CN113913049A - Photocatalyst fluorescent ink and preparation method thereof - Google Patents
Photocatalyst fluorescent ink and preparation method thereof Download PDFInfo
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- CN113913049A CN113913049A CN202111411665.8A CN202111411665A CN113913049A CN 113913049 A CN113913049 A CN 113913049A CN 202111411665 A CN202111411665 A CN 202111411665A CN 113913049 A CN113913049 A CN 113913049A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
The invention discloses photocatalyst fluorescent ink and a preparation method thereof, and relates to the technical field of ink. The self-made fluorescent agent is frozen into a microspherical shape, and then titanium dioxide is adsorbed on the surface of the self-made fluorescent agent by utilizing plasma, electrostatic spraying and microwaves, so that the stability of the ink is improved; then, through low-temperature plasma assisted radio frequency magnetron sputtering, the cerium oxide is chelated on the surface of the titanium dioxide microsphere in a coordination manner, the visible light activity of the titanium dioxide is improved, and the ink can be catalytically degraded under visible light; the self-made fluorescent agent is prepared from veratone, pyrene formaldehyde and boron trifluoride, so that the ink can show patterns only under the irradiation of infrared wavelengths, is not easily decomposed by illumination under the 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
The invention relates to the technical field of ink, in particular to photocatalyst fluorescent ink and a preparation method thereof.
Background
For a long time, the information security problem is very important for the country, the enterprise and the individual, and the combination of paper and ink is an important medium for transmitting information; although the current network technology is rapidly developed, and much data and information are transmitted and stored through the network, in many occasions and some special units, the important and even confidential documents stored still remain paper printed matters or handwritten matters.
How to protect the contents of these paper confidential documents from being stolen becomes an important issue. At present, two methods, namely invisible ink and document crushing, are mainly adopted as protection measures; although the file crushing treatment method is simple, a large amount of waste is caused, the company cost is increased, and certain harm is caused to the environment; the invisible ink on the market is mainly developed under the stimulation of heating, acid-base solution and the like, although the invisible confidentiality effect can be achieved, once stolen, the invisible ink cannot disappear before copying and propagation, so that the invisible ink can be synthesized into visible-light-decomposable fading ink by utilizing a photocatalyst technology and used for writing confidential documents, and the possibility of information leakage is reduced to the greatest extent.
Disclosure of Invention
The invention aims to provide photocatalyst fluorescent ink and a preparation method thereof, and aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of photocatalyst fluorescent ink is characterized by mainly comprising the following preparation steps:
(1) mixing veratone with pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl etherate to prepare a self-made fluorescent agent;
(2) placing the self-made fluorescer in a spray freeze dryer, spraying out, keeping the temperature at minus 45 ℃ for 30-40 min, heating to minus 20 ℃ at the speed of 1-3 ℃/min, and keeping the temperature for 50-60 min to obtain fluorescer microspheres;
(3) placing the self-made fluorescer microspheres in cold plasma modification treatment equipment, pretreating for 120-130 s, placing the pretreated microspheres in a receiving device, placing a titanium dioxide solution in an injector, wherein the mass ratio of titanium dioxide to hydrochloric acid with the mass fraction of 65% is 1: 3-4, establishing a high-voltage electrostatic field in a nozzle of the injector and the receiving device, the injection speed is 0.01-0.02 mm/s, spraying for 100-120 s, washing with 10% sodium hydroxide until the pH value is 6-7, washing with deionized water for 5-7 times, placing the washed microspheres in a microwave reactor, and treating for 4-6 min to obtain titanium dioxide porous microspheres;
(4) placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 30-40 s, then placing in a magnetron sputtering processor, and processing for 50-70 s to obtain composite microspheres;
(5) mixing the composite microspheres, ethylene glycol, glycerol and softened water according to the formula amount, and stirring at 50-100 rpm for 5-10 min to obtain the photocatalyst fluorescent ink.
Further, the specific preparation process of the self-made fluorescent agent in the step (1) is as follows:
a. dissolving veratone in absolute ethyl alcohol with the weight 5.5-6 times of that of the veratone, stirring at the speed of 50-60 rpm, adding pyrene formaldehyde with the weight 0.6-1.2 times of that of the veratone, then adjusting the stirring speed to 200-300 rpm, adding a sodium hydroxide solution with the weight fraction of 10% and the weight 6-6.5 times of that of the veratone, stirring at the speed of 200-300 rpm for 4-5 h, filtering, washing with deionized water for 3-5 times, washing with an ethanol-water mixed solvent for 4-6 times, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying at room temperature for 6-7 h to obtain a chalcone compound;
b. adding a chalcone compound into methanol with the mass 8.5-9 times that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass 1-1.5 times that of the chalcone compound and diethylamine with the mass 0.8-0.85 time that of the chalcone compound, heating to 51-55 ℃, reacting for 7-8 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 6-7, adding dichloromethane with the mass 4-6 times that of the chalcone compound, and extracting to obtain an organic layer; washing the organic layer with deionized water and saturated sodium chloride for 4-5 times in sequence, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 4-6 h, and concentrating under reduced pressure at 200rpm and 65 ℃ for 2-3 h to obtain nitroketone compounds;
c. adding a nitroketone compound, absolute ethyl alcohol and ammonium acetate into a flask according to the mass ratio of 1: 13.5-14: 9-9.5, stirring at the speed of 100-200 rpm, heating to 80-85 ℃, reacting for 10-12 hours, cooling to room temperature, concentrating at 300rpm and 90 ℃ under reduced pressure for 3-5 hours, and filtering to obtain a dipyrrole compound;
d. putting a dipyrrole compound and dichloromethane with the mass of 80-85 times of that of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 0-5 ℃ in ice-water bath at 0 ℃, adding a triethylamine/dichloromethane mixed solution with 16-16.5 times of the mass of the dipyrrole compound in the nitrogen atmosphere, wherein the mass ratio of triethylamine to dichloromethane in the triethylamine/dichloromethane mixed solution is 1:6, adding boron trifluoride diethyl etherate/dichloromethane mixed liquid with the mass of 18-18.5 times of that of the dipyrrole compound at the speed of 10-15 drops/min, wherein the mass ratio of the boron trifluoride diethyl etherate to the dichloromethane in the boron trifluoride diethyl etherate/dichloromethane mixed liquid is 1:3, at room temperature, stirring at a speed of 100-200 rpm for 24-26 h, washing with deionized water and saturated sodium chloride for 4-6 times in sequence, and concentrating under reduced pressure at 300rpm and 40 ℃ for 3-4 h to obtain the fluorescent agent.
Further, the vacuum pressure of the spray freeze dryer in the step (2) is 35-40 Pa, and the cold air volume is 5.5-6 m3/min。
Further, the gas pressure of the cold plasma modification treatment equipment in the step (3) is 7-9 Pa, the discharge power is 100-120W, sulfur hexafluoride is introduced into the pure argon plasma, the introduction flow rate is 60sccm, and the flow rate ratio is 0.53.
Further, in the step (3), the injector nozzle is a 14-16G flat-end dispensing needle head, the receiving device is aluminum foil paper, the voltage is 30-40 kV, and the temperature is 100-120 ℃.
Further, the power of the microwave reactor in the step (3) is 160-200W, and the frequency is 2450 MHz.
Further, in the step (4), oxygen is used as a treatment atmosphere in the low-temperature plasma treatment machine, the gas flow is 0.8-1L/min, and the treatment power is 4-6 kW.
Further, in the magnetron sputtering processor in the step (4), the sputtering power is 100-120W, the vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on a glass substrate, the temperature of the substrate is 80-100 ℃, the target material is cerium oxide, and the distance from the target material to the glass substrate is 6-10 cm.
Further, the photocatalyst fluorescent ink prepared by the preparation method of the photocatalyst fluorescent ink mainly comprises, by weight, 30-40 parts of a 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.
Compared with the prior art, the invention has the following beneficial effects:
the ink is prepared through the steps of self-made fluorescent agent preparation, electrostatic assembly, cerium oxide plating and the like in sequence, so that the effects of good confidentiality, light stability and degradability are achieved.
Firstly, a self-made fluorescent agent is prepared from veratone, pyrene formaldehyde and boron trifluoride; condensing methyl of veratone and aldehyde group of pyrene formaldehyde to form a carbon-carbon double bond, carrying out addition reaction on the carbon-carbon double bond, and introducing nitryl to form a nitroketone compound; then, the nitro group and the ketone group of the veratone are utilized to form a ring, and the nitro ketone compounds are condensed to form a dipyrrolyl group; the imino on the dipyrroliyl group coordinates with boron trifluoride to form a nitrogen-doped boron fluoride dipyrrolide compound, so that the ink has a fluorescent effect; pyrene formaldehyde can expand a conjugated system of the aza-BODIPY compound, and the smaller steric hindrance of the pyrene formaldehyde enables the aza-BODIPY compound to tend to be planar, so that an energy gap is reduced, and a wavelength is red-shifted; in addition, by utilizing veratone, electron donating groups are introduced at two ends of the aza-BODIPY compound, so that the wavelength is further red-shifted, the ink can quickly generate photosensitive reaction only under the irradiation of infrared wavelength, a pattern is displayed, and the ink is not easily decomposed by illumination under the long-time infrared irradiation and has better light stability.
Secondly, the self-made fluorescent agent is prepared into a microspherical shape by utilizing spray freeze drying, so that the dispersibility of the self-made fluorescent agent is improved; preparing titanium dioxide porous microspheres by plasma, electrostatic spraying and microwave-assisted electrostatic self-assembly; in the plasma treatment process, electronegative gas is used for modifying the surface of the self-made fluorescent agent microsphere, so that the surface is negatively charged; titanium dioxide is atomized by utilizing electrostatic spraying to form liquid drops with positive charges, the liquid drops can be electrostatically adsorbed with the self-made fluorescer microspheres and uniformly deposited on the surface, microwave irradiation is utilized to accelerate titanium dioxide deposition, and collision between the self-made fluorescer microspheres and titanium dioxide atoms is promoted to generate interatomic reaction, so that the titanium dioxide and the self-made fluorescer microspheres are tightly crosslinked, the stability of the ink is improved, and the long-term storage of the ink is facilitated; and then, low-temperature plasma assisted radio frequency magnetron sputtering is carried out, so that the coordination of cerium oxide is chelated with active groups on the surface of the titanium dioxide microsphere, the visible light activity of the titanium dioxide is improved, free radicals and active oxygen with strong oxidizing capability are produced by excitation catalysis under the irradiation of visible light, the free radicals and the active oxygen react with a self-made fluorescent agent to break molecular chains, the ink is automatically degraded and faded, and the water generated by the reaction of the active oxygen and the self-made fluorescent agent can further dilute the ink, so that the characters are blurred and disappear, and the characters cannot be recovered.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are provided to illustrate the method for testing each index of the photocatalytic fluorescent ink prepared in the following examples as follows:
confidentiality: the confidentiality effect test was performed on the same volume of the examples and comparative examples, and the white paper was written and illuminated with different light sources.
Light stability: the light stability effect test is carried out on the embodiment and the comparative example with the same volume, after the embodiment and the comparative example are placed for 20 days at room temperature under natural light, the white paper is written, and the fluorescence intensity is observed by utilizing infrared light or visible light irradiation.
Degradability: the samples with the same volume and the comparative samples are taken for carrying out the degradability effect test, writing is carried out on white paper, and whether the characters disappear or not is checked after the white paper is irradiated for 2min by visible light.
Example 1
A photocatalyst fluorescent ink and a preparation method thereof are disclosed, which mainly comprise the following components in parts by weight: 30 parts of a 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.
A preparation method of photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) mixing veratone with pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl etherate to prepare a self-made fluorescent agent;
(2) placing the self-made fluorescer in a spray freeze dryer, spraying out, keeping the temperature at minus 45 ℃ for 30min, heating to minus 20 ℃ at the speed of 1 ℃/min, and keeping the temperature for 50min to obtain fluorescer-making microspheres;
(3) placing the self-made fluorescer microspheres in cold plasma modified treatment equipment, pretreating for 120s, placing the pretreated fluorescer microspheres in a receiving device, placing a titanium dioxide solution in an injector, wherein the mass ratio of titanium dioxide in the titanium dioxide solution to hydrochloric acid with the mass fraction of 65% is 1:3, establishing a high-voltage electrostatic field in the injector nozzle and the receiving device, the injection speed is 0.01mm/s, spraying for 120s, washing with sodium hydroxide with the mass fraction of 10% until the pH value is 6, washing with deionized water for 5 times, placing in a microwave reactor, and treating for 4min to obtain titanium dioxide porous microspheres;
(4) placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 30s, then placing in a magnetron sputtering processor, and processing for 50s to obtain composite microspheres;
(5) and mixing the composite microspheres, glycol, glycerol and softened water according to the formula amount, and stirring at 50rpm for 10min to obtain the photocatalyst fluorescent ink.
Further, the specific preparation process of the self-made fluorescent agent in the step (1) is as follows:
a. dissolving veratone in absolute ethyl alcohol with the weight 5.5 times of that of the veratone, adding pyrene formaldehyde with the weight 0.6 times of that of the veratone while stirring at the speed of 50rpm, adjusting the stirring speed to 200rpm, adding a sodium hydroxide solution with the weight fraction of 10 percent and the weight 6 times of that of the veratone, stirring for 5 hours at the speed of 200rpm, filtering, washing for 3 times by using deionized water, washing for 4 times by using an ethanol-water mixed solvent, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying for 6 hours at room temperature to obtain a chalcone compound;
b. adding a chalcone compound into methanol with the mass 8.5 times that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass 1 time that of the chalcone compound and diethylamine with the mass 0.8 time that of the chalcone compound, heating to 51 ℃, reacting for 8 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 6, adding dichloromethane with the mass 4 times that of the chalcone compound, and extracting to obtain an organic layer; washing the organic layer with deionized water and saturated sodium chloride for 4 times, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 4h, and concentrating under reduced pressure at 200rpm and 65 deg.C for 2h to obtain nitroketone compound;
c. adding nitroketone compounds, absolute ethyl alcohol and ammonium acetate into a flask according to the mass ratio of 1:13.5:9, stirring at the speed of 100rpm, heating to 80 ℃, reacting for 10 hours, cooling to room temperature, concentrating under reduced pressure at the temperature of 300rpm and 90 ℃ for 3 hours, and filtering to obtain dipyrrole compounds;
d. putting a dipyrrole compound and dichloromethane with the mass of 80 times of that of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 0 ℃ in ice-water bath at 0 ℃, adding a triethylamine/dichloromethane mixed solution with the mass of 16 times of that of the dipyrrole compound in a nitrogen atmosphere, wherein the mass ratio of triethylamine to dichloromethane in the triethylamine/dichloromethane mixed solution is 1:6, adding a boron trifluoride diethyl ether/dichloromethane mixed solution with the mass of 18 times of that of the dipyrrole compound at the speed of 10 drops/min, wherein the mass ratio of boron trifluoride diethyl ether to dichloromethane in the boron trifluoride diethyl ether/dichloromethane mixed solution is 1:3, stirring at room temperature at the speed of 100rpm for 26h, washing with deionized water and saturated sodium chloride for 4 times in sequence, and concentrating at 300rpm and 40 ℃ under reduced pressure for 3h to obtain the fluorescent agent.
Further, the vacuum pressure of the spray freeze dryer in the step (2) is 35Pa, and the cold air volume is 5.5m3/min。
Further, the gas pressure of the cold plasma modification treatment equipment in the step (3) is 7Pa, the discharge power is 100W, sulfur hexafluoride is introduced into the pure argon plasma, the introduction flow rate is 60sccm, and the flow rate ratio is 0.53.
Further, the injector nozzle in the step (3) is a 14G flat-end dispensing needle head, the receiving device is aluminum foil paper, the voltage is 30kV, and the temperature is 100 ℃.
Further, the power of the microwave reactor in the step (3) is 160W, and the frequency is 2450 MHz.
Further, in the low-temperature plasma processor in the step (4), oxygen is used as a processing atmosphere, the gas flow is 0.8L/min, and the processing power is 4 kW.
Further, in the magnetron sputtering processor in the step (4), the sputtering power is 100W, the vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on the glass substrate, the temperature of the substrate is 80 ℃, the target material is cerium oxide, and the distance from the target material to the glass substrate is 6 cm.
Example 2
A photocatalyst fluorescent ink and a preparation method thereof are disclosed, which mainly comprise the following components in parts 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.
A preparation method of photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) mixing veratone with pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl etherate to prepare a self-made fluorescent agent;
(2) placing the self-made fluorescer in a spray freeze dryer, spraying out, keeping the temperature at minus 45 ℃ for 40min, heating to minus 20 ℃ at the speed of 3 ℃/min, and keeping the temperature for 60min to obtain fluorescer-making microspheres;
(3) placing the self-made fluorescer microspheres in cold plasma modified treatment equipment, pretreating for 130s, placing the pretreated fluorescer microspheres in a receiving device, placing a titanium dioxide solution in an injector, wherein the mass ratio of titanium dioxide in the titanium dioxide solution to hydrochloric acid with the mass fraction of 65% is 1:4, establishing a high-voltage electrostatic field in the injector nozzle and the receiving device, the injection speed is 0.02mm/s, spraying for 100s, washing with sodium hydroxide with the mass fraction of 10% until the pH is 7, washing with deionized water for 7 times, placing the washed mixture in a microwave reactor, and treating for 6min to obtain titanium dioxide porous microspheres;
(4) placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 40s, placing in a magnetron sputtering processor, and processing for 70s to obtain composite microspheres;
(5) and mixing the composite microspheres, glycol, glycerol and softened water according to the formula amount, and stirring at 100rpm for 5min to obtain the photocatalyst fluorescent ink.
Further, the specific preparation process of the self-made fluorescent agent in the step (1) is as follows:
a. dissolving veratone in absolute ethyl alcohol with the weight 6 times of that of the veratone, adding pyrene formaldehyde with the weight 1.2 times of that of the veratone while stirring at the speed of 60rpm, adjusting the stirring speed to 300rpm, adding a sodium hydroxide solution with the weight fraction of 10 percent and the weight 6.5 times of that of the veratone, stirring for 4 hours at the speed of 300rpm, filtering, washing for 5 times by deionized water, washing for 6 times by an ethanol-water mixed solvent, drying for 7 hours at room temperature, and obtaining a chalcone compound, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10: 7;
b. adding a chalcone compound into methanol with the mass 9 times that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass 1.5 times that of the chalcone compound and diethylamine with the mass 0.85 time that of the chalcone compound, heating to 55 ℃, reacting for 8 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 7, adding dichloromethane with the mass 6 times that of the chalcone compound, and extracting to obtain an organic layer; washing the organic layer with deionized water and saturated sodium chloride for 5 times, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 6h, and concentrating under reduced pressure at 200rpm and 65 deg.C for 3h to obtain nitroketone compound;
c. adding nitroketone compounds, absolute ethyl alcohol and ammonium acetate into a flask according to the mass ratio of 1:14:9.5, stirring at the speed of 200rpm, heating to 85 ℃, reacting for 12 hours, cooling to room temperature, concentrating under reduced pressure at the temperature of 300rpm and 90 ℃ for 5 hours, and filtering to obtain a dipyrrole compound;
d. putting a dipyrrole compound and dichloromethane which is 85 times of the dipyrrole compound in mass into a three-neck flask, stirring and dissolving, cooling to 5 ℃ in an ice-water bath at 0 ℃, adding a triethylamine/dichloromethane mixed solution which is 16.5 times of the dipyrrole compound in mass in a nitrogen atmosphere, wherein the mass ratio of triethylamine to dichloromethane in the triethylamine/dichloromethane mixed solution is 1:6, adding a boron trifluoride diethyl etherate/dichloromethane mixed solution which is 18.5 times of the dipyrrole compound in mass at a speed of 15 drops/min, wherein the mass ratio of boron trifluoride diethyl etherate to dichloromethane in the boron trifluoride diethyl etherate/dichloromethane mixed solution is 1:3, stirring at room temperature and a speed of 200rpm for 24 hours, washing with deionized water and saturated sodium chloride for 6 times in sequence, and concentrating under reduced pressure at 300rpm and 40 ℃ for 4 hours to obtain the fluorescent agent.
Further, the vacuum pressure of the spray freeze dryer in the step (2) is 40Pa, and the cold air volume is 6m3/min。
Further, the gas pressure of the cold plasma modification treatment equipment in the step (3) is 9Pa, the discharge power is 120W, sulfur hexafluoride is introduced into the pure argon plasma, the introduction flow rate is 60sccm, and the flow rate ratio is 0.53.
Further, the injector nozzle in the step (3) is a 16G flat-end dispensing needle head, the receiving device is aluminum foil paper, the voltage is 40kV, and the temperature is 120 ℃.
Further, the power of the microwave reactor in the step (3) is 200W, and the frequency is 2450 MHz.
Further, in the low-temperature plasma processor in the step (4), oxygen is used as a processing atmosphere, the gas flow is 1L/min, and the processing power is 6 kW.
Further, in the magnetron sputtering processor in the step (4), the sputtering power is 120W, the vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on the glass substrate, the temperature of the substrate is 100 ℃, the target material is cerium oxide, and the distance from the target material to the glass substrate is 10 cm.
Comparative example 1
A photocatalyst fluorescent ink and a preparation method thereof are disclosed, which mainly comprise the following components in parts by weight: 32 parts of BODIPY, 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.
A preparation method of photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) placing BODIPY in a spray freeze dryer, spraying out, keeping the temperature at-45 ℃ for 35min, heating to-20 ℃ at the speed of 2 ℃/min, and keeping the temperature for 54min to obtain BODIPY microspheres;
(2) placing BODIPY microspheres in cold plasma modification treatment equipment, pretreating for 126 seconds, placing the treated BODIPY microspheres in a receiving device, placing a titanium dioxide solution in an injector, wherein the mass ratio of titanium dioxide in the titanium dioxide solution to 65% hydrochloric acid is 1:3.12, establishing a high-voltage electrostatic field in the injector nozzle and the receiving device, the injection speed is 0.02mm/s, spraying for 117 seconds, washing with 10% sodium hydroxide until the pH is 7, washing with deionized water for 6 times, placing the washed BODIPY microspheres in a microwave reactor, and treating for 5 minutes to obtain titanium dioxide porous microspheres;
(3) placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 36s, then placing in a magnetron sputtering processor, and processing for 64s to obtain composite microspheres;
(4) and mixing the composite microspheres, glycol, glycerol and softened water according to the formula amount, and stirring at 70rpm for 8min to obtain the photocatalyst fluorescent ink.
Further, the vacuum pressure of the spray freeze dryer in the step (1) is 38Pa, and the cold air volume is 5.7m3/min。
Further, the gas pressure of the cold plasma modification treatment equipment in the step (2) is 8Pa, the discharge power is 110W, sulfur hexafluoride is introduced into the pure argon plasma, the introduction flow is 60sccm, and the flow ratio is 0.53; the power of the microwave reactor is 180W, and the frequency is 2450 MHz.
Further, the preparation steps of the titanium dioxide precursor solution in the step (2) are as follows: taking anhydrous ethanol with the mass of 1.72 times of that of tetra-n-butyl titanate and the anhydrous ethanol with the mass of 2.78 times of that of the tetra-n-butyl titanate, adding anhydrous ethanol mixed solution with the mass of 2.78 times of that of the tetra-n-butyl titanate into ice water bath at the temperature of 0 ℃ while stirring at the speed of 140rpm, wherein the mass ratio of the anhydrous ethanol to distilled water to glacial acetic acid in the anhydrous ethanol mixed solution is 1:0.32:0.33, and aging for 25h at room temperature to obtain the titanium dioxide precursor solution.
Further, the injector nozzle in the step (2) is a 15G flat dispensing needle, the receiving device is aluminum foil paper, the voltage is 35kV, and the temperature is 117 ℃.
Further, in the low-temperature plasma processor in the step (3), oxygen is used as a processing atmosphere, the gas flow is 0.9L/min, and the processing power is 5 kW.
Further, in the magnetron sputtering processor in the step (3), the sputtering power is 115W, the vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on the glass substrate, the temperature of the substrate is 91 ℃, the target material is cerium oxide, and the distance from the target material to the glass substrate is 7 cm.
Comparative example 2
A photocatalyst fluorescent ink and a preparation method thereof are disclosed, which mainly comprise the following components in parts by weight: 32 parts of a 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.
A preparation method of photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) mixing veratone with pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl etherate to prepare a self-made fluorescent agent;
(2) placing the self-made fluorescer in a spray freeze dryer, spraying out, keeping the temperature at minus 45 ℃ for 35min, heating to minus 20 ℃ at the speed of 2 ℃/min, and keeping the temperature for 54min to obtain fluorescer-making microspheres;
(3) placing the self-made fluorescer microsphere in a receiving device, placing a titanium dioxide solution in an injector, wherein the mass ratio of titanium dioxide in the titanium dioxide solution to hydrochloric acid with the mass fraction of 65% is 1:3.12, establishing a high-voltage electrostatic field in the injector nozzle and the receiving device, the injection speed is 0.02mm/s, spraying 117s of the solution, washing the solution with sodium hydroxide with the mass fraction of 10% until the pH value is 7, washing the solution with deionized water for 6 times, placing the solution in a microwave reactor, and treating the solution for 5min to obtain the titanium dioxide porous microsphere;
(4) placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 36s, then placing in a magnetron sputtering processor, and processing for 64s to obtain composite microspheres;
(5) and mixing the composite microspheres, glycol, glycerol and softened water according to the formula amount, and stirring at 70rpm for 8min to obtain the photocatalyst fluorescent ink.
Further, the specific preparation process of the self-made fluorescent agent in the step (1) is as follows:
a. dissolving veratone in absolute ethyl alcohol with the weight 5.77 times of that of the veratone, adding pyrene formaldehyde with the weight 1.09 times of that of the veratone while stirring at 56rpm, adjusting the stirring speed to 220rpm, adding a sodium hydroxide solution with the weight fraction of 10 percent and the weight 6.35 times of that of the veratone, stirring for 4.5 hours at 260rpm, filtering, washing for 4 times with deionized water, washing for 5 times with an ethanol-water mixed solvent, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying for 6.5 hours at room temperature to obtain a chalcone compound;
b. adding a chalcone compound into methanol with the mass 8.71 times that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass 1.29 times that of the chalcone compound and diethylamine with the mass 0.83 times that of the chalcone compound, heating to 54 ℃, reacting for 7.5 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 6, adding dichloromethane with the mass 5.13 times that of the chalcone compound, and extracting to obtain an organic layer; sequentially washing the organic layer with deionized water and saturated sodium chloride for 4 times, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 5.5h, and concentrating under reduced pressure at 200rpm and 65 deg.C for 2.5h to obtain nitrone compounds;
c. adding nitroketone compound, absolute ethyl alcohol and ammonium acetate into a flask according to the mass ratio of 1:13.59:9.32, stirring at the speed of 150rpm, heating to 83 ℃, reacting for 11.5 hours, cooling to room temperature, concentrating under reduced pressure at the temperature of 300rpm and 90 ℃ for 4 hours, and filtering to obtain a dipyrrole compound;
d. putting a dipyrrole compound and dichloromethane which is 83.21 times of the mass of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 4 ℃ in an ice-water bath at 0 ℃, adding a triethylamine/dichloromethane mixed solution which is 16.31 times of the mass of the dipyrrole compound into the mixed solution under a nitrogen atmosphere, wherein the mass ratio of triethylamine to dichloromethane in the triethylamine/dichloromethane mixed solution is 1:6, adding a boron trifluoride diethyl ether/dichloromethane mixed solution which is 18.31 times of the mass of the dipyrrole compound into the mixed solution at a speed of 13 drops/min, wherein the mass ratio of boron trifluoride diethyl ether to dichloromethane in the boron trifluoride diethyl ether/dichloromethane mixed solution is 1:3, stirring at room temperature and a speed of 110rpm for 25.5h, washing with deionized water and saturated sodium chloride for 5 times in sequence, and concentrating under reduced pressure at 300rpm and 40 ℃ for 3.5h to obtain the fluorescent agent.
Further, the vacuum pressure of the spray freeze dryer in the step (2) is 38Pa, and the cold air volume is 5.7m3/min。
Further, the injector nozzle in the step (3) is a 15G flat-end dispensing needle head, the receiving device is aluminum foil paper, the voltage is 35kV, and the temperature is 117 ℃.
Further, the power of the microwave reactor in the step (3) is 180W, and the frequency is 2450 MHz.
Further, in the low-temperature plasma processor in the step (4), oxygen is used as a processing atmosphere, the gas flow is 0.9L/min, and the processing power is 5 kW.
Further, in the magnetron sputtering processor in the step (4), the sputtering power is 115W, the vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on the glass substrate, the temperature of the substrate is 91 ℃, the target material is cerium oxide, and the distance from the target material to the glass substrate is 7 cm.
Comparative example 3
A photocatalyst fluorescent ink and a preparation method thereof are disclosed, which mainly comprise the following components in parts by weight: 32 parts of a 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.
A preparation method of photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) mixing veratone with pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl etherate to prepare a self-made fluorescent agent;
(2) placing the self-made fluorescer in a spray freeze dryer, spraying out, keeping the temperature at minus 45 ℃ for 35min, heating to minus 20 ℃ at the speed of 2 ℃/min, and keeping the temperature for 54min to obtain fluorescer-making microspheres;
(3) placing the self-made fluorescer microspheres in cold plasma modification treatment equipment, pretreating for 126s, adding titanium dioxide, placing in a microwave reactor, and treating for 5min to obtain titanium dioxide porous microspheres;
(4) placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 36s, then placing in a magnetron sputtering processor, and processing for 64s to obtain composite microspheres;
(5) and mixing the composite microspheres, glycol, glycerol and softened water according to the formula amount, and stirring at 70rpm for 8min to obtain the photocatalyst fluorescent ink.
Further, the specific preparation process of the self-made fluorescent agent in the step (1) is as follows:
a. dissolving veratone in absolute ethyl alcohol with the weight 5.77 times of that of the veratone, adding pyrene formaldehyde with the weight 1.09 times of that of the veratone while stirring at 56rpm, adjusting the stirring speed to 220rpm, adding a sodium hydroxide solution with the weight fraction of 10 percent and the weight 6.35 times of that of the veratone, stirring for 4.5 hours at 260rpm, filtering, washing for 4 times with deionized water, washing for 5 times with an ethanol-water mixed solvent, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying for 6.5 hours at room temperature to obtain a chalcone compound;
b. adding a chalcone compound into methanol with the mass 8.71 times that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass 1.29 times that of the chalcone compound and diethylamine with the mass 0.83 times that of the chalcone compound, heating to 54 ℃, reacting for 7.5 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 6, adding dichloromethane with the mass 5.13 times that of the chalcone compound, and extracting to obtain an organic layer; sequentially washing the organic layer with deionized water and saturated sodium chloride for 4 times, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 5.5h, and concentrating under reduced pressure at 200rpm and 65 deg.C for 2.5h to obtain nitrone compounds;
c. adding nitroketone compound, absolute ethyl alcohol and ammonium acetate into a flask according to the mass ratio of 1:13.59:9.32, stirring at the speed of 150rpm, heating to 83 ℃, reacting for 11.5 hours, cooling to room temperature, concentrating under reduced pressure at the temperature of 300rpm and 90 ℃ for 4 hours, and filtering to obtain a dipyrrole compound;
d. putting a dipyrrole compound and dichloromethane which is 83.21 times of the mass of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 4 ℃ in an ice-water bath at 0 ℃, adding a triethylamine/dichloromethane mixed solution which is 16.31 times of the mass of the dipyrrole compound into the mixed solution under a nitrogen atmosphere, wherein the mass ratio of triethylamine to dichloromethane in the triethylamine/dichloromethane mixed solution is 1:6, adding a boron trifluoride diethyl ether/dichloromethane mixed solution which is 18.31 times of the mass of the dipyrrole compound into the mixed solution at a speed of 13 drops/min, wherein the mass ratio of boron trifluoride diethyl ether to dichloromethane in the boron trifluoride diethyl ether/dichloromethane mixed solution is 1:3, stirring at room temperature and a speed of 110rpm for 25.5h, washing with deionized water and saturated sodium chloride for 5 times in sequence, and concentrating under reduced pressure at 300rpm and 40 ℃ for 3.5h to obtain the fluorescent agent.
Further, the vacuum pressure of the spray freeze dryer in the step (2) is 38Pa, and the cold air volume is 5.7m3/min。
Further, the gas pressure of the cold plasma modification treatment equipment in the step (3) is 8Pa, the discharge power is 110W, sulfur hexafluoride is introduced into the pure argon plasma, the introduction flow rate is 60sccm, and the flow rate ratio is 0.53.
Further, the power of the microwave reactor in the step (3) is 180W, and the frequency is 2450 MHz.
Further, in the low-temperature plasma processor in the step (4), oxygen is used as a processing atmosphere, the gas flow is 0.9L/min, and the processing power is 5 kW.
Further, in the magnetron sputtering processor in the step (4), the sputtering power is 115W, the vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on the glass substrate, the temperature of the substrate is 91 ℃, the target material is cerium oxide, and the distance from the target material to the glass substrate is 7 cm.
Comparative example 4
A photocatalyst fluorescent ink and a preparation method thereof are disclosed, which mainly comprise the following components in parts by weight: 32 parts of a 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.
A preparation method of photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) mixing veratone with pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl etherate to prepare a self-made fluorescent agent;
(2) placing the self-made fluorescer in a spray freeze dryer, spraying out, keeping the temperature at minus 45 ℃ for 35min, heating to minus 20 ℃ at the speed of 2 ℃/min, and keeping the temperature for 54min to obtain fluorescer-making microspheres;
(3) placing the self-made fluorescer microspheres in cold plasma modification treatment equipment, pretreating for 126 seconds, placing the pretreated self-made fluorescer microspheres in a receiving device, placing a titanium dioxide solution in an injector, wherein the mass ratio of titanium dioxide in the titanium dioxide solution to hydrochloric acid with the mass fraction of 65% is 1:3.12, establishing a high-voltage electrostatic field in a nozzle of the injector and the receiving device, the injection speed is 0.02mm/s, spraying for 117 seconds, washing with sodium hydroxide with the mass fraction of 10% until the pH value is 7, and washing with deionized water for 6 times to obtain titanium dioxide porous microspheres;
(4) placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 36s, then placing in a magnetron sputtering processor, and processing for 64s to obtain composite microspheres;
(5) and mixing the composite microspheres, glycol, glycerol and softened water according to the formula amount, and stirring at 70rpm for 8min to obtain the photocatalyst fluorescent ink.
Further, the specific preparation process of the self-made fluorescent agent in the step (1) is as follows:
a. dissolving veratone in absolute ethyl alcohol with the weight 5.77 times of that of the veratone, adding pyrene formaldehyde with the weight 1.09 times of that of the veratone while stirring at 56rpm, adjusting the stirring speed to 220rpm, adding a sodium hydroxide solution with the weight fraction of 10 percent and the weight 6.35 times of that of the veratone, stirring for 4.5 hours at 260rpm, filtering, washing for 4 times with deionized water, washing for 5 times with an ethanol-water mixed solvent, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying for 6.5 hours at room temperature to obtain a chalcone compound;
b. adding a chalcone compound into methanol with the mass 8.71 times that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass 1.29 times that of the chalcone compound and diethylamine with the mass 0.83 times that of the chalcone compound, heating to 54 ℃, reacting for 7.5 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 6, adding dichloromethane with the mass 5.13 times that of the chalcone compound, and extracting to obtain an organic layer; sequentially washing the organic layer with deionized water and saturated sodium chloride for 4 times, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 5.5h, and concentrating under reduced pressure at 200rpm and 65 deg.C for 2.5h to obtain nitrone compounds;
c. adding nitroketone compound, absolute ethyl alcohol and ammonium acetate into a flask according to the mass ratio of 1:13.59:9.32, stirring at the speed of 150rpm, heating to 83 ℃, reacting for 11.5 hours, cooling to room temperature, concentrating under reduced pressure at the temperature of 300rpm and 90 ℃ for 4 hours, and filtering to obtain a dipyrrole compound;
d. putting a dipyrrole compound and dichloromethane which is 83.21 times of the mass of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 4 ℃ in an ice-water bath at 0 ℃, adding a triethylamine/dichloromethane mixed solution which is 16.31 times of the mass of the dipyrrole compound into the mixed solution under a nitrogen atmosphere, wherein the mass ratio of triethylamine to dichloromethane in the triethylamine/dichloromethane mixed solution is 1:6, adding a boron trifluoride diethyl ether/dichloromethane mixed solution which is 18.31 times of the mass of the dipyrrole compound into the mixed solution at a speed of 13 drops/min, wherein the mass ratio of boron trifluoride diethyl ether to dichloromethane in the boron trifluoride diethyl ether/dichloromethane mixed solution is 1:3, stirring at room temperature and a speed of 110rpm for 25.5h, washing with deionized water and saturated sodium chloride for 5 times in sequence, and concentrating under reduced pressure at 300rpm and 40 ℃ for 3.5h to obtain the fluorescent agent.
Further, the vacuum pressure of the spray freeze dryer in the step (2) is 38Pa, and the cold air volume is 5.7m3/min。
Further, the gas pressure of the cold plasma modification treatment equipment in the step (3) is 8Pa, the discharge power is 110W, sulfur hexafluoride is introduced into the pure argon plasma, the introduction flow rate is 60sccm, and the flow rate ratio is 0.53.
Further, the injector nozzle in the step (3) is a 15G flat-end dispensing needle head, the receiving device is aluminum foil paper, the voltage is 35kV, and the temperature is 117 ℃.
Further, in the low-temperature plasma processor in the step (4), oxygen is used as a processing atmosphere, the gas flow is 0.9L/min, and the processing power is 5 kW.
Further, in the magnetron sputtering processor in the step (4), the sputtering power is 115W, the vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on the glass substrate, the temperature of the substrate is 91 ℃, the target material is cerium oxide, and the distance from the target material to the glass substrate is 7 cm.
Comparative example 5
A photocatalyst fluorescent ink and a preparation method thereof are disclosed, which mainly comprise the following components in parts 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.
A preparation method of photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) mixing veratone with pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl etherate to prepare a self-made fluorescent agent;
(2) placing the self-made fluorescer in a spray freeze dryer, spraying out, keeping the temperature at minus 45 ℃ for 35min, heating to minus 20 ℃ at the speed of 2 ℃/min, and keeping the temperature for 54min to obtain fluorescer-making microspheres;
(3) placing the self-made fluorescer microspheres in cold plasma modification treatment equipment, pretreating for 126 seconds, placing the pretreated fluorescer microspheres in a receiving device, placing a titanium dioxide solution in an injector, wherein the mass ratio of titanium dioxide in the titanium dioxide solution to hydrochloric acid with the mass fraction of 65% is 1:3.12, establishing a high-voltage electrostatic field in the injector nozzle and the receiving device, the injection speed is 0.02mm/s, spraying for 117 seconds, washing with sodium hydroxide with the mass fraction of 10% until the pH value is 7, washing with deionized water for 6 times, placing in a microwave reactor, and treating for 5min to obtain titanium dioxide porous microspheres;
(4) mixing the titanium dioxide porous microspheres, glycol, glycerol and softened water according to the formula amount, and stirring at 70rpm for 8min to obtain the photocatalyst fluorescent ink.
Further, the specific preparation process of the self-made fluorescent agent in the step (1) is as follows:
a. dissolving veratone in absolute ethyl alcohol with the weight 5.77 times of that of the veratone, adding pyrene formaldehyde with the weight 1.09 times of that of the veratone while stirring at 56rpm, adjusting the stirring speed to 220rpm, adding a sodium hydroxide solution with the weight fraction of 10 percent and the weight 6.35 times of that of the veratone, stirring for 4.5 hours at 260rpm, filtering, washing for 4 times with deionized water, washing for 5 times with an ethanol-water mixed solvent, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying for 6.5 hours at room temperature to obtain a chalcone compound;
b. adding a chalcone compound into methanol with the mass 8.71 times that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass 1.29 times that of the chalcone compound and diethylamine with the mass 0.83 times that of the chalcone compound, heating to 54 ℃, reacting for 7.5 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 6, adding dichloromethane with the mass 5.13 times that of the chalcone compound, and extracting to obtain an organic layer; sequentially washing the organic layer with deionized water and saturated sodium chloride for 4 times, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 5.5h, and concentrating under reduced pressure at 200rpm and 65 deg.C for 2.5h to obtain nitrone compounds;
c. adding nitroketone compound, absolute ethyl alcohol and ammonium acetate into a flask according to the mass ratio of 1:13.59:9.32, stirring at the speed of 150rpm, heating to 83 ℃, reacting for 11.5 hours, cooling to room temperature, concentrating under reduced pressure at the temperature of 300rpm and 90 ℃ for 4 hours, and filtering to obtain a dipyrrole compound;
d. putting a dipyrrole compound and dichloromethane which is 83.21 times of the mass of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 4 ℃ in an ice-water bath at 0 ℃, adding a triethylamine/dichloromethane mixed solution which is 16.31 times of the mass of the dipyrrole compound into the mixed solution under a nitrogen atmosphere, wherein the mass ratio of triethylamine to dichloromethane in the triethylamine/dichloromethane mixed solution is 1:6, adding a boron trifluoride diethyl ether/dichloromethane mixed solution which is 18.31 times of the mass of the dipyrrole compound into the mixed solution at a speed of 13 drops/min, wherein the mass ratio of boron trifluoride diethyl ether to dichloromethane in the boron trifluoride diethyl ether/dichloromethane mixed solution is 1:3, stirring at room temperature and a speed of 110rpm for 25.5h, washing with deionized water and saturated sodium chloride for 5 times in sequence, and concentrating under reduced pressure at 300rpm and 40 ℃ for 3.5h to obtain the fluorescent agent.
Further, the vacuum pressure of the spray freeze dryer in the step (2) is 38Pa, and the cold air volume is 5.7m3/min。
Further, the gas pressure of the cold plasma modification treatment equipment in the step (3) is 8Pa, the discharge power is 110W, sulfur hexafluoride is introduced into the pure argon plasma, the introduction flow rate is 60sccm, and the flow rate ratio is 0.53.
Further, the injector nozzle in the step (3) is a 15G flat-end dispensing needle head, the receiving device is aluminum foil paper, the voltage is 35kV, and the temperature is 117 ℃.
Further, the power of the microwave reactor in the step (3) is 180W, and the frequency is 2450 MHz.
Comparative example 6
A photocatalyst fluorescent ink and a preparation method thereof are disclosed, which mainly comprise the following components in parts by weight: 32 parts of BODIPY, 23 parts of titanium dioxide, 6 parts of ethylene glycol, 2 parts of glycerol and 60 parts of softened water.
A preparation method of photocatalyst fluorescent ink mainly comprises the following preparation steps:
(1) placing BODIPY in a spray freeze dryer, spraying out, keeping the temperature at-45 ℃ for 35min, heating to-20 ℃ at the speed of 2 ℃/min, and keeping the temperature for 54min to obtain microspheres;
(2) mixing the microspheres, titanium dioxide, ethylene glycol, glycerol and softened water according to the formula ratio, and stirring at 70rpm for 8min to obtain the photocatalyst fluorescent ink.
Further, the vacuum pressure of the spray freeze dryer in the step (1) is 38Pa, and the cold air volume is 5.7m3/min。
Examples of effects
Table 1 below shows the results of performance analysis using the photocatalyst fluorescent inks of examples 1 to 2 and comparative examples 1 to 6 of the present invention.
TABLE 1
From the comparison of the experimental data of examples 1 and 2 and comparative example 6, it can be found that the use of the self-made fluorescent agent in the product allows the ink to develop color only under the infrared light and to have photostability; the titanium dioxide microspheres are prepared by utilizing plasma, electrostatic spraying and microwave, so that the titanium dioxide and the self-made fluorescent agent are tightly crosslinked, the stability of the ink is improved, and the visible light activity of the titanium dioxide is improved by introducing cerium oxide, so that the ink can be degraded and disappear under the visible light, and the confidentiality is good; from the comparison of experimental data of examples 1 and 2 and comparative example 1, it can be found that if the self-made fluorescent agent is prepared without veratone, pyrene formaldehyde and boron trifluoride, a conjugated system and small steric hindrance of pyrene formaldehyde cannot be utilized, so that the energy gap of the self-made fluorescent agent is large, and an electron donating group cannot be introduced, so that the wavelength is in a visible light range, and therefore the ink can develop color under visible light, and the confidentiality of the ink is poor; compared with the experimental data of the embodiment 1 and the embodiment 2 and the comparative example 2, it can be found that electric negative ions cannot be introduced to the surface of the self-made fluorescer microsphere without using a plasma source in the process of preparing the titanium dioxide porous microsphere, so that the electrostatic adsorption with the titanium dioxide is weak, the stability of the ink is influenced, the surface titanium dioxide is less, only a small amount of cerium oxide can be introduced, the molecular chain of the self-made fluorescer cannot be completely broken, and the degradability of the ink is influenced; compared with the experimental data of the embodiment 1 and the embodiment 2 and the comparative example 3, it can be found that titanium dioxide cannot be atomized and cannot be uniformly deposited on the surface of the self-made fluorescent agent microsphere without electrostatic spraying in the process of preparing the titanium dioxide porous microsphere, so that agglomeration is easy to occur, the crosslinking degree of the titanium dioxide and the self-made fluorescent agent microsphere is influenced, and the stability of the ink is reduced; from the comparison of the experimental data of examples 1 and 2 and comparative example 4, it can be found that the self-made fluorescent agent and titanium dioxide atoms cannot react without microwave treatment in the process of preparing the titanium dioxide porous microspheres, and the self-made fluorescent agent and the titanium dioxide atoms cannot be tightly cross-linked, so that the stability of the ink is affected; from the comparison of the experimental data of examples 1 and 2 and comparative example 5, it can be found that if cerium oxide is not introduced, the wavelength range of titanium dioxide cannot be widened, the visible light activity of titanium dioxide is weakened, so that titanium dioxide cannot catalyze and produce free radicals and active oxygen under visible light, the self-made fluorescent agent cannot be damaged, the ink still exists on paper and cannot be degraded, and the confidentiality of the ink is poor.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (9)
1. A preparation method of photocatalyst fluorescent ink is characterized by mainly comprising the following preparation steps:
(1) mixing veratone with pyrene formaldehyde to prepare a chalcone compound, and adding nitromethane and boron trifluoride diethyl etherate to prepare a self-made fluorescent agent;
(2) placing the self-made fluorescer in a spray freeze dryer, spraying out, keeping the temperature at minus 45 ℃ for 30-40 min, heating to minus 20 ℃ at the speed of 1-3 ℃/min, and keeping the temperature for 50-60 min to obtain fluorescer microspheres;
(3) placing the self-made fluorescer microspheres in cold plasma modification treatment equipment, pretreating for 120-130 s, placing the pretreated microspheres in a receiving device, placing a titanium dioxide solution in an injector, wherein the mass ratio of titanium dioxide to hydrochloric acid with the mass fraction of 65% is 1: 3-4, establishing a high-voltage electrostatic field in a nozzle of the injector and the receiving device, the injection speed is 0.01-0.02 mm/s, spraying for 100-120 s, washing with 10% sodium hydroxide until the pH value is 6-7, washing with deionized water for 5-7 times, placing the washed microspheres in a microwave reactor, and treating for 4-6 min to obtain titanium dioxide porous microspheres;
(4) placing the titanium dioxide porous microspheres in a low-temperature plasma processor, processing for 30-40 s, then placing in a magnetron sputtering processor, and processing for 50-70 s to obtain composite microspheres;
(5) mixing the composite microspheres, ethylene glycol, glycerol and softened water according to the formula amount, and stirring at 50-100 rpm for 5-10 min to obtain the photocatalyst fluorescent ink.
2. The method for preparing photocatalyst fluorescent ink according to claim 1, wherein the self-made fluorescent agent in the step (1) is prepared by the following specific steps:
a. dissolving veratone in absolute ethyl alcohol with the weight 5.5-6 times of that of the veratone, stirring at the speed of 50-60 rpm, adding pyrene formaldehyde with the weight 0.6-1.2 times of that of the veratone, then adjusting the stirring speed to 200-300 rpm, adding a sodium hydroxide solution with the weight fraction of 10% and the weight 6-6.5 times of that of the veratone, stirring at the speed of 200-300 rpm for 4-5 h, filtering, washing with deionized water for 3-5 times, washing with an ethanol-water mixed solvent for 4-6 times, wherein the volume ratio of ethanol to water in the ethanol-water mixed solvent is 10:7, and drying at room temperature for 6-7 h to obtain a chalcone compound;
b. adding a chalcone compound into methanol with the mass 8.5-9 times that of the chalcone compound, stirring and dissolving, adding nitromethane with the mass 1-1.5 times that of the chalcone compound and diethylamine with the mass 0.8-0.85 time that of the chalcone compound, heating to 51-55 ℃, reacting for 7-8 hours, cooling to room temperature, adding hydrochloric acid with the mass fraction of 10% until the pH value of the solution is 6-7, adding dichloromethane with the mass 4-6 times that of the chalcone compound, and extracting to obtain an organic layer; washing the organic layer with deionized water and saturated sodium chloride for 4-5 times in sequence, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 4-6 h, and concentrating under reduced pressure at 200rpm and 65 ℃ for 2-3 h to obtain nitroketone compounds;
c. adding a nitroketone compound, absolute ethyl alcohol and ammonium acetate into a flask according to the mass ratio of 1: 13.5-14: 9-9.5, stirring at the speed of 100-200 rpm, heating to 80-85 ℃, reacting for 10-12 hours, cooling to room temperature, concentrating at 300rpm and 90 ℃ under reduced pressure for 3-5 hours, and filtering to obtain a dipyrrole compound;
d. putting a dipyrrole compound and dichloromethane with the mass of 80-85 times of that of the dipyrrole compound into a three-neck flask, stirring and dissolving, cooling to 0-5 ℃ in ice-water bath at 0 ℃, adding a triethylamine/dichloromethane mixed solution with 16-16.5 times of the mass of the dipyrrole compound in the nitrogen atmosphere, wherein the mass ratio of triethylamine to dichloromethane in the triethylamine/dichloromethane mixed solution is 1:6, adding boron trifluoride diethyl etherate/dichloromethane mixed liquid with the mass of 18-18.5 times of that of the dipyrrole compound at the speed of 10-15 drops/min, wherein the mass ratio of the boron trifluoride diethyl etherate to the dichloromethane in the boron trifluoride diethyl etherate/dichloromethane mixed liquid is 1:3, at room temperature, stirring at a speed of 100-200 rpm for 24-26 h, washing with deionized water and saturated sodium chloride for 4-6 times in sequence, and concentrating under reduced pressure at 300rpm and 40 ℃ for 3-4 h to obtain the fluorescent agent.
3. The method for preparing photocatalyst fluorescent ink as claimed in claim 2, wherein the vacuum pressure of the spray freeze dryer in the step (2) is 35 to 40Pa, and the cold air volume is 5.5 to 6m3/min。
4. The method for preparing photocatalyst fluorescent ink as claimed in claim 3, wherein the gas pressure of the cold plasma modification treatment device in step (3) is 7-9 Pa, the discharge power is 100-120W, sulfur hexafluoride is introduced into the pure argon plasma, the flow rate is 60sccm, and the flow rate ratio is 0.53.
5. The method according to claim 4, wherein the injector nozzle in step (3) is a 14-16G flat dispensing needle, the receiver is aluminum foil paper, the voltage is 30-40 kV, and the temperature is 100-120 ℃.
6. The method of claim 5, wherein the microwave reactor in step (3) has a power of 160-200W and a frequency of 2450 MHz.
7. The method according to claim 6, wherein the low-temperature plasma processor in step (4) uses oxygen as a processing atmosphere, the gas flow rate is 0.8-1L/min, and the processing power is 4-6 kW.
8. The method for preparing photocatalyst fluorescent ink according to claim 7, wherein sputtering power in the magnetron sputtering processor in the step (4) is 100-120W, vacuum degree is 0.001Pa, the titanium dioxide porous microspheres are placed on a glass substrate, the temperature of the substrate is 80-100 ℃, the target material is cerium oxide, and the distance from the target material to the glass substrate is 6-10 cm.
9. The method for preparing the photocatalyst fluorescent ink as claimed in claim 8, wherein the photocatalyst fluorescent ink prepared by the method for preparing the photocatalyst fluorescent ink mainly comprises, by weight, 30-40 parts of a 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.
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