @ Ce-MOF-2.
The loaded solid powder sample is brown, and the color of the sample begins to change from brown to purple after the sample is irradiated by ultraviolet light with the wavelength of 365nm for 20 s; after standing for 15min under visible light, the color changed from purple to brown completely.
The solid sample powder and Polydimethylsiloxane (PDMS) are doped into a mold according to the proportion of 0.2%, the mixture is dried for 1 hour in a vacuum drying oven, the temperature is 80 ℃, after the film is solidified, the mixture is cooled to room temperature, the color of the solidified sample begins to change from transparent color to purple after being irradiated by ultraviolet light with the wavelength of 365nm for 20 seconds, the color-changed sample is heated for 15min at the temperature of 80 ℃ and completely reverts to transparent color, and the sample still has good color change after being repeatedly cycled for 50 times.
Example 12
(1) Preparation of cerium-based Metal-organic frameworks (Ce-MOF)
The preparation method is the same as example 11.
(2) Spiropyran (SP-CH)3) Supported Ce-MOF (solvent adsorption)
Weighing SP-CH3(32mg) was placed in a glass bottle, and toluene (1mL) was further added to prepare a spiropyran solution having a concentration of 0.1 mol/L. Ce-MOF (200mg) was weighed into a 10mL glass vial, and then a spiropyran solution (0.4 mg) was weighed outmL) was left to stand in a glass bottle at room temperature for 4 hours, and then put into a vacuum oven to be dried to remove the solvent, and finally washed three times with toluene and dried at room temperature. Obtaining a sample SP @ Ce-MOF-5.
The loaded solid powder sample is brown, and the color of the sample begins to change from brown to purple after the sample is irradiated by ultraviolet light with the wavelength of 365nm for 20 s; after standing for 15min under visible light, the color is completely changed from purple to brown, and the good color change is still realized after 50 times of repeated circulation.
The solid sample powder and Polydimethylsiloxane (PDMS) are doped into a mold according to the proportion of 0.2%, the mixture is dried for 1 hour in a vacuum drying oven, the temperature is 80 ℃, after the film is solidified, the mixture is cooled to room temperature, the color of the solidified sample begins to change from transparent color to purple after being irradiated by ultraviolet light with the wavelength of 365nm for 20 seconds, the color-changed sample is heated for 15min at the temperature of 80 ℃ and completely reverts to transparent color, and the sample still has good color change after being repeatedly cycled for 50 times.
Example 13
(1) Preparation of dysprosium-based Metal-organic frameworks (Dy-MOF)
At room temperature, adding terephthalic acid (300mg, 1.8mmol) and dysprosium nitrate hexahydrate (1.608g, 3.6mmol) into a 250mL reaction bottle, adding N, N-dimethylformamide (180mL), absolute ethyl alcohol (12mL) and deionized water (16.2mL) into the reaction bottle, heating at 80 ℃ for 48 hours, slowly cooling to room temperature at the speed of 10 ℃ per hour after the reaction is finished, repeatedly washing with N, N-dimethylformamide for three times, and centrifugally drying to obtain white solid powder, namely dysprosium-based metal organic framework (Dy-MOF).
(2) Spiropyran (SP-CH)3) Supported Dy-MOF (liquid auxiliary grinding)
Dy-MOF (50mg) and SP-CH3(25mg) in a ratio of 2:1, placing the mixture into an agate mortar, adding 0.2mL of toluene solution into the agate mortar, grinding until the solvent is volatilized, then adding 0.2mL of toluene solution, continuing grinding, continuously repeating the steps, grinding for 1 hour, finally washing with toluene for three times, and drying at room temperature. Obtaining a sample SP @ Dy-MOF-2.
The loaded solid powder sample is brown, and the color of the sample begins to change from brown to purple after the sample is irradiated by ultraviolet light with the wavelength of 365nm for 20 s; after standing for 15min under visible light, the color changed from purple to brown completely.
The solid sample powder and Polydimethylsiloxane (PDMS) are doped into a mold according to the proportion of 0.2%, the mixture is dried for 1 hour in a vacuum drying oven, the temperature is 80 ℃, after the film is solidified, the mixture is cooled to room temperature, the color of the solidified sample begins to change from transparent color to purple after being irradiated by ultraviolet light with the wavelength of 365nm for 20 seconds, the color-changed sample is heated for 15min at the temperature of 80 ℃ and completely reverts to transparent color, and the sample still has good color change after being repeatedly cycled for 50 times.
Example 14
(1) Preparation of dysprosium-based Metal-organic frameworks (Dy-MOF)
The preparation method is the same as example 13.
(2) Spiropyran (SP-CH)3) Supported Dy-MOF
Weighing SP-CH3(32mg) was placed in a glass bottle, and toluene (1mL) was further added to prepare a spiropyran solution having a concentration of 0.1 mol/L. Dy-MOF (200mg) was weighed into a 10mL glass bottle, then a spiropyran solution (0.4mL) was weighed into a glass bottle, allowed to stand at room temperature for 4 hours, then placed in a vacuum oven for drying to remove the solvent, and finally washed three times with toluene and dried at room temperature. Obtaining a sample SP @ Dy-MOF-5.
The loaded solid powder sample is brown, and the color of the sample begins to change from brown to purple after the sample is irradiated by ultraviolet light with the wavelength of 365nm for 20 s; after standing for 15min under visible light, the color is completely changed from purple to brown, and the good color change is still realized after 50 times of repeated circulation.
The solid sample powder and Polydimethylsiloxane (PDMS) are doped into a mold according to the proportion of 0.2%, the mixture is dried for 1 hour in a vacuum drying oven, the temperature is 80 ℃, after the film is solidified, the mixture is cooled to room temperature, the color of the solidified sample begins to change from transparent color to purple after being irradiated by ultraviolet light with the wavelength of 365nm for 20 seconds, the color-changed sample is heated for 15min at the temperature of 80 ℃ and completely reverts to transparent color, and the sample still has good color change after being repeatedly cycled for 50 times.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (10)

1. The photochromic material is a spiropyran-loaded lanthanide metal-organic framework photochromic material.
2. The photochromic material of claim 1 wherein the lanthanide metal is one of europium, terbium, cerium or dysprosium.
3. The photochromic material of claim 1 wherein the ligand of the lanthanide metal-organic framework is terephthalic acid.
4. A process for the preparation of a photochromic material according to any one of claims 1 to 3, comprising the following steps:
the spiropyran is loaded in a lanthanide metal-organic framework by means of liquid-assisted grinding or solvent adsorption.
5. The method for preparing the photochromic material according to claim 4, wherein when the liquid-assisted grinding mode is adopted, the method comprises the following steps:
and (3) grinding the lanthanide metal-organic framework and the spiropyran in the presence of toluene, and drying after grinding to obtain the photochromic material.
6. The method for preparing a photochromic material according to claim 5, wherein the mass ratio of the lanthanide metal-organic framework to the spiropyran is 1-2: 1.
7. The method for preparing a photochromic material according to claim 5, wherein the grinding time is 30min to 1h, and the temperature of the drying treatment is room temperature.
8. The method for preparing the photochromic material according to claim 4, wherein when the solvent adsorption method is adopted, the method comprises the following steps:
(1) preparing a spiropyran toluene solution with the concentration of 0.1-0.3 mol/L;
(2) mixing the lanthanide metal-organic framework and the spiropyran toluene solution, standing at room temperature, and drying to remove the solvent after standing to obtain the photochromic material.
9. The method for preparing a photochromic material according to claim 8, wherein the mass-to-volume ratio of the lanthanide metal-organic framework to the spiropyran toluene solution is 200 mg: 0.4-1.2 mL.
10. Use of a photochromic material according to any one of claims 1 to 3 for the prevention of counterfeiting of information.
CN202110300954.4A 2021-03-22 2021-03-22 Spiropyran-loaded metal-organic framework photochromic material and preparation method thereof Pending CN113024570A (en)

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CN114479825A (en) * 2022-02-22 2022-05-13 浙江大学 Dye/metal-organic framework composite material for anti-counterfeiting and information encryption and preparation method thereof
CN115779866A (en) * 2022-11-21 2023-03-14 盐城工学院 Spiropyran functionalized photoresponse adsorption material and preparation method and application thereof

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CN112409846A (en) * 2020-11-24 2021-02-26 陕西科技大学 Photochromic ink-jet printable aqueous fluorescent ink and preparation method thereof
CN112458795A (en) * 2020-11-24 2021-03-09 陕西科技大学 Photochromic fluorescent nano-paper based on lanthanide metal organic framework and preparation method thereof

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CN112409846A (en) * 2020-11-24 2021-02-26 陕西科技大学 Photochromic ink-jet printable aqueous fluorescent ink and preparation method thereof
CN112458795A (en) * 2020-11-24 2021-03-09 陕西科技大学 Photochromic fluorescent nano-paper based on lanthanide metal organic framework and preparation method thereof

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CN114479825A (en) * 2022-02-22 2022-05-13 浙江大学 Dye/metal-organic framework composite material for anti-counterfeiting and information encryption and preparation method thereof
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