CN112691622B - Nitrogen-doped nano titanium dioxide/aromatic microcapsule and preparation method and application thereof - Google Patents
Nitrogen-doped nano titanium dioxide/aromatic microcapsule and preparation method and application thereof Download PDFInfo
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- CN112691622B CN112691622B CN202011431141.0A CN202011431141A CN112691622B CN 112691622 B CN112691622 B CN 112691622B CN 202011431141 A CN202011431141 A CN 202011431141A CN 112691622 B CN112691622 B CN 112691622B
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
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- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
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- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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Abstract
The invention relates to the field of air purification, and discloses a nitrogen-doped nano titanium dioxide/aromatic microcapsule, and a preparation method and application thereof. The core material of the microcapsule is photocatalyst particles and water-soluble essence, and the wall material is polyurea; the water-soluble essence is loaded in the photocatalyst particles; the photocatalyst particles include nitrogen-doped titanium dioxide. The nitrogen-doped nano titanium dioxide/aromatic microcapsule adopts nitrogen-doped titanium dioxide as a core material, so that the problem of reduction of the photocatalytic activity of the titanium dioxide after polyurea coating can be solved, and the microcapsule is ensured to have a better air purification effect; polyurea is adopted as a wall material, so that direct contact between titanium dioxide and chemical fibers can be reduced, and the titanium dioxide is prevented from accelerating chemical fiber aging; the spontaneous release of the essence can be reduced, and the durability and controllability of the air freshening effect of the essence are realized; and the polyurea has good optical stability and chemical resistance, and is not easy to degrade and lose efficacy.
Description
Technical Field
The invention relates to the field of air purification, in particular to a nitrogen-doped nano titanium dioxide/aromatic microcapsule and a preparation method and application thereof.
Background
In China, 90% of newly decorated houses have standard exceeding pollution, particularly, formaldehyde standard exceeding is more serious, and more than 95% of newly decorated houses do not meet the standard. Statistics of the united states environmental protection agency show that the indoor air pollution level is often 2-5 times that of the outdoor air, sometimes even more than 100 times, and more than 80% of the time is spent indoors. This poses a great threat to human health. Therefore, in order to realize sustainable development of the air purification industry, a green and environment-friendly air pollutant degradation technology must be researched and developed.
The photocatalysis technology is a high-tech leading edge purification technology which is started in recent years, and semiconductor nano particles can directly decompose pollutants such as formaldehyde, benzene, ammonia and the like in the air into harmless inorganic small molecules such as CO under the irradiation of ultraviolet rays2、H2O、N2And the like, and can kill microorganisms with protein structures, such as bacteria, viruses and the like, thereby achieving the aim of purifying air. Nano TiO 22The catalyst is favored by the advantages of strong pollutant adsorption capacity, high photocatalytic activity, chemical and photo corrosion resistance, stable property, no toxicity, low price and the like, and is an environment-friendly catalyst with development prospect.
In addition, the natural aromatic substances in the essence have the functions of sedation, sterilization, health care and the like, and can endow the air purification material with the unique use function. However, in order to improve the sustained release property and the use safety, the essence is usually encapsulated in a polymer film by utilizing the coacervation of natural or synthetic polymer film-forming materials to form fragrant microcapsules, and the fragrance is slowly and regularly released only by gradually or through the damage of certain external stimuli (such as heat or physical friction) on the wall material.
The photocatalysis technology and the aromatic microcapsule technology are combined, so that better air pollutant degradation and air refreshing effects can be obtained. For example, chinese patent application No. CN201711014951.4 discloses a method for preparing polyurethane elastic fiber with persistent fragrance, which comprises using a mixture of mesoporous material and water-soluble essence as the core of the microcapsule, and performing interfacial polymerization on pyromellitic chloride and diamine to prepare aromatic microcapsule with polyimide as the capsule wall; polyether glycol, diisocyanate and an amine chain extender react in a polar solvent to obtain a polyurethane urea solution; adding aromatic microcapsules and auxiliary materials and auxiliaries into the polyurethane urea solution to obtain the polyurethane urea spinning solution. After curing and filtering, the polyurethane elastic fiber with lasting fragrance is prepared by a dry spinning technology. The aromatic microcapsules obtained by this method have the following problems: although the release of essence can be slowed down by the coating of polyimide, the absorption of titanium dioxide to ultraviolet light can be reduced, so that the photocatalytic activity of the microcapsule is low, and the degradation effect on air pollutants is poor.
Disclosure of Invention
In order to solve the technical problems, the invention provides a nitrogen-doped nano titanium dioxide/aromatic microcapsule, and a preparation method and application thereof. The microcapsule adopts nitrogen-doped titanium dioxide, and has a good air pollutant degradation effect.
The specific technical scheme of the invention is as follows:
a nitrogen-doped nano titanium dioxide/aromatic microcapsule is characterized in that a core material of the microcapsule is photocatalyst particles and water-soluble essence, and a wall material is polyurea; the water-soluble essence is loaded in the photocatalyst particles; the photocatalyst particles include nitrogen-doped titanium dioxide.
In the microcapsule structure of the present invention, polyurea is used to coat titanium dioxide, so that when applied to textile materials, direct contact between titanium dioxide and chemical fibers can be reduced, and accelerated aging of chemical fibers by titanium dioxide can be prevented, and air pollutants (such as formaldehyde, toluene, etc.) can be adsorbed into titanium dioxide, and thus, the titanium dioxide can still be sufficiently contacted. However, polyurea coatings can result in reduced exposure of titanium dioxide to ultraviolet light, affecting its photocatalytic activity.
In the present invention, the photocatalytic activity of nitrogen-doped titanium dioxide is utilized to degrade air pollutants and kill bacteria, viruses, and other microorganisms having a protein structure. Compared with common titanium dioxide which can only absorb ultraviolet light, the nitrogen-doped titanium dioxide has the advantages that due to lattice distortion, the energy gap is reduced, the maximum absorption wavelength is red-shifted, and the nitrogen-doped titanium dioxide also has an absorption effect on visible light, so that the sunlight utilization rate is higher, the problem of reduction of the photocatalytic activity of the titanium dioxide coated by polyurea can be solved, and the microcapsule is ensured to have a better air purification effect.
The essence is loaded in the photocatalyst particles, and polyurea is coated outside the photocatalyst particles, so that spontaneous release of the essence can be reduced, but the essence can be released when the essence is rubbed, and therefore, the microcapsule disclosed by the invention is suitable for an air purification textile material, and is beneficial to realizing the durability and controllability of the air freshening effect of the essence. In addition, the polyurea is adopted as the wall material, and the advantages are also as follows: the polyurea has good optical stability, can not be degraded due to the photocatalysis of the titanium dioxide, and has good chemical resistance.
Preferably, the water-soluble essence comprises at least one of lemon essence, rose essence, mint essence and jasmine essence.
Preferably, the photocatalyst particles are nitrogen-doped titanium dioxide particles, and the preparation method comprises the following steps: uniformly mixing urea and titanium dioxide according to the mass ratio of 1:4-5, calcining at the temperature of 450-550 ℃, and grinding to obtain the nitrogen-doped titanium dioxide particles.
Furthermore, the particle size of the titanium dioxide is 50-100 nm.
Further, the particle size of the nitrogen-doped titanium dioxide is 20-70 nm.
Preferably, the photocatalyst particles are modified activated carbon @ nitrogen-doped titanium dioxide particles, and the preparation method comprises the following steps:
(1.1) preparing acrylate modified activated carbon: dispersing mesoporous activated carbon with the particle size of 400-500nm into N, N-dimethylacetamide, adding tetraethylammonium bromide, uniformly mixing, and dropwise adding acrylic glycidyl ether under stirring, wherein the mass ratio of the acrylic glycidyl ether to the mesoporous activated carbon is 4-6: 1; after the dropwise addition is finished, reacting for 3-5h at the temperature of 120-130 ℃, and filtering and washing to obtain the acrylate modified activated carbon;
in the step (1.1), carboxyl on the surface of the mesoporous activated carbon and epoxy in the glycidyl acrylate ether are subjected to ring-opening reaction under the catalysis of tetraethylammonium bromide, so that the glycidyl acrylate ether is grafted to the mesoporous activated carbon.
(1.2) preparing modified activated carbon: dispersing acrylate modified activated carbon into N, N-dimethylacetamide, dropwise adding an N, N-dimethylacetamide solution of a light stabilizer SEED into the reaction liquid under stirring, wherein the mass ratio of the light stabilizer SEED to the acrylate modified activated carbon is 5-10: 1; after the dropwise addition, reacting at 70-80 ℃ for 3-4h, filtering, washing and drying to obtain modified activated carbon;
in the step (1.2), the imino group in the light stabilizer SEED (i.e. N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide) and the alkenyl group (from acrylic acid glycidyl ether) on the acrylate modified activated carbon undergo an addition reaction, so that the light stabilizer SEED is grafted to the mesoporous activated carbon.
(1.3) preparation of nitrogen-doped titanium dioxide: uniformly mixing urea and titanium dioxide according to the mass ratio of 1:4-5, calcining at the temperature of 450-550 ℃, and grinding to prepare nitrogen-doped titanium dioxide with the particle size of 5-10 nm;
(1.4) preparing modified activated carbon @ nitrogen-doped titanium dioxide particles: mixing the modified activated carbon and the nitrogen-doped titanium dioxide according to the mass ratio of 2-4:1, ball-milling for 2-3h at the speed of 600r/min under 500-.
The nitrogen-doped titanium dioxide generates a hole-electron pair under the excitation of light, a part of electrons are combined with oxygen to generate OH, and the OH with strong oxidizing property can cause the oxidative decomposition of essence loaded in the nitrogen-doped titanium dioxide, thereby influencing the durability of the aromatic effect of the microcapsule.
In the modified activated carbon @ nitrogen-doped titanium dioxide particles, light stabilizers SEED are grafted on the surfaces and in pores of mesoporous activated carbon, and the modified activated carbon is coated with the nitrogen-doped titanium dioxide. The essence loaded in the modified activated carbon can not be in contact with the nitrogen-doped titanium dioxide to be oxidized and decomposed; and the SEED can quench free radicals, so that the free radicals generated by the nitrogen-doped titanium dioxide can be better prevented from contacting with the essence loaded in the modified activated carbon. Therefore, the modified activated carbon @ nitrogen-doped titanium dioxide particles are used as the core material, so that the decomposition of essence loaded in the photocatalyst particles caused by the photocatalytic action of the nitrogen-doped titanium dioxide can be reduced, and the durability of the aromatic action of the microcapsule can be improved.
Further, in the step (1.1), the mass ratio of the tetraethylammonium bromide to the mesoporous activated carbon is 1-2: 1.
Further, in the step (1.1), the mass ratio of the mesoporous activated carbon to the N, N-dimethylacetamide is 1: 8-10.
Further, in the step (1.2), when the acrylate modified activated carbon is dispersed into the N, N-dimethylacetamide, the mass ratio of the acrylate modified activated carbon to the N, N-dimethylacetamide is 1: 6-8; in the N, N-dimethylacetamide solution of the light stabilizer SEED, the mass ratio of the light stabilizer SEED to the N, N-dimethylacetamide is 1: 1.5-2.5.
A preparation method of the microcapsule comprises the following steps:
(2.1) preparation of photocatalyst particle Dispersion: dispersing photocatalyst particles into water, adding a dispersing agent, and performing ultrasonic dispersion uniformly to obtain a photocatalyst particle dispersion liquid, wherein the mass fraction of the dispersing agent is 8-12%, and the mass fraction of the photocatalyst particles is 4-6%;
(2.2) preparing nitrogen-doped titanium dioxide/aromatic microcapsules: adding water-soluble essence into the photocatalyst particle dispersion liquid, wherein the mass ratio of the photocatalyst particles to the water-soluble essence is 1:20-25, uniformly stirring, then adding isophorone diisocyanate, a catalyst and an emulsifier, wherein the mass ratio of the photocatalyst particles to the isophorone diisocyanate is 4-5:1, stirring and reacting for 4-5h at 75-85 ℃, filtering, and drying to obtain the nitrogen-doped titanium dioxide/aromatic microcapsule.
In the step (2.2), the lemon essence enters pores of photocatalyst particles (nitrogen-doped titanium dioxide particles or modified activated carbon @ nitrogen-doped titanium dioxide particles), isophorone diisocyanate reacts with water under the action of a catalyst to generate polyurea, and the polyurea is coated outside the photocatalyst particles to form a shell of the microcapsule.
For the scheme of adopting the modified activated carbon @ nitrogen-doped titanium dioxide particles as photocatalyst particles, when the microcapsule is prepared, part of essence is loaded in the activated carbon, and part of essence is loaded in the nitrogen-doped titanium dioxide, the former cannot be contacted with free radicals generated by the nitrogen-doped titanium dioxide, so that the part of essence can be prevented from being oxidized and decomposed, and the durability of the aromatic effect of the microcapsule is improved.
Preferably, in step (2.1), the dispersant is sodium dodecylbenzene sulfonate and/or sodium dodecyl sulfate.
The dispersant is used for promoting the nitrogen-doped titanium dioxide to be dispersed in water and preventing the nitrogen-doped titanium dioxide from agglomerating, so that the finally prepared microcapsule has uniform particle size. When the inventors compare the dispersing effects of sodium dodecylbenzene sulfonate and sodium dodecyl sulfate, the nitrogen-doped titanium dioxide of the present invention has a more stable dispersion with sodium dodecylbenzene sulfonate within 2 hours, resulting in a slower rate of delamination, but after 2 hours, a more stable dispersion with sodium dodecyl sulfate. Therefore, if the microcapsule is prepared within 2 hours after the photocatalyst particle dispersion is prepared, sodium dodecylbenzenesulfonate may be used; if the microcapsules are prepared after 2h, sodium lauryl sulfate may be used.
Preferably, in the step (2.2), the catalyst is tetramethylethylenediamine, and the mass ratio of the catalyst to the photocatalyst particles is 3-5: 100.
Preferably, in the step (2.2), the emulsifier is polyvinyl alcohol, and the mass ratio of the emulsifier to the photocatalyst particles is 1: 18-23.
The choice of emulsifier affects the morphology of the microcapsules produced and not all emulsifiers are suitable for use in the preparation of the nitrogen-doped titanium dioxide/fragrance microcapsules of the invention, for example, the inventors found during experimentation that: when the gum arabic is used as an emulsifier, the isophorone diisocyanate is difficult to form uniform coating on the surface of the nitrogen-doped titanium dioxide, and the prepared microcapsule has serious surface depression; when sodium dodecyl sulfate is used as an emulsifier, the wall layer of the prepared microcapsule is too thick, so that aromatic substances are difficult to permeate through the wall layer and volatilize into air, and air pollutants are difficult to permeate through the wall layer and contact with nitrogen-doped titanium dioxide; when polyvinyl alcohol is used as an emulsifier, the prepared microcapsule has regular surface and proper particle size.
In the emulsifying process, the emulsifier plays roles in reducing the interfacial tension between the water phase and the oil phase, stabilizing dispersed liquid drops, reducing the agglomeration probability of the liquid drops and the like, and the appearance of the finally prepared microcapsule is influenced by the selection of the emulsifier.
Preferably, in the step (2.2), the mass ratio of the photocatalyst particles to isophorone diisocyanate is 4: 1.
When the core material ratio is too large, the microcapsules are damaged in the drying process and the like, so that complete microcapsules cannot be obtained; when the core material ratio is too small, although the microcapsule can be obtained, the reaction of the isophorone diisocyanate and water is too violent due to too high concentration of the isophorone diisocyanate, and a large number of wrinkles appear on the surface of the microcapsule; by controlling the core material ratio to be 4:1, the microcapsules which are complete and smooth in surface and free from wrinkles can be obtained.
Preferably, in the step (2.1), the time for ultrasonic dispersion is 15-20 min.
Preferably, in step (2.2), the temperature of the drying is 60 to 90 ℃.
A method for preparing an air filtration purification textile material by using the microcapsule, comprising the following steps:
(3.1) preparing a finishing liquid: dispersing the microcapsules in water, adding a binder, and performing ultrasonic dispersion uniformly to obtain a finishing liquid, wherein the mass fraction of the microcapsules is 1-9%, and the mass fraction of the binder is 5-10%;
(3.2) preparing an air filtering and purifying textile material: and (3) soaking the polyester fabric in water, padding in finishing liquor, drying, and repeating the padding and drying processes for 1-3 times to obtain the air filtering and purifying textile material.
Preferably, in step (1.1), the binder is triethoxysilane.
Preferably, in the step (3.2), the padding process is double-padding and double-rolling.
Preferably, in the step (3.2), the drying temperature is 55-65 ℃.
Compared with the prior art, the invention has the following advantages:
(1) the nitrogen-doped titanium dioxide is used as a core material, so that the problem of reduction of the photocatalytic activity of the titanium dioxide after polyurea coating can be solved, and the microcapsule is ensured to have a good air purification effect;
(2) polyurea is adopted as a wall material, so that direct contact between titanium dioxide and chemical fibers can be reduced, and the titanium dioxide is prevented from accelerating chemical fiber aging; the spontaneous release of the essence can be reduced, and the durability and controllability of the air freshening effect of the essence are realized; the polyurea has good optical stability and chemical resistance, and is not easy to degrade and lose efficacy;
(3) the modified activated carbon @ nitrogen-doped titanium dioxide particles are used as the core material, so that the decomposition of essence loaded in the modified activated carbon due to the photocatalytic action of the nitrogen-doped titanium dioxide can be avoided, and the durability of the aromatic action of the microcapsule can be improved.
Drawings
FIG. 1 is a TEM image of microcapsules made with different core ratios; wherein the core ratio of figure (a) is 3:1, the core ratio of figure (b) is 4:1, and the core ratio of figure (c) is 5: 1;
FIG. 2 is a particle size diagram of a photocatalyst particle dispersion obtained in example 1;
FIG. 3 is a TEM image of a photocatalyst particle dispersion obtained in example 1; wherein, the image (a) is a TEM image with a scale of 100nm, and the image (b) is a TEM image with a scale of 50 nm;
FIG. 4 is a TEM image of microcapsules prepared with different emulsifiers; wherein, the emulsifier adopted in the diagram (a) is polyvinyl alcohol, the emulsifier adopted in the diagram (b) is Arabic gum, and the emulsifier adopted in the diagram (c) is sodium dodecyl sulfate;
FIG. 5 is an EDS spectrum of titanium dioxide and nitrogen doped titanium dioxide; wherein, the graph (a) is an EDS spectrum of titanium dioxide, and the graph (b) is an EDS spectrum of nitrogen-doped titanium dioxide.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A nitrogen-doped nano titanium dioxide/aromatic microcapsule is characterized in that a core material of the microcapsule is photocatalyst particles and water-soluble essence, and a wall material is polyurea; the water-soluble essence is loaded in the photocatalyst particles; the photocatalyst particles include nitrogen-doped titanium dioxide. The water-soluble essence comprises at least one of lemon essence, rose essence, mint essence and jasmine essence.
A preparation method of the nitrogen-doped nano titanium dioxide/aromatic microcapsule comprises the following steps:
(1) preparing photocatalyst particles, wherein the photocatalyst particles are nitrogen-doped titanium dioxide particles: uniformly mixing urea and titanium dioxide with the particle size of 50-100nm according to the mass ratio of 1:4-5, calcining at the temperature of 450-550 ℃, and grinding to prepare the nitrogen-doped titanium dioxide particles with the particle size of 20-70 nm.
(2) Preparing microcapsules:
(2.1) preparation of photocatalyst particle Dispersion: dispersing photocatalyst particles into water, adding a dispersing agent, and performing ultrasonic dispersion for 15-20min to obtain a photocatalyst particle dispersion liquid, wherein the dispersing agent is sodium dodecyl benzene sulfonate and/or sodium dodecyl sulfate, the mass fraction of the dispersing agent is 8-12%, and the mass fraction of the photocatalyst particles is 4-6%;
(2.2) preparing nitrogen-doped titanium dioxide/aromatic microcapsules: adding water-soluble essence into a photocatalyst particle dispersion liquid, wherein the mass ratio of photocatalyst particles to the water-soluble essence is 1:20-25, uniformly stirring, then adding isophorone diisocyanate, a catalyst and an emulsifier, wherein the mass ratio of the photocatalyst particles to the isophorone diisocyanate is 4-5:1, the catalyst is tetramethylethylenediamine, the mass ratio of the catalyst to the photocatalyst particles is 3-5:100, the emulsifier is polyvinyl alcohol, and the mass ratio of the emulsifier to the photocatalyst particles is 1: 18-23; stirring and reacting for 4-5h at 75-85 ℃, filtering, and drying at 60-90 ℃ to obtain the nitrogen-doped titanium dioxide/aromatic microcapsule.
A method for preparing an air filtration purification textile material by using the microcapsule, comprising the following steps:
(3.1) preparing a finishing liquid: dispersing the microcapsules in water, adding a binder, and performing ultrasonic dispersion uniformly to obtain a finishing liquid, wherein the mass fraction of the microcapsules is 1-9%, the binder is triethoxysilane, and the mass fraction of the binder is 5-10%;
(3.2) preparing an air filtering and purifying textile material: and (3) soaking the polyester fabric in water, performing secondary soaking and secondary rolling in finishing liquor, drying at 55-65 ℃, and repeating the processes of soaking, rolling and drying for 1-3 times to obtain the air filtration and purification textile material.
Optionally, step (1) is replaced by: preparing photocatalyst particles, wherein the photocatalyst particles are modified activated carbon @ nitrogen-doped titanium dioxide particles:
(1.1) preparing acrylate modified activated carbon: dispersing mesoporous activated carbon with the particle size of 400-500nm into N, N-dimethylacetamide, wherein the mass ratio of the mesoporous activated carbon to the N, N-dimethylacetamide is 1:8-10, adding tetraethylammonium bromide, wherein the mass ratio of the tetraethylammonium bromide to the mesoporous activated carbon is 1-2:1, uniformly mixing, and then dropwise adding acrylic glycidyl ether under stirring, wherein the mass ratio of the acrylic glycidyl ether to the mesoporous activated carbon is 4-6: 1; after the dropwise addition is finished, reacting for 3-5h at the temperature of 120-130 ℃, and filtering and washing to obtain the acrylate modified activated carbon;
(1.2) preparing modified activated carbon: dispersing acrylate modified activated carbon into N, N-dimethylacetamide, wherein the mass ratio of the acrylate modified activated carbon to the N, N-dimethylacetamide is 1:6-8, dropwise adding an N, N-dimethylacetamide solution of a light stabilizer SEED (wherein the mass ratio of the light stabilizer SEED to the N, N-dimethylacetamide is 1:1.5-2.5) into a reaction liquid under stirring, and the mass ratio of the light stabilizer SEED to the acrylate modified activated carbon is 5-10: 1; after the dropwise addition, reacting at 70-80 ℃ for 3-4h, filtering, washing and drying to obtain modified activated carbon;
(1.3) preparation of nitrogen-doped titanium dioxide: uniformly mixing urea and titanium dioxide according to the mass ratio of 1:4-5, calcining at the temperature of 450-550 ℃, and grinding to prepare nitrogen-doped titanium dioxide with the particle size of 5-10 nm;
(1.4) preparing modified activated carbon @ nitrogen-doped titanium dioxide particles: mixing the modified activated carbon and the nitrogen-doped titanium dioxide according to the mass ratio of 2-4:1, ball-milling for 2-3h at the speed of 500-.
Example 1
A nitrogen-doped nano titanium dioxide/aromatic microcapsule is characterized in that a core material of the microcapsule is photocatalyst particles and water-soluble essence, and a wall material is polyurea; the water-soluble essence is loaded in the photocatalyst particles; the photocatalyst particles are nitrogen-doped titanium dioxide particles. The water-soluble essence is lemon essence.
A preparation method of the nitrogen-doped nano titanium dioxide/aromatic microcapsule comprises the following steps:
(1) preparing photocatalyst particles: uniformly mixing urea and titanium dioxide with the average particle size of 50nm according to the mass ratio of 1:4, calcining at 500 ℃, and grinding to obtain nitrogen-doped titanium dioxide particles with the average particle size of 34.02 nm.
(2) Preparing microcapsules:
(2.1) preparation of photocatalyst particle Dispersion: dispersing photocatalyst particles into water, adding a dispersing agent, and performing ultrasonic dispersion for 15min to obtain a photocatalyst particle dispersion liquid, wherein the dispersing agent is sodium dodecyl benzene sulfonate, the mass fraction of the dispersing agent is 10%, and the mass fraction of the photocatalyst particles is 5%;
(2.2) preparing nitrogen-doped titanium dioxide/aromatic microcapsules: adding water-soluble essence into a photocatalyst particle dispersion liquid, wherein the mass ratio of photocatalyst particles to the water-soluble essence is 1:20, uniformly stirring, then adding isophorone diisocyanate, a catalyst and an emulsifier, wherein the mass ratio of the photocatalyst particles to the isophorone diisocyanate is 4:1, the catalyst is tetramethylethylenediamine, the mass ratio of the catalyst to the photocatalyst particles is 3:100, the emulsifier is polyvinyl alcohol, and the mass ratio of the emulsifier to the photocatalyst particles is 1: 20; stirring and reacting for 4h at 80 ℃, filtering, and drying at 80 ℃ to obtain the nitrogen-doped titanium dioxide/aromatic microcapsule.
A method for preparing an air filtration purification textile material by using the microcapsule, comprising the following steps:
(3.1) preparing a finishing liquid: dispersing the microcapsules into water, adding a binder, and uniformly dispersing by ultrasonic to prepare a finishing liquid, wherein the mass fraction of the microcapsules is 6%, the binder is triethoxysilane, and the mass fraction of the binder is 5%;
(3.2) preparing an air filtering and purifying textile material: soaking 10 x 10cm of polyester fabric in water, soaking twice and rolling twice in finishing liquid, drying at 60 ℃, and soaking, rolling again and drying to obtain the air filtering and purifying textile material.
Example 2
A nitrogen-doped nano titanium dioxide/aromatic microcapsule is characterized in that a core material of the microcapsule is photocatalyst particles and water-soluble essence, and a wall material is polyurea; the water-soluble essence is loaded in the photocatalyst particles; the photocatalyst particles are nitrogen-doped titanium dioxide particles. The water-soluble essence is lemon essence.
A preparation method of the nitrogen-doped nano titanium dioxide/aromatic microcapsule comprises the following steps:
(1) preparing photocatalyst particles: uniformly mixing urea and titanium dioxide with the average particle size of 75nm according to the mass ratio of 1:4.5, calcining at 450 ℃, and grinding to obtain nitrogen-doped titanium dioxide particles with the average particle size of 33.52 nm.
(2) Preparing microcapsules:
(2.1) preparation of photocatalyst particle Dispersion: dispersing photocatalyst particles into water, adding a dispersing agent, and performing ultrasonic dispersion for 18min to obtain a photocatalyst particle dispersion liquid, wherein the dispersing agent is sodium dodecyl benzene sulfonate, the mass fraction of the dispersing agent is 8%, and the mass fraction of the photocatalyst particles is 3%;
(2.2) preparing nitrogen-doped titanium dioxide/aromatic microcapsules: adding water-soluble essence into a photocatalyst particle dispersion liquid, wherein the mass ratio of photocatalyst particles to the water-soluble essence is 1:23, uniformly stirring, then adding isophorone diisocyanate, a catalyst and an emulsifier, wherein the mass ratio of the photocatalyst particles to the isophorone diisocyanate is 4:1, the catalyst is tetramethylethylenediamine, the mass ratio of the catalyst to the photocatalyst particles is 1:25, the emulsifier is polyvinyl alcohol, and the mass ratio of the emulsifier to the photocatalyst particles is 1: 18; stirring and reacting for 5h at 75 ℃, filtering, and drying at 60 ℃ to obtain the nitrogen-doped titanium dioxide/aromatic microcapsule.
A method for preparing an air filtration purification textile material by using the microcapsule, comprising the following steps:
(3.1) preparing a finishing liquid: dispersing the microcapsules in water, adding a binder, and performing ultrasonic dispersion uniformly to obtain a finishing liquid, wherein the mass fraction of the microcapsules is 1%, the binder is triethoxysilane, and the mass fraction of the binder is 8%;
(3.2) preparing an air filtering and purifying textile material: soaking 10 x 10cm of polyester fabric in water, soaking twice and rolling twice in finishing liquid, drying at 55 ℃, and soaking, rolling again and drying to obtain the air filtering and purifying textile material.
Example 3
A nitrogen-doped nano titanium dioxide/aromatic microcapsule is characterized in that a core material of the microcapsule is photocatalyst particles and water-soluble essence, and a wall material is polyurea; the water-soluble essence is loaded in the photocatalyst particles; the photocatalyst particles are nitrogen-doped titanium dioxide particles. The water-soluble essence is lemon essence.
A preparation method of the nitrogen-doped nano titanium dioxide/aromatic microcapsule comprises the following steps:
(1) preparing photocatalyst particles: uniformly mixing urea and titanium dioxide with the average particle size of 100nm according to the mass ratio of 1:5, calcining at 550 ℃, and grinding to obtain nitrogen-doped titanium dioxide particles with the average particle size of 38.93 nm.
(2) Preparing microcapsules:
(2.1) preparation of photocatalyst particle Dispersion: dispersing photocatalyst particles into water, adding a dispersing agent, and performing ultrasonic dispersion for 20min to obtain a photocatalyst particle dispersion liquid, wherein the dispersing agent is sodium dodecyl benzene sulfonate, the mass fraction of the dispersing agent is 12%, and the mass fraction of the photocatalyst particles is 4%;
(2.2) preparing nitrogen-doped titanium dioxide/aromatic microcapsules: adding water-soluble essence into a photocatalyst particle dispersion liquid, wherein the mass ratio of photocatalyst particles to the water-soluble essence is 1:25, uniformly stirring, then adding isophorone diisocyanate, a catalyst and an emulsifier, wherein the mass ratio of the photocatalyst particles to the isophorone diisocyanate is 4:1, the catalyst is tetramethylethylenediamine, the mass ratio of the catalyst to the photocatalyst particles is 1:20, the emulsifier is polyvinyl alcohol, and the mass ratio of the emulsifier to the photocatalyst particles is 1: 23; stirring and reacting for 4.5h at 85 ℃, filtering and drying at 90 ℃ to prepare the nitrogen-doped titanium dioxide/aromatic microcapsule.
A method for preparing an air filtration purification textile material by using the microcapsule, comprising the following steps:
(3.1) preparing a finishing liquid: dispersing the microcapsules into water, adding a binder, and performing ultrasonic dispersion uniformly to obtain a finishing liquid, wherein the mass fraction of the microcapsules is 9%, the binder is triethoxysilane, and the mass fraction of the binder is 10%;
(3.2) preparing an air filtering and purifying textile material: soaking 10 x 10cm of polyester fabric in water, soaking twice and rolling twice in finishing liquid, drying at 65 ℃, and soaking, rolling again and drying to obtain the air filtering and purifying textile material.
Example 4
A nitrogen-doped nano titanium dioxide/aromatic microcapsule comprises a core material of photocatalyst particles and water-soluble essence, and a wall material of polyurea; the water-soluble essence is loaded in the photocatalyst particles; the photocatalyst particles are modified activated carbon @ nitrogen-doped titanium dioxide particles. The water-soluble essence is lemon essence.
A preparation method of the nitrogen-doped nano titanium dioxide/aromatic microcapsule comprises the following steps:
(1) preparing photocatalyst particles:
(1.1) preparing acrylate modified activated carbon: dispersing mesoporous activated carbon with the average particle size of 400nm into N, N-dimethylacetamide, wherein the mass ratio of the mesoporous activated carbon to the N, N-dimethylacetamide is 1:8, adding tetraethylammonium bromide, wherein the mass ratio of the tetraethylammonium bromide to the mesoporous activated carbon is 1:1, uniformly mixing, and then dropwise adding acrylic glycidyl ether under stirring, wherein the mass ratio of the acrylic glycidyl ether to the mesoporous activated carbon is 4: 1; after the dropwise addition, reacting for 3 hours at 130 ℃, filtering and washing to obtain the acrylate modified activated carbon;
(1.2) preparing modified activated carbon: dispersing acrylate modified activated carbon into N, N-dimethylacetamide, wherein the mass ratio of the acrylate modified activated carbon to the N, N-dimethylacetamide is 1:6, dropwise adding an N, N-dimethylacetamide solution of a light stabilizer SEED (wherein the mass ratio of the light stabilizer SEED to the N, N-dimethylacetamide is 1:2.5) into a reaction liquid under stirring, and the mass ratio of the light stabilizer SEED to the acrylate modified activated carbon is 5: 1; after the dropwise addition, reacting at 80 ℃ for 3h, filtering, washing and drying to obtain modified activated carbon;
(1.3) preparation of nitrogen-doped titanium dioxide: uniformly mixing urea and titanium dioxide according to the mass ratio of 1:4, calcining at 500 ℃, and grinding to obtain nitrogen-doped titanium dioxide with the average particle size of 5 nm;
(1.4) preparing modified activated carbon @ nitrogen-doped titanium dioxide particles: mixing the modified activated carbon and the nitrogen-doped titanium dioxide according to the mass ratio of 2:1, ball-milling for 3h at the speed of 500r/min, and sintering for 1.5h at the temperature of 500 ℃ to obtain the modified activated carbon @ nitrogen-doped titanium dioxide particles.
(2) Preparing microcapsules:
(2.1) preparation of photocatalyst particle Dispersion: dispersing photocatalyst particles into water, adding a dispersing agent, and performing ultrasonic dispersion for 15min to obtain a photocatalyst particle dispersion liquid, wherein the dispersing agent is sodium dodecyl benzene sulfonate, the mass fraction of the dispersing agent is 10%, and the mass fraction of the photocatalyst particles is 5%;
(2.2) preparing nitrogen-doped titanium dioxide/aromatic microcapsules: adding water-soluble essence into a photocatalyst particle dispersion liquid, wherein the mass ratio of the photocatalyst particles to the water-soluble essence is 1:20, uniformly stirring, then adding isophorone diisocyanate, a catalyst and an emulsifier, wherein the mass ratio of the photocatalyst particles to the isophorone diisocyanate is 4:1, the catalyst is tetramethylethylenediamine, the mass ratio of the catalyst to the photocatalyst particles is 3:100, the emulsifier is polyvinyl alcohol, and the mass ratio of the emulsifier to the photocatalyst particles is 1: 20; stirring and reacting for 4h at 80 ℃, filtering, and drying at 80 ℃ to obtain the nitrogen-doped titanium dioxide/aromatic microcapsule.
A method for preparing an air filtration purification textile material by using the microcapsule, comprising the following steps:
(3.1) preparing finishing liquid: dispersing the microcapsules in water, adding a binder, and performing ultrasonic dispersion uniformly to obtain a finishing liquid, wherein the mass fraction of the microcapsules is 6%, the binder is triethoxysilane, and the mass fraction of the binder is 5%;
(3.2) preparing an air filtering and purifying textile material: soaking 10 x 10cm of polyester fabric in water, soaking twice and rolling twice in finishing liquid, drying at 60 ℃, and soaking, rolling again and drying to obtain the air filtering and purifying textile material.
Example 5
A nitrogen-doped nano titanium dioxide/aromatic microcapsule is characterized in that a core material of the microcapsule is photocatalyst particles and water-soluble essence, and a wall material is polyurea; the water-soluble essence is loaded in the photocatalyst particles; the photocatalyst particles are modified activated carbon @ nitrogen-doped titanium dioxide particles. The water-soluble essence is lemon essence.
A preparation method of the nitrogen-doped nano titanium dioxide/aromatic microcapsule comprises the following steps:
(1) preparing photocatalyst particles:
(1.1) preparing acrylate modified activated carbon: dispersing mesoporous activated carbon with the average particle size of 450nm into N, N-dimethylacetamide, wherein the mass ratio of the mesoporous activated carbon to the N, N-dimethylacetamide is 1:9, adding tetraethylammonium bromide, wherein the mass ratio of the tetraethylammonium bromide to the mesoporous activated carbon is 1.5:1, uniformly mixing, and then dropwise adding acrylic glycidyl ether under stirring, wherein the mass ratio of the acrylic glycidyl ether to the mesoporous activated carbon is 5: 1; after the dropwise addition, reacting for 4 hours at 125 ℃, filtering and washing to obtain the acrylate modified activated carbon;
(1.2) preparing modified activated carbon: dispersing acrylate modified activated carbon into N, N-dimethylacetamide, wherein the mass ratio of the acrylate modified activated carbon to the N, N-dimethylacetamide is 1:7, dropwise adding an N, N-dimethylacetamide solution of a light stabilizer SEED (wherein the mass ratio of the light stabilizer SEED to the N, N-dimethylacetamide is 1:2) into a reaction liquid under stirring, and the mass ratio of the light stabilizer SEED to the acrylate modified activated carbon is 8: 1; after the dropwise addition, reacting at 75 ℃ for 3.5h, filtering, washing and drying to obtain modified activated carbon;
(1.3) preparation of nitrogen-doped titanium dioxide: uniformly mixing urea and titanium dioxide according to the mass ratio of 1:4, calcining at 500 ℃, and grinding to obtain nitrogen-doped titanium dioxide with the average particle size of 8 nm;
(1.4) preparing modified activated carbon @ nitrogen-doped titanium dioxide particles: mixing the modified activated carbon and the nitrogen-doped titanium dioxide according to the mass ratio of 3:1, ball-milling for 2.5h at the speed of 550r/min, and sintering for 1h at 530 ℃ to obtain the modified activated carbon @ nitrogen-doped titanium dioxide particles.
(2) Preparing microcapsules:
(2.1) preparation of photocatalyst particle Dispersion: dispersing photocatalyst particles into water, adding a dispersing agent, and performing ultrasonic dispersion for 15min to obtain a photocatalyst particle dispersion liquid, wherein the dispersing agent is sodium dodecyl benzene sulfonate, the mass fraction of the dispersing agent is 10%, and the mass fraction of the photocatalyst particles is 5%;
(2.2) preparing nitrogen-doped titanium dioxide/aromatic microcapsules: adding water-soluble essence into a photocatalyst particle dispersion liquid, wherein the mass ratio of photocatalyst particles to the water-soluble essence is 1:20, uniformly stirring, then adding isophorone diisocyanate, a catalyst and an emulsifier, wherein the mass ratio of the photocatalyst particles to the isophorone diisocyanate is 4:1, the catalyst is tetramethylethylenediamine, the mass ratio of the catalyst to the photocatalyst particles is 3:100, the emulsifier is polyvinyl alcohol, and the mass ratio of the emulsifier to the photocatalyst particles is 1: 20; stirring and reacting for 4h at 80 ℃, filtering, and drying at 80 ℃ to obtain the nitrogen-doped titanium dioxide/aromatic microcapsule.
A method for preparing an air filtration purification textile material by using the microcapsule, comprising the following steps:
(3.1) preparing a finishing liquid: dispersing the microcapsules in water, adding a binder, and performing ultrasonic dispersion uniformly to obtain a finishing liquid, wherein the mass fraction of the microcapsules is 6%, the binder is triethoxysilane, and the mass fraction of the binder is 5%;
(3.2) preparing an air filtering and purifying textile material: soaking 10 x 10cm of polyester fabric in water, soaking twice and rolling twice in finishing liquid, drying at 60 ℃, and soaking, rolling again and drying to obtain the air filtering and purifying textile material.
Example 6
A nitrogen-doped nano titanium dioxide/aromatic microcapsule is characterized in that a core material of the microcapsule is photocatalyst particles and water-soluble essence, and a wall material is polyurea; the water-soluble essence is loaded in the photocatalyst particles; the photocatalyst particles are modified activated carbon @ nitrogen-doped titanium dioxide particles. The water-soluble essence is lemon essence.
A preparation method of the nitrogen-doped nano titanium dioxide/aromatic microcapsule comprises the following steps:
(1) preparing photocatalyst particles:
(1.1) preparing acrylate modified activated carbon: dispersing mesoporous activated carbon with the average particle size of 500nm into N, N-dimethylacetamide, wherein the mass ratio of the mesoporous activated carbon to the N, N-dimethylacetamide is 1:10, adding tetraethylammonium bromide, wherein the mass ratio of the tetraethylammonium bromide to the mesoporous activated carbon is 2:1, uniformly mixing, and then dropwise adding acrylic glycidyl ether under stirring, wherein the mass ratio of the acrylic glycidyl ether to the mesoporous activated carbon is 6: 1; after the dropwise addition, reacting for 5 hours at 120 ℃, filtering and washing to obtain the acrylate modified activated carbon;
(1.2) preparing modified activated carbon: dispersing acrylate modified activated carbon into N, N-dimethylacetamide, wherein the mass ratio of the acrylate modified activated carbon to the N, N-dimethylacetamide is 1:8, dropwise adding an N, N-dimethylacetamide solution of a light stabilizer SEED (wherein the mass ratio of the light stabilizer SEED to the N, N-dimethylacetamide is 1:2.5) into a reaction liquid under stirring, and the mass ratio of the light stabilizer SEED to the acrylate modified activated carbon is 10: 1; after the dropwise addition, reacting for 4 hours at 70 ℃, filtering, washing and drying to obtain modified activated carbon;
(1.3) preparation of nitrogen-doped titanium dioxide: uniformly mixing urea and titanium dioxide according to the mass ratio of 1:4, and calcining at 500 ℃ to prepare nitrogen-doped titanium dioxide with the average particle size of 10 nm;
(1.4) preparing modified activated carbon @ nitrogen-doped titanium dioxide particles: mixing the modified activated carbon and the nitrogen-doped titanium dioxide according to the mass ratio of 4:1, ball-milling for 2h at the speed of 600r/min, and sintering for 0.5h at the temperature of 550 ℃ to obtain the modified activated carbon @ nitrogen-doped titanium dioxide particles.
(2) Preparing microcapsules:
(2.1) preparation of photocatalyst particle Dispersion: dispersing photocatalyst particles into water, adding a dispersing agent, and performing ultrasonic dispersion for 15min to obtain a photocatalyst particle dispersion liquid, wherein the dispersing agent is sodium dodecyl benzene sulfonate, the mass fraction of the dispersing agent is 10%, and the mass fraction of the photocatalyst particles is 5%;
(2.2) preparing nitrogen-doped titanium dioxide/aromatic microcapsules: adding water-soluble essence into a photocatalyst particle dispersion liquid, wherein the mass ratio of photocatalyst particles to the water-soluble essence is 1:20, uniformly stirring, then adding isophorone diisocyanate, a catalyst and an emulsifier, wherein the mass ratio of the photocatalyst particles to the isophorone diisocyanate is 4:1, the catalyst is tetramethylethylenediamine, the mass ratio of the catalyst to the photocatalyst particles is 3:100, the emulsifier is polyvinyl alcohol, and the mass ratio of the emulsifier to the photocatalyst particles is 1: 20; stirring and reacting for 4h at 80 ℃, filtering, and drying at 80 ℃ to obtain the nitrogen-doped titanium dioxide/aromatic microcapsule.
A method for preparing an air filtration purification textile material by using the microcapsule, comprising the following steps:
(3.1) preparing a finishing liquid: dispersing the microcapsules in water, adding a binder, and performing ultrasonic dispersion uniformly to obtain a finishing liquid, wherein the mass fraction of the microcapsules is 6%, the binder is triethoxysilane, and the mass fraction of the binder is 5%;
(3.2) preparing an air filtering and purifying textile material: soaking 10 x 10cm of polyester fabric in water, soaking twice and rolling twice in finishing liquid, drying at 60 ℃, and soaking, rolling again and drying to obtain the air filtering and purifying textile material.
Example 7
This example differs from example 1 in that in step (2.1) the dispersant is sodium lauryl sulfate.
The photocatalyst particle dispersions (stock solutions) without the addition of a dispersant and the photocatalyst particle dispersions obtained in the steps (2.1) of examples 1 and 7 were subjected to a settling test (all of the photocatalysts were nitrogen-doped titanium dioxide particles): after standing for 1 hour, 2 hours, 4 hours, 8 hours, and 24 hours, respectively, the state of the dispersion was observed, and the height of the precipitate was measured, and the results are shown in table 1.
TABLE 1 sedimentation height with different dispersants
| Numbering | Dispersing agent | 0h | 1h | 2h | 4h | 8h | 24h |
| Stock solution | Is free of | 2.9cm | 2.6cm | 2.5cm | 2.5cm | 2.5cm | 2.2cm |
| Example 1 | Sodium dodecyl benzene sulfonate | 0cm | 0.2cm | 0.3cm | 0.4cm | 0.5cm | 0.5cm |
| Example 7 | Sodium dodecyl sulfate | 0cm | 0.3cm | 0.3cm | 0.3cm | 0.3cm | 0.4cm |
Through the settlement experiment, the following results are found: the stock solution without the dispersant has the worst stability, serious precipitation and obvious layering; the dispersion (example 7) using sodium lauryl sulfate as the dispersant was stable but slightly delaminated with time, with a slow delamination rate; the dispersion (example 1) using dodecylbenzene sulfonic acid as the dispersant was stable, resulted in slower delamination initially than the dispersion of example 7, and then faster delamination with time, and was greater and more pronounced after 2h of standing than the dispersion of example 7. Based on the above experimental results, if the microcapsule is prepared within 2 hours after the photocatalyst particle dispersion is prepared, sodium dodecylbenzenesulfonate may be used as a dispersant; if the microcapsules are prepared after 2h, sodium lauryl sulfate may be used.
The dispersion obtained in step (2.1) of example 1 was used to examine the particle size of the nitrogen-doped titanium dioxide, and as shown in FIG. 2, the particle size was concentrated and the average particle size was 34.02nm, indicating that the photocatalyst particle dispersion had high stability. When the photocatalyst particle dispersion liquid prepared in the step (2.1) of example 1 is observed under an electron microscope, as shown in fig. 3, the nitrogen-doped titanium dioxide has good dispersibility, the size is in the nanometer range, is about 30nm, and is consistent with the result of a particle size test chart, which shows that sodium dodecylbenzenesulfonate as a dispersant can well stabilize the photocatalyst particle dispersion liquid.
Example 8
This example differs from example 1 in that in step (2.2) the mass of the photocatalyst particles and isophorone diisocyanate is 5: 1.
Comparative example 1
This comparative example differs from example 1 in that in step (2.2) the mass of the photocatalyst particles to isophorone diisocyanate was 3: 1.
The microcapsules prepared in example 8, example 1 and comparative example 1 were observed under an electron microscope, as shown in FIGS. 1(a) to (c), respectively, from which it can be seen that: in fig. 1(a), there are a lot of membranes and it is difficult to find complete microcapsules; in the figure 1(b), the microcapsules have regular shapes, smooth surfaces and no depressions; in fig. 3(a), a large number of wrinkles are present on the surface of the microcapsule. The above results indicate that when the core material ratio is too large, complete microcapsules cannot be formed, presumably due to breakage during drying or the like; when the core material ratio is too small, a large number of depressions appear on the surface of the microcapsule, presumably because the reaction of isophorone diisocyanate with water is too violent due to too high concentration of isophorone diisocyanate; the core material ratio is controlled to be 4:1, and the microcapsules which are complete and smooth in surface and free from wrinkles can be obtained.
Comparative examples 2 to 3
Comparative example 2 differs from example 1 in that in step (2.2) the emulsifier is gum arabic.
Comparative example 3 differs from example 1 in that in step (2.2) the emulsifier is sodium lauryl sulfate.
The microcapsules prepared in example 1, comparative example 2 and comparative example 3 were observed under an electron microscope as shown in fig. 4(a) to (c), respectively, from which it can be seen that: the microcapsules in FIG. 4(a) are spherical with smooth surface; the surface of the microcapsule in FIG. 4(b) is severely concaved; in FIG. 4(c), the microcapsule particle size is too large. The above results indicate that when gum arabic is used as an emulsifier, isophorone diisocyanate is difficult to form a uniform coating on the surface of nitrogen-doped titanium dioxide; when sodium dodecyl sulfate is used as an emulsifier, the wall layer of the prepared microcapsule is too thick, which may cause that aromatic substances are difficult to permeate through the wall layer and volatilize into air, and air pollutants cannot permeate through the wall layer and contact with nitrogen-doped titanium dioxide; when polyvinyl alcohol is used as an emulsifier, the prepared microcapsule has regular surface and proper particle size.
Comparative example 4
A titanium dioxide/aromatic microcapsule, the core material of the said microcapsule is photocatalyst particle and water soluble essence, the wall material is polyurea; the water-soluble essence is loaded in the photocatalyst particles; the photocatalyst particles are titanium dioxide particles. The water-soluble essence is lemon essence.
A preparation method of the titanium dioxide/aromatic microcapsule comprises the following steps:
(2.1) preparation of photocatalyst particle Dispersion: dispersing titanium dioxide with the average particle size of 35nm into water, adding a dispersing agent, and performing ultrasonic dispersion for 15min to prepare photocatalyst particle dispersion liquid, wherein the dispersing agent is sodium dodecyl benzene sulfonate, the mass fraction of the dispersing agent is 10%, and the mass fraction of the titanium dioxide is 5%;
(2.2) preparation of titanium dioxide/fragrance microcapsules: adding water-soluble essence into a titanium dioxide dispersion liquid, wherein the mass ratio of titanium dioxide to the water-soluble essence is 1:20, uniformly stirring, then adding isophorone diisocyanate, a catalyst and an emulsifier, wherein the mass ratio of the titanium dioxide to the isophorone diisocyanate is 4:1, the catalyst is tetramethylethylenediamine, the mass ratio of the catalyst to the titanium dioxide is 3:100, the emulsifier is polyvinyl alcohol, and the mass ratio of the emulsifier to the titanium dioxide is 1: 20; stirring and reacting for 4 hours at the temperature of 80 ℃, filtering and drying to prepare the nitrogen-doped titanium dioxide/aromatic microcapsule.
A method for preparing an air filtration purification textile material by using the microcapsule, comprising the following steps:
(3.1) preparing finishing liquid: dispersing the microcapsules in water, adding a binder, and performing ultrasonic dispersion uniformly to obtain a finishing liquid, wherein the mass fraction of the microcapsules is 6%, the binder is triethoxysilane, and the mass fraction of the binder is 5%;
(3.2) preparing an air filtering and purifying textile material: soaking the polyester fabric in water, performing secondary soaking and secondary rolling in finishing liquid, drying at the temperature of 60 ℃, and performing secondary soaking and rolling and drying to obtain the air filtration and purification textile material.
The titanium dioxide used in the step (2.1) of the comparative example 4 and the nitrogen-doped titanium dioxide prepared in the step (1) of the example 1 were analyzed for the element composition and content by EDS spectrogram, as shown in FIG. 5, titanium dioxide contains Ti and O elements, and nitrogen-doped titanium dioxide contains N elements in addition to Ti and O elements, which indicates that N was successfully doped in TiO2In (1).
Performance testing
1 dust removal Effect test
The dust removal efficiency of the air filtration and purification textile materials prepared in examples 1-6 and comparative example 4 was tested with reference to GB/T14295-.
TABLE 2 dust removal effect of air filtration and purification textile material
As can be seen from Table 2, the air filtration and purification textile material obtained by the method of the present invention has a good dust removal effect, and the filtration efficiencies of examples 1-6 for particles with a diameter greater than 0.5 μm are all over 80%.
2 air pollutant degradation effect test
The air contaminant degradation effects of the air filtration purification textile materials prepared in examples 1 to 6 and comparative example 4 were tested with formaldehyde and toluene as research objects, the acting time was 24 hours, and the results are shown in table 3.
TABLE 3 air contaminant degradation Effect of air filtration purification textile Material
As can be seen from Table 3, the air filtration and purification textile material obtained by the method of the invention has a good air pollutant degradation effect, and after 24 hours, the removal rate of formaldehyde and the removal rate of toluene in examples 1-6 can reach more than 87%.
Example 1 differs from comparative example 3 in that polyvinyl alcohol was used as an emulsifier in example 1, while sodium lauryl sulfate was used in comparative example 3. As can be seen from Table 3, the air-filtering purification textile material prepared in comparative example 3 has significantly lower removal rate of formaldehyde and toluene than that of example 1. The reason is that: when sodium lauryl sulfate is used as an emulsifier, the wall layers of the resulting microcapsules are too thick (as can be seen in fig. 4), which results in the wall layers being less permeable to air contaminants and in contact with the nitrogen-doped titanium dioxide.
Example 1 is different from comparative example 4 in that nitrogen-doped titanium dioxide particles are used as photocatalyst particles in example 1, and titanium dioxide particles are used in comparative example 4. As can be seen from table 3, the air filtration and purification textile material prepared in example 1 has significantly higher formaldehyde and toluene removal rate than comparative example 4. The reason is that: compared with common titanium dioxide which can only absorb ultraviolet light, the nitrogen-doped titanium dioxide has the advantages that due to lattice distortion, the energy gap is reduced, the maximum absorption wavelength red shift is realized, and the visible light is absorbed, so that the sunlight utilization rate is higher, the problem of reduction of the photocatalytic activity of the titanium dioxide after polyurea coating can be solved, and the microcapsule has a better air purification effect.
Examples 4-6 differ from example 1 in that nitrogen-doped titanium dioxide pellets were used as photocatalyst particles in example 1, and modified activated carbon @ nitrogen-doped titanium dioxide pellets were used in examples 4-6. As can be seen from Table 3, the air filtration purification textile materials obtained in examples 4 to 6 had a small decrease in the removal rate of formaldehyde and toluene as compared with example 1. The reason is that: in the modified activated carbon @ nitrogen-doped titanium dioxide particles, although the content of nitrogen-doped titanium dioxide is reduced, the activated carbon has an adsorption effect on air pollutants such as formaldehyde, toluene and the like, and can improve the supplement speed of formaldehyde and toluene on the surface of the nitrogen-doped titanium dioxide to a certain extent, so that the photocatalytic degradation efficiency of the nitrogen-doped titanium dioxide on the formaldehyde and the toluene is improved.
3 fragrance retention effect test
The fragrance retention effect of the air filtration purification textile materials prepared in examples 1-6 and comparative example 4 was tested by a statistical evaluation method, 10 fixed testers were selected, and fragrance tests were performed after the textile materials were left for 0 day, 120 days, 180 days, 210 days, and 1 year, with the results shown in table 4.
TABLE 4 fragrance retaining effect of air filtration and purification textile material
| | Day | 0 | 120 days | 180 days | 210 days | 1 year | 1.5 years old |
| Example 1 | Rich in flavor | Rich in flavor | Rich in flavor | Rich in flavor | In general terms | Bland and bland | |
| Example 2 | Rich in flavor | Rich in flavor | Rich in flavor | In general terms | Bland and bland | Has no fragrance | |
| Example 3 | Rich in flavor | Rich in flavor | Rich in flavor | Rich in flavor | Rich in flavor | In general terms | |
| Example 4 | Rich in flavor | Rich in flavor | Rich in flavor | Rich in flavor | Rich in flavor | Rich in flavor | |
| Example 5 | Rich in flavor | Rich in flavor | Rich in flavor | Rich in flavor | Rich in flavor | Rich in flavor | |
| Example 6 | Rich in flavor | Rich in flavor | Rich in flavor | Rich in flavor | Rich in flavor | Rich in flavor | |
| Comparative example 3 | Rich in flavor | Rich in flavor | In general | Bland and bland | Has no fragrance | Has no fragrance | |
| Comparative example 4 | Rich in flavor | Rich in flavor | Rich in flavor | Rich in flavor | In general | Bland and bland |
As can be seen from Table 4, the air filtration and purification textile material obtained by the method of the invention has good fragrance retention effect, and the fragrance is still strong in 180 days.
Example 1 differs from comparative example 3 in that polyvinyl alcohol was used as the emulsifier in example 1, while sodium lauryl sulfate was used in comparative example 3. As can be seen from Table 3, the air-filtering purification textile material prepared in comparative example 3 has significantly lower removal rate of formaldehyde and toluene than that of example 1. The reason is that: when sodium lauryl sulfate is used as an emulsifier, the wall layer of the resulting microcapsules is too thick (as can be seen in fig. 4), which results in difficulty in the evaporation of fragrance materials into the air through the wall layer.
Examples 4-6 differ from example 1 in that nitrogen-doped titanium dioxide particles were used as photocatalyst particles in example 1 and modified activated carbon @ nitrogen-doped titanium dioxide particles were used in examples 4-6. As can be seen from Table 4, the air filtration purification textile materials prepared in examples 4 to 6 had longer fragrance retention time than those prepared in example 1. The reason is that: in the modified activated carbon @ nitrogen-doped titanium dioxide particles, light stabilizers SEED are grafted on the surfaces and in pores of mesoporous activated carbon, and the modified activated carbon is coated with the nitrogen-doped titanium dioxide. The essence loaded in the modified activated carbon cannot contact with the nitrogen-doped titanium dioxide; and the SEED can quench free radicals, so that the free radicals generated by the nitrogen-doped titanium dioxide can be better prevented from contacting with the essence loaded in the modified activated carbon. Therefore, the modified activated carbon @ nitrogen-doped titanium dioxide particles are used as the core material, so that the decomposition of essence loaded in the photocatalyst particles caused by the photocatalytic action of the nitrogen-doped titanium dioxide can be reduced, and the durability of the aromatic action of the microcapsule can be improved.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (7)
1. A nitrogen-doped nano titanium dioxide/aromatic microcapsule is characterized in that the core material of the microcapsule is photocatalyst particles and water-soluble essence, and the wall material is polyurea; the water-soluble essence is loaded in the photocatalyst particles; the photocatalyst particles comprise nitrogen-doped titanium dioxide; the photocatalyst particles are modified active carbon @ nitrogen-doped titanium dioxide particles, and the preparation method comprises the following steps:
(1.1) preparing acrylate modified activated carbon: dispersing mesoporous activated carbon with the particle size of 400-500nm into N, N-dimethylacetamide, adding tetraethylammonium bromide, uniformly mixing, and dropwise adding acrylic glycidyl ether under stirring, wherein the mass ratio of the acrylic glycidyl ether to the mesoporous activated carbon is 4-6: 1; after the dropwise addition is finished, reacting for 3-5h at the temperature of 120-130 ℃, and filtering and washing to obtain the acrylate modified activated carbon;
(1.2) preparing modified activated carbon: dispersing acrylate modified activated carbon into N, N-dimethylacetamide, dropwise adding an N, N-dimethylacetamide solution of a light stabilizer SEED into the reaction liquid under stirring, wherein the mass ratio of the light stabilizer SEED to the acrylate modified activated carbon is 5-10: 1; after the dropwise addition is finished, reacting for 3-4h at 70-80 ℃, and filtering, washing and drying to obtain modified activated carbon;
(1.3) preparation of nitrogen-doped titanium dioxide: uniformly mixing urea and titanium dioxide according to the mass ratio of 1:4-5, calcining at the temperature of 450-550 ℃, and grinding to prepare nitrogen-doped titanium dioxide with the particle size of 5-10 nm;
(1.4) preparing modified activated carbon @ nitrogen-doped titanium dioxide particles: mixing the modified activated carbon and the nitrogen-doped titanium dioxide according to the mass ratio of 2-4:1, ball-milling for 2-3h at the speed of 600r/min under 500-.
2. The microcapsule of claim 1, wherein the water-soluble flavor comprises at least one of lemon flavor, rose flavor, peppermint flavor, and jasmine flavor.
3. A process for the preparation of microcapsules according to claim 1 or 2, comprising the steps of:
(2.1) preparation of photocatalyst particle Dispersion: dispersing photocatalyst particles into water, adding a dispersing agent, and performing ultrasonic dispersion uniformly to obtain a photocatalyst particle dispersion liquid, wherein the mass fraction of the dispersing agent is 8-12%, and the mass fraction of the photocatalyst particles is 4-6%;
(2.2) preparing nitrogen-doped titanium dioxide/aromatic microcapsules: adding water-soluble essence into the photocatalyst particle dispersion liquid, wherein the mass ratio of the photocatalyst particles to the water-soluble essence is 1:20-25, uniformly stirring, then adding isophorone diisocyanate, a catalyst and an emulsifier, wherein the mass ratio of the photocatalyst particles to the isophorone diisocyanate is 4-5:1, stirring and reacting for 4-5h at 75-85 ℃, filtering, and drying to obtain the nitrogen-doped titanium dioxide/aromatic microcapsule.
4. The method of claim 3, wherein:
in the step (2.1), the dispersing agent is sodium dodecyl benzene sulfonate and/or sodium dodecyl sulfate; and/or
In the step (2.2), the catalyst is tetramethylethylenediamine, and the mass ratio of the catalyst to the photocatalyst particles is 3-5: 100; and/or
In the step (2.2), the emulsifier is polyvinyl alcohol, and the mass ratio of the emulsifier to the photocatalyst particles is 1: 18-23.
5. The method according to claim 3, wherein in the step (2.2), the mass ratio of the photocatalyst particles to isophorone diisocyanate is 4: 1.
6. A process for preparing an air filtration purification textile material using microcapsules according to claim 1 or 2, comprising the steps of:
(3.1) preparing a finishing liquid: dispersing the microcapsules in water, adding a binder, and performing ultrasonic dispersion uniformly to obtain a finishing liquid, wherein the mass fraction of the microcapsules is 1-9%, and the mass fraction of the binder is 5-10%;
(3.2) preparing an air filtering and purifying textile material: soaking the polyester fabric in water, padding in finishing liquid, drying, and repeating the padding and drying processes for 1-3 times to obtain the air filtration and purification textile material.
7. The method of claim 6, wherein in step (3.1), the binder is triethoxysilane.
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