Photocatalyst fluorescent ink

Abstract

The invention discloses photocatalyst fluorescent ink, and relates to the technical field of ink. According to the invention, the self-made fluorescent agent is frozen into microspheres, and titanium dioxide is adsorbed on the surface of the self-made fluorescent agent by using plasma, electrostatic spraying and microwaves, so that the stability of the ink is improved; then, through low-temperature plasma assisted radio frequency magnetron sputtering, cerium oxide is coordinated and chelated on the surfaces of the titanium dioxide microspheres, so that the visible light activity of titanium dioxide is improved, and ink can be catalytically degraded under visible light; wherein the self-made fluorescent agent is prepared from veratrone, pyrenecarboxaldehyde and boron trifluoride, so that the ink can display patterns only under infrared wavelength irradiation, is not easy to decompose by illumination under long-time infrared irradiation, and has better light stability. The photocatalyst fluorescent ink prepared by the invention has the effects of good confidentiality, light stability and degradability.

Description

Technical Field

[0001] This invention relates to the field of ink technology, specifically to a photocatalytic fluorescent ink. Background Technology

[0002] Information security has long been a crucial issue for nations, businesses, and individuals. Paper and ink have been an essential medium for transmitting information throughout history. Although network technology is developing rapidly and many documents and information are transmitted and stored online, important or even confidential documents are still often printed or handwritten in many situations and by certain organizations.

[0003] Protecting the contents of confidential paper documents from theft has become a crucial issue. Currently, the main protective measures are invisible ink and document shredding. While document shredding is simple, it involves significant waste, increases company costs, and poses a certain degree of environmental harm. Invisible inks on the market primarily develop color under stimulation such as heating or acid / alkali solutions. Although they achieve an invisible and confidential effect, once stolen, they cannot disappear before being copied and distributed. Therefore, this invention utilizes photocatalytic technology to synthesize an ink that can be decomposed and faded by visible light, for use when writing confidential documents, thereby minimizing the possibility of information leakage. Summary of the Invention

[0004] The purpose of this invention is to provide a photocatalytic fluorescent ink and its preparation method to solve the problems existing in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a method for preparing photocatalytic fluorescent ink, characterized by mainly including the following preparation steps: (1) Chalcone compound was prepared by mixing veratrone and pyrene formaldehyde, and a self-made fluorescent agent was prepared by adding nitromethane and boron trifluoride ether; (2) Place the self-made fluorescent agent in a spray freeze dryer, spray it out, keep it at -45℃ for 30~40min, raise the temperature to -20℃ at a rate of 1~3℃ / min, and keep it at the temperature for 50~60min to obtain the self-made fluorescent agent microspheres; (3) Place the self-made fluorescent agent microspheres in a cold plasma modification treatment device, pre-treat for 120~130s, then place them in a receiving device, place the titanium dioxide solution in a syringe, the mass ratio of titanium dioxide and hydrochloric acid with a mass fraction of 65% in the titanium dioxide solution is 1:3~4, establish a high voltage electrostatic field in the syringe nozzle and the receiving device, the injection speed is 0.01~0.02mm / s, spray for 100~120s, wash with sodium hydroxide with a mass fraction of 10% until the pH is 6~7, then wash with deionized water 5~7 times, place in a microwave reactor, treat for 4~6min to obtain porous titanium dioxide microspheres; (4) Place the porous titanium dioxide microspheres in a low-temperature plasma treatment machine and treat for 30-40s, then place them in a magnetron sputtering treatment machine and treat for 50-70s to obtain composite microspheres; (5) Mix the composite microspheres, ethylene glycol, glycerin and softened water according to the formula amount, and stir at 50~100 rpm for 5~10 min to obtain photocatalytic fluorescent ink.

[0006] Furthermore, the specific preparation process of the self-made fluorescent agent in step (1) is as follows: a. Dissolve resveratrol in anhydrous ethanol at 5.5-6 times the mass of resveratrol. While stirring at 50-60 rpm, add 0.6-1.2 times the mass of pyrene-formaldehyde. Then, adjust the stirring speed to 200-300 rpm and add 6-6.5 times the mass of resveratrol in a 10% sodium hydroxide solution. Stir at 200-300 rpm for 4-5 hours. Filter the solution, wash 3-5 times with deionized water, and then wash 4-6 times with an ethanol-water mixed solvent (ethanol:water volume ratio 10:7). Dry at room temperature for 6-7 hours to obtain the chalcone compound. b. Add the chalcone compound to methanol at 8.5-9 times its mass, stir to dissolve, then add nitromethane at 1-1.5 times its mass and diethylamine at 0.8-0.85 times its mass. Heat to 51-55°C and react for 7-8 hours. Cool to room temperature, add 10% hydrochloric acid to adjust the pH to 6-7, then add dichloromethane at 4-6 times its mass. Extract to obtain an organic layer. Wash the organic layer 4-5 times with deionized water and saturated sodium chloride. Add anhydrous magnesium sulfate until no lumps appear. Dry for 4-6 hours and concentrate under reduced pressure at 200 rpm and 65°C for 2-3 hours to obtain nitroketone compounds. c. Add nitroketone compounds, anhydrous ethanol and ammonium acetate in a mass ratio of 1:13.5~14:9~9.5 into a flask, heat to 80~85℃ while stirring at 100~200 rpm, react for 10~12 h, cool to room temperature, concentrate under reduced pressure at 300 rpm and 90℃ for 3~5 h, and filter to obtain dipyrrole compounds. d. Place the dipyrrole compound and 80-85 times its mass of dichloromethane in a three-necked flask, stir to dissolve, and cool to 0-5°C in an ice-water bath at 0°C. Under a nitrogen atmosphere, add a triethylamine / dichloromethane mixture with a mass ratio of 1:6 to 16:16. Add a boron trifluoride ether / dichloromethane mixture with a mass ratio of 1:3 to 18:18.5 to 10:15 drops / min. Stir at 100-200 rpm for 24-26 hours at room temperature, then wash with deionized water and saturated sodium chloride 4-6 times. Concentrate under reduced pressure at 300 rpm and 40°C for 3-4 hours to obtain the self-made fluorescent agent.

[0007] Furthermore, the vacuum pressure of the spray freeze dryer in step (2) is 35~40 Pa, and the cold air volume is 5.5~6 m³ / h. 3 / min.

[0008] Furthermore, in step (3), the gas pressure of the cold plasma modification treatment equipment is 7~9 Pa, the discharge power is 100~120 W, and sulfur hexafluoride is introduced into the pure argon plasma at a flow rate of 60 sccm and a flow ratio of 0.53.

[0009] Furthermore, in step (3), the syringe nozzle is a 14~16G flat-mouth dispensing needle, the receiving device is aluminum foil, the voltage is 30~40kV, and the temperature is 100~120℃.

[0010] Furthermore, the microwave reactor described in step (3) has a power of 160~200W and a frequency of 2450MHz.

[0011] Furthermore, in step (4), oxygen is used as the processing atmosphere in the low-temperature plasma processor, the gas flow rate is 0.8~1L / min, and the processing power is 4~6kW.

[0012] Furthermore, in step (4), the sputtering power of the magnetron sputtering machine is 100~120W, the vacuum degree is 0.001Pa, the porous titanium dioxide microspheres are placed on the glass substrate, the substrate temperature is 80~100℃, the target material is cerium oxide, and the distance between the target material and the glass substrate is 6~10cm.

[0013] Furthermore, the photocatalytic fluorescent ink prepared by the aforementioned method mainly comprises, by weight, 30-40 parts of self-made fluorescent agent, 20-30 parts of titanium dioxide, 10-15 parts of cerium oxide, 5-8 parts of ethylene glycol, 1-3 parts of glycerol, and 55-65 parts of softened water.

[0014] Compared with the prior art, the beneficial effects achieved by the present invention are: The present invention produces ink by sequentially preparing a self-made fluorescent agent, electrostatic assembly, and cerium oxide plating, so as to achieve good confidentiality, light stability, and biodegradability.

[0015] First, the self-made fluorescent agent is prepared from veratrol, pyrene formaldehyde, and boron trifluoride. The methyl group of veratrol condenses with the aldehyde group of pyrene formaldehyde to form a carbon-carbon double bond, and then an addition reaction is carried out on the carbon-carbon double bond to introduce a nitro group, forming a nitro ketone compound. Then, the nitro group forms a ring with the ketone group of veratrol, and the nitro ketone compounds condense with each other to form a dipyrrole group. The imino group on the dipyrrole group coordinates with boron trifluoride to form an azirbromo-boron dipyrrole compound, which gives the ink a fluorescent effect. Pyrene formaldehyde can expand the conjugated system of the azirbromo-boron dipyrrole compound, and the small steric hindrance of pyrene formaldehyde makes the azirbromo-boron dipyrrole compound tend to be planar, reducing the band gap and causing a red shift in wavelength. In addition, using veratrol, electron-donating groups are introduced at both ends of the azirbromo-boron dipyrrole compound, which further red-shifts the wavelength, so that the ink only undergoes a rapid photosensitive reaction under infrared wavelength irradiation to display the pattern, and is not easily decomposed by light under long-term infrared irradiation, thus having good photostability.

[0016] Secondly, the self-made fluorescent agent was prepared into microspheres by spray freeze-drying, improving its dispersibility. Porous titanium dioxide microspheres were then prepared through plasma, electrostatic spraying, and microwave-assisted electrostatic self-assembly. During plasma treatment, an electronegative gas was used to modify the surface of the self-made fluorescent agent microspheres, giving them a negative charge. Electrostatic spraying atomized titanium dioxide into positively charged droplets, which could electrostatically adsorb onto the self-made fluorescent agent microspheres, resulting in uniform deposition on the surface. Microwave irradiation accelerated the deposition of titanium dioxide and promoted collisions between the self-made fluorescent agent microspheres and titanium dioxide atoms. The collision causes an interatomic reaction, resulting in a tight cross-linking between the two, which improves the stability of the ink and is beneficial for its long-term preservation. Then, through low-temperature plasma-assisted radio frequency magnetron sputtering, cerium oxide is coordinated and chelated onto the active groups on the surface of titanium dioxide microspheres, which enhances the visible light activity of titanium dioxide. Under visible light irradiation, it is excited to catalyze the production of free radicals and reactive oxygen species with strong oxidizing power. These react with the self-made fluorescent agent, causing the molecular chain to break, resulting in the automatic degradation and fading of the ink. Furthermore, the water generated by the reaction of reactive oxygen species and self-made fluorescent agent can further dilute the ink, causing the text to blur and disappear, which is irreversible. Detailed Implementation

[0017] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0018] To more clearly illustrate the method provided by the present invention, the following embodiments are provided in detail. The testing methods for various indicators of the photocatalytic fluorescent ink prepared in the following embodiments are as follows: Confidentiality: Confidentiality effects were tested by taking examples and comparative examples of equal volume, writing on white paper, and irradiating with different light sources.

[0019] Photostability: Equal volumes of the examples and comparative examples were tested for photostability. After being placed at room temperature and under natural light for 20 days, writing was done on white paper, and the fluorescence intensity was observed by irradiating with infrared or visible light.

[0020] Degradability: Equal volumes of the examples and comparative examples were tested for degradability. Writing was done on white paper, and after irradiating with visible light for 2 minutes, the text was checked to see if it disappeared.

[0021] Example 1 A photocatalytic fluorescent ink and its preparation method, comprising, by weight, 30 parts of self-made fluorescent agent, 20 parts of titanium dioxide, 10 parts of cerium oxide, 5 parts of ethylene glycol, 1 part of glycerol, and 55 parts of softened water.

[0022] A method for preparing a photocatalytic fluorescent ink, the method mainly comprising the following preparation steps: (1) Chalcone compound was prepared by mixing veratrone and pyrene formaldehyde, and a self-made fluorescent agent was prepared by adding nitromethane and boron trifluoride ether; (2) Place the self-made fluorescent agent in a spray freeze dryer, spray it out, keep it at -45℃ for 30 min, raise the temperature to -20℃ at a rate of 1℃ / min, and keep it at the temperature for 50 min to obtain the self-made fluorescent agent microspheres; (3) The self-made fluorescent agent microspheres were placed in a cold plasma modification treatment device and pretreated for 120s. Then, they were placed in a receiving device. The titanium dioxide solution was placed in a syringe. The mass ratio of titanium dioxide and hydrochloric acid with a mass fraction of 65% in the titanium dioxide solution was 1:3. A high voltage electrostatic field was established in the syringe nozzle and the receiving device. The injection speed was 0.01 mm / s. After spraying for 120s, the microspheres were washed with sodium hydroxide with a mass fraction of 10% until the pH was 6. Then, they were washed with deionized water 5 times. The microspheres were placed in a microwave reactor and treated for 4min to obtain porous titanium dioxide microspheres. (4) Place the porous titanium dioxide microspheres in a low-temperature plasma treatment machine and treat for 30s, then place them in a magnetron sputtering treatment machine and treat for 50s to obtain composite microspheres. (5) Mix the composite microspheres, ethylene glycol, glycerol and softened water according to the formula amount, and stir at 50 rpm for 10 min to obtain photocatalytic fluorescent ink.

[0023] Furthermore, the specific preparation process of the self-made fluorescent agent in step (1) is as follows: a) Dissolve resveratrol in anhydrous ethanol at 5.5 times the mass of resveratrol. While stirring at 50 rpm, add pyrene formaldehyde at 0.6 times the mass of resveratrol. Then, adjust the stirring speed to 200 rpm and add sodium hydroxide solution at 10% mass fraction at 6 times the mass of resveratrol. Stir at 200 rpm for 5 hours, filter, wash 3 times with deionized water, and then wash 4 times with a mixed ethanol-water solvent with a volume ratio of ethanol to water of 10:7. Dry at room temperature for 6 hours to obtain chalcone compound. b. Add the chalcone compound to methanol at 8.5 times its mass, stir to dissolve, then add nitromethane at 1 times its mass and diethylamine at 0.8 times its mass. Heat to 51°C and react for 8 hours. Cool to room temperature, add 10% hydrochloric acid to adjust the pH of the solution to 6, then add dichloromethane at 4 times its mass. Extract to obtain an organic layer. Wash the organic layer four times with deionized water and saturated sodium chloride. Add anhydrous magnesium sulfate until no lumps appear. Dry for 4 hours and concentrate under reduced pressure at 200 rpm and 65°C for 2 hours to obtain nitroketone compounds. c. Nitroketone compounds, anhydrous ethanol and ammonium acetate were added to a flask in a mass ratio of 1:13.5:9. The mixture was stirred at 100 rpm and heated to 80 °C. After reacting for 10 h, the mixture was cooled to room temperature and concentrated under reduced pressure at 300 rpm and 90 °C for 3 h. The mixture was then filtered to obtain dipyrrole compounds. d. Place the dipyrrole compound and 80 times its mass of dichloromethane in a three-necked flask, stir to dissolve, and cool to 0°C in an ice-water bath. Under a nitrogen atmosphere, add a triethylamine / dichloromethane mixture with a mass ratio of 1:6 to 1:6, with a boron trifluoride ether / dichloromethane mixture with a mass ratio of 1:3 to 1:3. Stir at 100 rpm for 26 h at room temperature, then wash four times with deionized water and saturated sodium chloride. Concentrate under reduced pressure at 300 rpm and 40°C for 3 h to obtain the self-made fluorescent agent.

[0024] Furthermore, in step (2), the vacuum pressure of the spray freeze dryer is 35 Pa, and the cold air volume is 5.5 m³ / s. 3 / min.

[0025] Furthermore, in step (3), the gas pressure of the cold plasma modification treatment equipment is 7 Pa, the discharge power is 100 W, and sulfur hexafluoride is introduced into the pure argon plasma at a flow rate of 60 sccm and a flow ratio of 0.53.

[0026] Furthermore, in step (3), the syringe nozzle is a 14G flat-tipped dispensing needle, the receiving device is aluminum foil, the voltage is 30kV, and the temperature is 100℃.

[0027] Furthermore, the microwave reactor described in step (3) has a power of 160W and a frequency of 2450MHz.

[0028] Furthermore, in step (4), oxygen is used as the processing atmosphere in the low-temperature plasma processor, the gas flow rate is 0.8 L / min, and the processing power is 4 kW.

[0029] Furthermore, in step (4), the sputtering power of the magnetron sputtering machine is 100W, the vacuum degree is 0.001Pa, the porous titanium dioxide microspheres are placed on the glass substrate, the substrate temperature is 80℃, the target material is cerium oxide, and the distance between the target material and the glass substrate is 6cm.

[0030] Example 2 A photocatalytic fluorescent ink and its preparation method, comprising, by weight, 40 parts of self-made fluorescent agent, 30 parts of titanium dioxide, 15 parts of cerium oxide, 8 parts of ethylene glycol, 3 parts of glycerol, and 65 parts of softened water.

[0031] A method for preparing a photocatalytic fluorescent ink, the method mainly comprising the following preparation steps: (1) Chalcone compound was prepared by mixing veratrone and pyrene formaldehyde, and a self-made fluorescent agent was prepared by adding nitromethane and boron trifluoride ether; (2) Place the self-made fluorescent agent in a spray freeze dryer, spray it out, keep it at -45℃ for 40 min, raise the temperature to -20℃ at a rate of 3℃ / min, and keep it at the temperature for 60 min to obtain the self-made fluorescent agent microspheres; (3) The self-made fluorescent agent microspheres were placed in a cold plasma modification treatment device and pretreated for 130s. Then, they were placed in a receiving device. The titanium dioxide solution was placed in a syringe. The mass ratio of titanium dioxide and hydrochloric acid with a mass fraction of 65% in the titanium dioxide solution was 1:4. A high voltage electrostatic field was established in the syringe nozzle and the receiving device. The injection speed was 0.02mm / s. After spraying for 100s, the microspheres were washed with sodium hydroxide with a mass fraction of 10% until the pH was 7. Then, they were washed with deionized water 7 times. The microspheres were placed in a microwave reactor and treated for 6min to obtain porous titanium dioxide microspheres. (4) Place the porous titanium dioxide microspheres in a low-temperature plasma treatment machine and treat for 40s, then place them in a magnetron sputtering treatment machine and treat for 70s to obtain composite microspheres. (5) Mix the composite microspheres, ethylene glycol, glycerol and softened water according to the formula amount, and stir at 100 rpm for 5 min to obtain photocatalytic fluorescent ink.

[0032] Furthermore, the specific preparation process of the self-made fluorescent agent in step (1) is as follows: a) Dissolve resveratrol in anhydrous ethanol at 6 times the mass of resveratrol. While stirring at 60 rpm, add pyrene formaldehyde at 1.2 times the mass of resveratrol. Then, adjust the stirring speed to 300 rpm and add sodium hydroxide solution at 10% mass fraction at 6.5 times the mass of resveratrol. Stir at 300 rpm for 4 hours. Filter, wash 5 times with deionized water, and then wash 6 times with a mixed ethanol-water solvent with a volume ratio of ethanol to water of 10:7. Dry at room temperature for 7 hours to obtain chalcone compound. b. Add the chalcone compound to methanol at 9 times its mass, stir to dissolve, then add nitromethane at 1.5 times its mass and diethylamine at 0.85 times its mass. Heat to 55°C and react for 8 hours. Cool to room temperature, add 10% hydrochloric acid to adjust the pH to 7, then add dichloromethane at 6 times its mass. Extract to obtain an organic layer. Wash the organic layer 5 times with deionized water and saturated sodium chloride. Add anhydrous magnesium sulfate until no lumps appear. Dry for 6 hours and concentrate under reduced pressure at 200 rpm and 65°C for 3 hours to obtain nitroketone compounds. c. Nitroketone compounds, anhydrous ethanol and ammonium acetate were added to a flask in a mass ratio of 1:14:9.5. The mixture was stirred at 200 rpm and heated to 85°C. After reacting for 12 h, the mixture was cooled to room temperature and concentrated under reduced pressure at 300 rpm and 90°C for 5 h. The mixture was then filtered to obtain dipyrrole compounds. d. Place the dipyrrole compound and 85 times its mass of dichloromethane in a three-necked flask, stir to dissolve, and cool to 5°C in an ice-water bath at 0°C. Under a nitrogen atmosphere, add a mixture of triethylamine / dichloromethane at 16.5 times its mass of the dipyrrole compound, with a mass ratio of triethylamine to dichloromethane of 1:6. Add a mixture of boron trifluoride ether / dichloromethane at 18.5 times its mass of the dipyrrole compound, with a mass ratio of boron trifluoride ether to dichloromethane of 1:3, at a rate of 15 drops / min. Stir at 200 rpm for 24 hours at room temperature, then wash 6 times with deionized water and saturated sodium chloride. Concentrate under reduced pressure at 300 rpm and 40°C for 4 hours to obtain the self-made fluorescent agent.

[0033] Furthermore, the vacuum pressure of the spray freeze dryer in step (2) is 40 Pa, and the cold air volume is 6 m³ / s. 3 / min.

[0034] Furthermore, in step (3), the gas pressure of the cold plasma modification treatment equipment is 9 Pa, the discharge power is 120 W, and sulfur hexafluoride is introduced into the pure argon plasma at a flow rate of 60 sccm and a flow ratio of 0.53.

[0035] Furthermore, in step (3), the syringe nozzle is a 16G flat-mouth dispensing needle, the receiving device is aluminum foil, the voltage is 40kV, and the temperature is 120℃.

[0036] Furthermore, the microwave reactor described in step (3) has a power of 200W and a frequency of 2450MHz.

[0037] Furthermore, in step (4), oxygen is used as the processing atmosphere in the low-temperature plasma processor, the gas flow rate is 1L / min, and the processing power is 6kW.

[0038] Furthermore, in step (4), the sputtering power of the magnetron sputtering machine is 120W, the vacuum degree is 0.001Pa, the porous titanium dioxide microspheres are placed on the glass substrate, the substrate temperature is 100℃, the target material is cerium oxide, and the distance from the target material to the glass substrate is 10cm.

[0039] Comparative Example 1 A photocatalytic fluorescent ink and its preparation method, comprising, by weight, 32 parts of fluoroboron dipyrrole, 23 parts of titanium dioxide, 11 parts of cerium oxide, 6 parts of ethylene glycol, 2 parts of glycerol, and 60 parts of softened water.

[0040] A method for preparing a photocatalytic fluorescent ink, the method mainly comprising the following preparation steps: (1) Place fluoroboron dipyrrole in a spray freeze dryer, spray it out, keep it at -45℃ for 35 min, raise the temperature to -20℃ at a rate of 2℃ / min, and keep it at the temperature for 54 min to obtain fluoroboron dipyrrole microspheres; (2) Fluoroboron dipyrrole microspheres were placed in a cold plasma modification treatment device and pretreated for 126s. Then, they were placed in a receiving device. Titanium dioxide solution was placed in a syringe. The mass ratio of titanium dioxide to hydrochloric acid with a mass fraction of 65% was 1:3.12. A high voltage electrostatic field was established in the syringe nozzle and the receiving device. The injection speed was 0.02mm / s. After spraying for 117s, the microspheres were washed with sodium hydroxide with a mass fraction of 10% until the pH was 7. Then, they were washed with deionized water 6 times. The microspheres were placed in a microwave reactor and treated for 5min to obtain porous titanium dioxide microspheres. (3) The porous titanium dioxide microspheres were placed in a low-temperature plasma treatment machine and treated for 36s. Then, they were placed in a magnetron sputtering treatment machine and treated for 64s to obtain composite microspheres. (4) Mix the composite microspheres, ethylene glycol, glycerol and softened water according to the formula amount, and stir at 70 rpm for 8 min to obtain photocatalytic fluorescent ink.

[0041] Furthermore, the vacuum pressure of the spray freeze dryer in step (1) is 38 Pa, and the cold air volume is 5.7 m³ / s. 3 / min.

[0042] Furthermore, in step (2), the gas pressure of the cold plasma modification treatment equipment is 8 Pa, the discharge power is 110 W, sulfur hexafluoride is introduced into the pure argon plasma at a flow rate of 60 sccm and a flow ratio of 0.53, and the power of the microwave reactor is 180 W and the frequency is 2450 MHz.

[0043] Further, the preparation steps of the titanium dioxide precursor solution in step (2) are as follows: take tetrabutyl titanate and anhydrous ethanol at a mass of 1.72 times that of tetrabutyl titanate, and add anhydrous ethanol mixture at a speed of 2.5 mL / min while stirring at a speed of 140 rpm in an ice-water bath. The mass ratio of anhydrous ethanol, distilled water and glacial acetic acid in the anhydrous ethanol mixture is 1:0.32:0.33. Aging at room temperature for 25 h yields the titanium dioxide precursor solution.

[0044] Furthermore, in step (2), the syringe nozzle is a 15G flat-mouth dispensing needle, the receiving device is aluminum foil, the voltage is 35kV, and the temperature is 117℃.

[0045] Furthermore, in step (3), the low-temperature plasma processor uses oxygen as the processing atmosphere, with a gas flow rate of 0.9 L / min and a processing power of 5 kW.

[0046] Furthermore, in step (3), the sputtering power of the magnetron sputtering machine is 115W, the vacuum degree is 0.001Pa, the porous titanium dioxide microspheres are placed on the glass substrate, the substrate temperature is 91℃, the target material is cerium oxide, and the distance between the target material and the glass substrate is 7cm.

[0047] Comparative Example 2 A photocatalytic fluorescent ink and its preparation method, comprising, by weight, 32 parts of self-made fluorescent agent, 23 parts of titanium dioxide, 11 parts of cerium oxide, 6 parts of ethylene glycol, 2 parts of glycerol, and 60 parts of softened water.

[0048] A method for preparing a photocatalytic fluorescent ink, the method mainly comprising the following preparation steps: (1) Chalcone compound was prepared by mixing veratrone and pyrene formaldehyde, and a self-made fluorescent agent was prepared by adding nitromethane and boron trifluoride ether; (2) The self-made fluorescent agent was placed in a spray freeze dryer, sprayed out, kept at -45℃ for 35 min, and heated to -20℃ at a rate of 2℃ / min, and kept at the temperature for 54 min to obtain the self-made fluorescent agent microspheres; (3) Place the self-made fluorescent microspheres in the receiving device and place the titanium dioxide solution in the syringe. The mass ratio of titanium dioxide and hydrochloric acid with a mass fraction of 65% in the titanium dioxide solution is 1:3.12. Establish a high voltage electrostatic field in the syringe nozzle and the receiving device. The injection speed is 0.02 mm / s. After spraying for 117 s, wash with sodium hydroxide with a mass fraction of 10% until the pH is 7. Then wash with deionized water 6 times. Place in a microwave reactor and process for 5 min to obtain porous titanium dioxide microspheres. (4) The porous titanium dioxide microspheres were placed in a low-temperature plasma treatment machine and treated for 36s. Then, they were placed in a magnetron sputtering treatment machine and treated for 64s to obtain composite microspheres. (5) Mix the composite microspheres, ethylene glycol, glycerol and softened water according to the formula amount, and stir at 70 rpm for 8 min to obtain photocatalytic fluorescent ink.

[0049] Furthermore, the specific preparation process of the self-made fluorescent agent in step (1) is as follows: a) Dissolve resveratrol in anhydrous ethanol at 5.77 times the mass of resveratrol. While stirring at 56 rpm, add pyrene formaldehyde at 1.09 times the mass of resveratrol. Then, adjust the stirring speed to 220 rpm and add sodium hydroxide solution at 6.35 times the mass of resveratrol (10% by mass). Stir at 260 rpm for 4.5 h, filter, wash 4 times with deionized water, and then wash 5 times with a mixed ethanol-water solvent (ethanol:water volume ratio of 10:7). Dry at room temperature for 6.5 h to obtain chalcone compound. b. Add the chalcone compound to methanol at 8.71 times its mass, stir to dissolve, then add nitromethane at 1.29 times its mass and diethylamine at 0.83 times its mass. Heat to 54°C and react for 7.5 h. Cool to room temperature, add 10% hydrochloric acid to adjust the pH to 6, then add dichloromethane at 5.13 times its mass. Extract to obtain an organic layer. Wash the organic layer four times with deionized water and saturated sodium chloride, add anhydrous magnesium sulfate until no lumps appear, dry for 5.5 h, and concentrate under reduced pressure at 200 rpm and 65°C for 2.5 h to obtain nitroketone compounds. c. Nitroketone compounds, anhydrous ethanol and ammonium acetate were added to a flask in a mass ratio of 1:13.59:9.32. The mixture was stirred at 150 rpm and heated to 83 °C. After reacting for 11.5 h, the mixture was cooled to room temperature and concentrated under reduced pressure at 300 rpm and 90 °C for 4 h. The mixture was then filtered to obtain dipyrrole compounds. d. Place the dipyrrole compound and 83.21 times its mass of dichloromethane in a three-necked flask, stir to dissolve, and cool to 4°C in an ice-water bath at 0°C. Under a nitrogen atmosphere, add a triethylamine / dichloromethane mixture with a mass ratio of 1:6 to 1:16, with a boron trifluoride ether / dichloromethane mixture with a mass ratio of 1:3 to 1:13. Stir at 110 rpm for 25.5 h at room temperature, then wash five times with deionized water and saturated sodium chloride. Concentrate under reduced pressure at 300 rpm and 40°C for 3.5 h to obtain the self-made fluorescent agent.

[0050] Furthermore, the vacuum pressure of the spray freeze dryer in step (2) is 38 Pa, and the cold air volume is 5.7 m³ / s. 3 / min.

[0051] Furthermore, in step (3), the syringe nozzle is a 15G flat-mouth dispensing needle, the receiving device is aluminum foil, the voltage is 35kV, and the temperature is 117℃.

[0052] Furthermore, the microwave reactor described in step (3) has a power of 180W and a frequency of 2450MHz.

[0053] Furthermore, in step (4), oxygen is used as the processing atmosphere in the low-temperature plasma processor, the gas flow rate is 0.9 L / min, and the processing power is 5 kW.

[0054] Furthermore, in step (4), the sputtering power of the magnetron sputtering machine is 115W, the vacuum degree is 0.001Pa, the porous titanium dioxide microspheres are placed on the glass substrate, the substrate temperature is 91℃, the target material is cerium oxide, and the distance from the target material to the glass substrate is 7cm.

[0055] Comparative Example 3 A photocatalytic fluorescent ink and its preparation method, comprising, by weight, 32 parts of self-made fluorescent agent, 23 parts of titanium dioxide, 11 parts of cerium oxide, 6 parts of ethylene glycol, 2 parts of glycerol, and 60 parts of softened water.

[0056] A method for preparing a photocatalytic fluorescent ink, the method mainly comprising the following preparation steps: (1) Chalcone compound was prepared by mixing veratrone and pyrene formaldehyde, and a self-made fluorescent agent was prepared by adding nitromethane and boron trifluoride ether; (2) The self-made fluorescent agent was placed in a spray freeze dryer, sprayed out, kept at -45℃ for 35 min, and heated to -20℃ at a rate of 2℃ / min, and kept at the temperature for 54 min to obtain the self-made fluorescent agent microspheres; (3) The self-made fluorescent agent microspheres were placed in a cold plasma modification treatment device, pretreated for 126s, titanium dioxide was added, and placed in a microwave reactor for 5min to obtain porous titanium dioxide microspheres. (4) The porous titanium dioxide microspheres were placed in a low-temperature plasma treatment machine and treated for 36s. Then, they were placed in a magnetron sputtering treatment machine and treated for 64s to obtain composite microspheres. (5) Mix the composite microspheres, ethylene glycol, glycerol and softened water according to the formula amount, and stir at 70 rpm for 8 min to obtain photocatalytic fluorescent ink.

[0057] Furthermore, the specific preparation process of the self-made fluorescent agent in step (1) is as follows: a) Dissolve resveratrol in anhydrous ethanol at 5.77 times the mass of resveratrol. While stirring at 56 rpm, add pyrene formaldehyde at 1.09 times the mass of resveratrol. Then, adjust the stirring speed to 220 rpm and add sodium hydroxide solution at 6.35 times the mass of resveratrol (10% by mass). Stir at 260 rpm for 4.5 h, filter, wash 4 times with deionized water, and then wash 5 times with a mixed ethanol-water solvent (ethanol:water volume ratio of 10:7). Dry at room temperature for 6.5 h to obtain chalcone compound. b. Add the chalcone compound to methanol at 8.71 times its mass, stir to dissolve, then add nitromethane at 1.29 times its mass and diethylamine at 0.83 times its mass. Heat to 54°C and react for 7.5 h. Cool to room temperature, add 10% hydrochloric acid to adjust the pH to 6, then add dichloromethane at 5.13 times its mass. Extract to obtain an organic layer. Wash the organic layer four times with deionized water and saturated sodium chloride, add anhydrous magnesium sulfate until no lumps appear, dry for 5.5 h, and concentrate under reduced pressure at 200 rpm and 65°C for 2.5 h to obtain nitroketone compounds. c. Nitroketone compounds, anhydrous ethanol and ammonium acetate were added to a flask in a mass ratio of 1:13.59:9.32. The mixture was stirred at 150 rpm and heated to 83 °C. After reacting for 11.5 h, the mixture was cooled to room temperature and concentrated under reduced pressure at 300 rpm and 90 °C for 4 h. The mixture was then filtered to obtain dipyrrole compounds. d. Place the dipyrrole compound and 83.21 times its mass of dichloromethane in a three-necked flask, stir to dissolve, and cool to 4°C in an ice-water bath at 0°C. Under a nitrogen atmosphere, add a triethylamine / dichloromethane mixture with a mass ratio of 1:6 to 1:16, with a boron trifluoride ether / dichloromethane mixture with a mass ratio of 1:3 to 1:13. Stir at 110 rpm for 25.5 h at room temperature, then wash five times with deionized water and saturated sodium chloride. Concentrate under reduced pressure at 300 rpm and 40°C for 3.5 h to obtain the self-made fluorescent agent.

[0058] Furthermore, the vacuum pressure of the spray freeze dryer in step (2) is 38 Pa, and the cold air volume is 5.7 m³ / s. 3 / min.

[0059] Furthermore, in step (3), the gas pressure of the cold plasma modification treatment equipment is 8 Pa, the discharge power is 110 W, and sulfur hexafluoride is introduced into the pure argon plasma at a flow rate of 60 sccm and a flow ratio of 0.53.

[0060] Furthermore, the microwave reactor described in step (3) has a power of 180W and a frequency of 2450MHz.

[0061] Furthermore, in step (4), oxygen is used as the processing atmosphere in the low-temperature plasma processor, the gas flow rate is 0.9 L / min, and the processing power is 5 kW.

[0062] Furthermore, in step (4), the sputtering power of the magnetron sputtering machine is 115W, the vacuum degree is 0.001Pa, the porous titanium dioxide microspheres are placed on the glass substrate, the substrate temperature is 91℃, the target material is cerium oxide, and the distance from the target material to the glass substrate is 7cm.

[0063] Comparative Example 4 A photocatalytic fluorescent ink and its preparation method, comprising, by weight, 32 parts of self-made fluorescent agent, 23 parts of titanium dioxide, 11 parts of cerium oxide, 6 parts of ethylene glycol, 2 parts of glycerol, and 60 parts of softened water.

[0064] A method for preparing a photocatalytic fluorescent ink, the method mainly comprising the following preparation steps: (1) Chalcone compound was prepared by mixing veratrone and pyrene formaldehyde, and a self-made fluorescent agent was prepared by adding nitromethane and boron trifluoride ether; (2) The self-made fluorescent agent was placed in a spray freeze dryer, sprayed out, kept at -45℃ for 35 min, and heated to -20℃ at a rate of 2℃ / min, and kept at the temperature for 54 min to obtain the self-made fluorescent agent microspheres; (3) The self-made fluorescent agent microspheres were placed in a cold plasma modification treatment device and pretreated for 126s. Then, they were placed in a receiving device. The titanium dioxide solution was placed in a syringe. The mass ratio of titanium dioxide and hydrochloric acid with a mass fraction of 65% in the titanium dioxide solution was 1:3.12. A high voltage electrostatic field was established in the syringe nozzle and the receiving device. The injection speed was 0.02mm / s. The spraying time was 117s. The microspheres were washed with sodium hydroxide with a mass fraction of 10% until the pH was 7. Then, they were washed with deionized water 6 times to obtain porous titanium dioxide microspheres. (4) The porous titanium dioxide microspheres were placed in a low-temperature plasma treatment machine and treated for 36s. Then, they were placed in a magnetron sputtering treatment machine and treated for 64s to obtain composite microspheres. (5) Mix the composite microspheres, ethylene glycol, glycerol and softened water according to the formula amount, and stir at 70 rpm for 8 min to obtain photocatalytic fluorescent ink.

[0065] Furthermore, the specific preparation process of the self-made fluorescent agent in step (1) is as follows: a) Dissolve resveratrol in anhydrous ethanol at 5.77 times the mass of resveratrol. While stirring at 56 rpm, add pyrene formaldehyde at 1.09 times the mass of resveratrol. Then, adjust the stirring speed to 220 rpm and add sodium hydroxide solution at 6.35 times the mass of resveratrol (10% by mass). Stir at 260 rpm for 4.5 h, filter, wash 4 times with deionized water, and then wash 5 times with a mixed ethanol-water solvent (ethanol:water volume ratio of 10:7). Dry at room temperature for 6.5 h to obtain chalcone compound. b. Add the chalcone compound to methanol at 8.71 times its mass, stir to dissolve, then add nitromethane at 1.29 times its mass and diethylamine at 0.83 times its mass. Heat to 54°C and react for 7.5 h. Cool to room temperature, add 10% hydrochloric acid to adjust the pH to 6, then add dichloromethane at 5.13 times its mass. Extract to obtain an organic layer. Wash the organic layer four times with deionized water and saturated sodium chloride, add anhydrous magnesium sulfate until no lumps appear, dry for 5.5 h, and concentrate under reduced pressure at 200 rpm and 65°C for 2.5 h to obtain nitroketone compounds. c. Nitroketone compounds, anhydrous ethanol and ammonium acetate were added to a flask in a mass ratio of 1:13.59:9.32. The mixture was stirred at 150 rpm and heated to 83 °C. After reacting for 11.5 h, the mixture was cooled to room temperature and concentrated under reduced pressure at 300 rpm and 90 °C for 4 h. The mixture was then filtered to obtain dipyrrole compounds. d. Place the dipyrrole compound and 83.21 times its mass of dichloromethane in a three-necked flask, stir to dissolve, and cool to 4°C in an ice-water bath at 0°C. Under a nitrogen atmosphere, add a triethylamine / dichloromethane mixture with a mass ratio of 1:6 to 1:16, with a boron trifluoride ether / dichloromethane mixture with a mass ratio of 1:3 to 1:13. Stir at 110 rpm for 25.5 h at room temperature, then wash five times with deionized water and saturated sodium chloride. Concentrate under reduced pressure at 300 rpm and 40°C for 3.5 h to obtain the self-made fluorescent agent.

[0066] Furthermore, the vacuum pressure of the spray freeze dryer in step (2) is 38 Pa, and the cold air volume is 5.7 m³ / s. 3 / min.

[0067] Furthermore, in step (3), the gas pressure of the cold plasma modification treatment equipment is 8 Pa, the discharge power is 110 W, and sulfur hexafluoride is introduced into the pure argon plasma at a flow rate of 60 sccm and a flow ratio of 0.53.

[0068] Furthermore, in step (3), the syringe nozzle is a 15G flat-mouth dispensing needle, the receiving device is aluminum foil, the voltage is 35kV, and the temperature is 117℃.

[0069] Furthermore, in step (4), oxygen is used as the processing atmosphere in the low-temperature plasma processor, the gas flow rate is 0.9 L / min, and the processing power is 5 kW.

[0070] Furthermore, in step (4), the sputtering power of the magnetron sputtering machine is 115W, the vacuum degree is 0.001Pa, the porous titanium dioxide microspheres are placed on the glass substrate, the substrate temperature is 91℃, the target material is cerium oxide, and the distance from the target material to the glass substrate is 7cm.

[0071] Comparative Example 5 A photocatalytic fluorescent ink and its preparation method, comprising, by weight, 32 parts of self-made fluorescent agent, 23 parts of titanium dioxide, 6 parts of ethylene glycol, 2 parts of glycerol, and 60 parts of softened water.

[0072] A method for preparing a photocatalytic fluorescent ink, the method mainly comprising the following preparation steps: (1) Chalcone compound was prepared by mixing veratrone and pyrene formaldehyde, and a self-made fluorescent agent was prepared by adding nitromethane and boron trifluoride ether; (2) The self-made fluorescent agent was placed in a spray freeze dryer, sprayed out, kept at -45℃ for 35 min, and heated to -20℃ at a rate of 2℃ / min, and kept at the temperature for 54 min to obtain the self-made fluorescent agent microspheres; (3) The self-made fluorescent agent microspheres were placed in a cold plasma modification treatment device and pretreated for 126s. Then, they were placed in a receiving device. The titanium dioxide solution was placed in a syringe. The mass ratio of titanium dioxide and hydrochloric acid with a mass fraction of 65% in the titanium dioxide solution was 1:3.12. A high voltage electrostatic field was established in the syringe nozzle and the receiving device. The injection speed was 0.02mm / s. After spraying for 117s, the microspheres were washed with sodium hydroxide with a mass fraction of 10% until the pH was 7. Then, they were washed with deionized water 6 times. The microspheres were placed in a microwave reactor and treated for 5min to obtain porous titanium dioxide microspheres. (4) Mix titanium dioxide porous microspheres, ethylene glycol, glycerol and softened water according to the formula amount, and stir at 70 rpm for 8 min to obtain photocatalytic fluorescent ink.

[0073] Furthermore, the specific preparation process of the self-made fluorescent agent in step (1) is as follows: a) Dissolve resveratrol in anhydrous ethanol at 5.77 times the mass of resveratrol. While stirring at 56 rpm, add pyrene formaldehyde at 1.09 times the mass of resveratrol. Then, adjust the stirring speed to 220 rpm and add sodium hydroxide solution at 6.35 times the mass of resveratrol (10% by mass). Stir at 260 rpm for 4.5 h, filter, wash 4 times with deionized water, and then wash 5 times with a mixed ethanol-water solvent (ethanol:water volume ratio of 10:7). Dry at room temperature for 6.5 h to obtain chalcone compound. b. Add the chalcone compound to methanol at 8.71 times its mass, stir to dissolve, then add nitromethane at 1.29 times its mass and diethylamine at 0.83 times its mass. Heat to 54°C and react for 7.5 h. Cool to room temperature, add 10% hydrochloric acid to adjust the pH to 6, then add dichloromethane at 5.13 times its mass. Extract to obtain an organic layer. Wash the organic layer four times with deionized water and saturated sodium chloride, add anhydrous magnesium sulfate until no lumps appear, dry for 5.5 h, and concentrate under reduced pressure at 200 rpm and 65°C for 2.5 h to obtain nitroketone compounds. c. Nitroketone compounds, anhydrous ethanol and ammonium acetate were added to a flask in a mass ratio of 1:13.59:9.32. The mixture was stirred at 150 rpm and heated to 83 °C. After reacting for 11.5 h, the mixture was cooled to room temperature and concentrated under reduced pressure at 300 rpm and 90 °C for 4 h. The mixture was then filtered to obtain dipyrrole compounds. d. Place the dipyrrole compound and 83.21 times its mass of dichloromethane in a three-necked flask, stir to dissolve, and cool to 4°C in an ice-water bath at 0°C. Under a nitrogen atmosphere, add a triethylamine / dichloromethane mixture with a mass ratio of 1:6 to 1:16, with a boron trifluoride ether / dichloromethane mixture with a mass ratio of 1:3 to 1:13. Stir at 110 rpm for 25.5 h at room temperature, then wash five times with deionized water and saturated sodium chloride. Concentrate under reduced pressure at 300 rpm and 40°C for 3.5 h to obtain the self-made fluorescent agent.

[0074] Furthermore, the vacuum pressure of the spray freeze dryer in step (2) is 38 Pa, and the cold air volume is 5.7 m³ / s. 3 / min.

[0075] Furthermore, in step (3), the gas pressure of the cold plasma modification treatment equipment is 8 Pa, the discharge power is 110 W, and sulfur hexafluoride is introduced into the pure argon plasma at a flow rate of 60 sccm and a flow ratio of 0.53.

[0076] Furthermore, in step (3), the syringe nozzle is a 15G flat-mouth dispensing needle, the receiving device is aluminum foil, the voltage is 35kV, and the temperature is 117℃.

[0077] Furthermore, the microwave reactor described in step (3) has a power of 180W and a frequency of 2450MHz.

[0078] Comparative Example 6 A photocatalytic fluorescent ink and its preparation method, comprising, by weight, 32 parts of fluoroboron dipyrrole, 23 parts of titanium dioxide, 6 parts of ethylene glycol, 2 parts of glycerol, and 60 parts of softened water.

[0079] A method for preparing a photocatalytic fluorescent ink, the method mainly comprising the following preparation steps: (1) Place fluoroboron dipyrrole in a spray freeze dryer, spray it out, keep it at -45℃ for 35 min, raise the temperature to -20℃ at a rate of 2℃ / min, and keep it at the temperature for 54 min to obtain microspheres; (2) Mix microspheres, titanium dioxide, ethylene glycol, glycerin and softened water according to the formula amount, and stir at 70 rpm for 8 min to obtain photocatalytic fluorescent ink.

[0080] Furthermore, the vacuum pressure of the spray freeze dryer in step (1) is 38 Pa, and the cold air volume is 5.7 m³ / s. 3 / min.

[0081] Example of effect Table 1 below shows the performance analysis results of the photocatalytic fluorescent inks used in Examples 1 to 2 and Comparative Examples 1 to 6 of the present invention.

[0082] Table 1 Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Light source Infrared light Infrared light Visible light Infrared light Infrared light Infrared light Infrared light Visible light Fluorescence intensity after 20 days powerful powerful generally none none weak generally none Text after being illuminated by visible light disappear disappear exist exist exist exist exist exist A comparison of the experimental data from Examples 1 and 2 with Comparative Example 6 reveals that using a self-made fluorescent agent in the product allows the ink to only display color under infrared light and exhibits photostability. The preparation of titanium dioxide microspheres using plasma, electrostatic spraying, and microwaves ensures a tight cross-linking between titanium dioxide and the self-made fluorescent agent, improving ink stability. Furthermore, the introduction of cerium oxide enhances the visible light activity of titanium dioxide, making the ink degrade and disappear under visible light, resulting in good confidentiality. A comparison of the experimental data from Examples 1 and 2 with Comparative Example 1 also shows that without the use of resveratrol, pyrene formaldehyde, and... Boron trifluoride was used to prepare a self-made fluorescent agent. However, the conjugated system of pyrene-formaldehyde and its relatively small steric hindrance resulted in a large band gap in the self-made fluorescent agent, and it was also impossible to introduce electron-donating groups. This resulted in the wavelength being within the visible light range, so the ink could develop color under visible light, leading to poor ink security. A comparison of the experimental data from Examples 1 and 2 with Comparative Example 2 revealed that without the use of a plasma source during the preparation of porous titanium dioxide microspheres, it was impossible to introduce negatively charged ions onto the surface of the self-made fluorescent agent microspheres, resulting in weak electrostatic adsorption with titanium dioxide and affecting the stability of the ink. Furthermore, the surface titanium dioxide content is low, allowing only a small amount of cerium oxide to be introduced, which cannot completely break the molecular chains of the self-made fluorescent agent, affecting the degradability of the ink. A comparison of the experimental data from Examples 1 and 2 with Comparative Example 3 reveals that without electrostatic spraying during the preparation of porous titanium dioxide microspheres, titanium dioxide cannot be atomized and cannot be uniformly deposited on the surface of the self-made fluorescent agent microspheres, easily leading to aggregation, affecting the degree of cross-linking between titanium dioxide and the self-made fluorescent agent microspheres, and reducing the stability of the ink. A comparison of the experimental data from Examples 1 and 2 with Comparative Example 4 reveals that during the preparation of… Without microwave treatment during the production of porous titanium dioxide microspheres, the self-made fluorescent agent and titanium dioxide atoms cannot react, and the two cannot be tightly cross-linked, affecting the stability of the ink. A comparison of the experimental data from Examples 1 and 2 with Comparative Example 5 shows that without the introduction of cerium oxide, the wavelength range of titanium dioxide cannot be broadened, and the visible light activity of titanium dioxide is weakened. As a result, titanium dioxide cannot catalyze the production of free radicals and reactive oxygen species under visible light, thus failing to destroy the self-made fluorescent agent. Consequently, the ink remains on the paper and cannot be degraded, resulting in poor ink confidentiality.

[0083] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A photocatalytic fluorescent ink, characterized in that: By weight, it mainly includes: 40 parts self-made fluorescent agent, 30 parts titanium dioxide, 15 parts cerium oxide, 8 parts ethylene glycol, 3 parts glycerin, and 65 parts softened water; The preparation method of the photocatalytic fluorescent ink mainly includes the following preparation steps: (1) Chalcone compound was prepared by mixing veratrone and pyrene formaldehyde, and a self-made fluorescent agent was prepared by adding nitromethane and boron trifluoride ether; (2) Place the self-made fluorescent agent in a spray freeze dryer, spray it out, keep it at -45℃ for 40 min, raise the temperature to -20℃ at a rate of 3℃ / min, and keep it at the temperature for 60 min to obtain the self-made fluorescent agent microspheres; (3) The self-made fluorescent agent microspheres were placed in a cold plasma modification treatment device and pretreated for 130s. Then, they were placed in a receiving device. The titanium dioxide solution was placed in a syringe. The mass ratio of titanium dioxide and hydrochloric acid with a mass fraction of 65% in the titanium dioxide solution was 1:

4. A high voltage electrostatic field was established in the syringe nozzle and the receiving device. The injection speed was 0.02 mm / s. After spraying for 100s, the microspheres were washed with sodium hydroxide with a mass fraction of 10% until the pH was 7. Then, they were washed with deionized water 7 times. The microspheres were placed in a microwave reactor and treated for 6min to obtain porous titanium dioxide microspheres. (4) Place the porous titanium dioxide microspheres in a low-temperature plasma treatment machine and treat for 40s, then place them in a magnetron sputtering treatment machine and treat for 70s to obtain composite microspheres. (5) Mix the composite microspheres, ethylene glycol, glycerin and softened water according to the formula amount, and stir at 100 rpm for 5 min to obtain photocatalytic fluorescent ink; The specific preparation process of the self-made fluorescent agent in step (1) is as follows: a) Dissolve resveratrol in anhydrous ethanol at 6 times the mass of resveratrol. While stirring at 60 rpm, add pyrene formaldehyde at 1.2 times the mass of resveratrol. Then, adjust the stirring speed to 300 rpm and add sodium hydroxide solution at 10% mass fraction at 6.5 times the mass of resveratrol. Stir at 300 rpm for 4 hours. Filter, wash 5 times with deionized water, and then wash 6 times with a mixed ethanol-water solvent with a volume ratio of ethanol to water of 10:

7. Dry at room temperature for 7 hours to obtain chalcone compound. b. Add the chalcone compound to methanol at 9 times its mass, stir to dissolve, then add nitromethane at 1.5 times its mass and diethylamine at 0.85 times its mass. Heat to 55°C and react for 8 hours. Cool to room temperature, add 10% hydrochloric acid to adjust the pH to 7, then add dichloromethane at 6 times its mass. Extract to obtain an organic layer. Wash the organic layer 5 times with deionized water and saturated sodium chloride. Add anhydrous magnesium sulfate until no lumps appear. Dry for 6 hours and concentrate under reduced pressure at 200 rpm and 65°C for 3 hours to obtain nitroketone compounds. c. Nitroketone compounds, anhydrous ethanol and ammonium acetate were added to a flask in a mass ratio of 1:14:9.

5. The mixture was stirred at 200 rpm and heated to 85°C. After reacting for 12 h, the mixture was cooled to room temperature and concentrated under reduced pressure at 300 rpm and 90°C for 5 h. The mixture was then filtered to obtain dipyrrole compounds. d. Place the dipyrrole compound and 85 times its mass of dichloromethane in a three-necked flask, stir to dissolve, and cool to 5°C in an ice-water bath at 0°C. Under a nitrogen atmosphere, add a triethylamine / dichloromethane mixture with a mass ratio of 1:6 to 1:6 with a mass ratio of 1:6 to 1:

15. Add a boron trifluoride ether / dichloromethane mixture with a mass ratio of 1:3 to 1:3 with a mass ratio of 1:3 to 1:

15. Stir at 200 rpm for 24 hours at room temperature. Wash the mixture 6 times with deionized water and saturated sodium chloride. Concentrate under reduced pressure at 300 rpm and 40°C for 4 hours to obtain the self-made fluorescent agent. The vacuum pressure of the spray freeze dryer in step (2) is 40 Pa, and the cold air volume is 6 m³ / s. 3 / min; The gas pressure of the cold plasma modification treatment equipment in step (3) is 9 Pa, the discharge power is 120 W, and sulfur hexafluoride is introduced into the pure argon plasma at a flow rate of 60 sccm and a flow ratio of 0.

53. The syringe nozzle in step (3) is a 16G flat-tip dispensing needle, the receiving device is aluminum foil, the voltage is 40kV, and the temperature is 120℃. The microwave reactor described in step (3) has a power of 200W and a frequency of 2450MHz; In step (4), oxygen is used as the processing atmosphere in the low-temperature plasma processor, the gas flow rate is 1L / min, and the processing power is 6kW. In step (4), the sputtering power of the magnetron sputtering machine is 120W, the vacuum degree is 0.001Pa, the porous titanium dioxide microspheres are placed on the glass substrate, the substrate temperature is 100℃, the target material is cerium oxide, and the distance between the target material and the glass substrate is 10cm.