CN109455759B - Nano hollow titanium dioxide microsphere with low refractive index and high catalytic activity and preparation method thereof - Google Patents
Nano hollow titanium dioxide microsphere with low refractive index and high catalytic activity and preparation method thereof Download PDFInfo
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- C01G23/047—Titanium dioxide
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Abstract
The invention relates to the technical field of nano core-shell materials, in particular to a nano hollow titanium dioxide microsphere with low refractive index and high catalytic activity and a preparation method thereof, wherein the method comprises the steps of firstly, introducing a special functional monomer-zwitter-ion reactive emulsifier SM-JR-1 to prepare a cationic polystyrene emulsion; then diluting the cationic polystyrene emulsion with a solvent, adding a titanium source and a chelating agent to perform hydrolysis reaction, and coating titanium dioxide on the surface of the cationic polystyrene microsphere to prepare the nano core-shell titanium dioxide microsphere with controllable particle size and shell thickness, and further preparing the nano hollow titanium dioxide microsphere. The method directly obtains the nano core-shell titanium dioxide microspheres with controllable particle sizes and shell thicknesses through a one-step method, greatly simplifies the preparation steps, and solves the technical problem that the polystyrene microspheres are easy to adhere and deform in the drying process so as to influence the appearance of the nano core-shell titanium dioxide microspheres.
Description
Technical Field
The invention relates to the technical field of nano core-shell materials, in particular to a nano hollow titanium dioxide microsphere with low refractive index and high catalytic activity and a preparation method thereof.
Background
TiO2High oxidation activity, high chemical stability, no harm to human body, low cost, no pollution and wide application rangeWide application range, is the nanometer photocatalytic material which is most widely applied at present, and is the green environment-friendly catalyst which has the greatest development prospect. The nano TiO2 has shown attractive application prospect in various fields such as national defense, agriculture, industry, medicine, medical treatment, health, petroleum, chemical industry, textile, environment, building industry and the like. Due to TiO2Has strong photocatalytic oxidation capability and super-hydrophilicity, and people coat a layer of nano TiO on the surface of common glass2The film and the glass surface have self-cleaning function. Self-cleaning glass was first developed in japan, and in the mid 90's last century, the east pottery (TOTO) company and the asahi glass company of japan coated the glass surface with a titanium dioxide photocatalyst. Several tens of titanium dioxide paints of various shapes have been developed. This product is also being actively developed by Piercun building materials, Inc. of British and PPG, Inc. of America, in addition to Japan, where TiO is available from Piercun2Self-cleaning glass is developed in the forefront of the world. Scientific research institutions in China are also actively researching and developing. This technique plates a layer of TiO on the glass2After film formation, due to TiO2The glass can generate good photocatalytic property under the action of ultraviolet rays and has super-hydrophilicity, so that small water drops are converged into large water drops and fall off under the action of gravity, and stains stained on the water drops can be easily washed away by water, so that the glass has the characteristic of easy cleaning. However, TiO2The refractive index is high and far greater than that of glass, the coating on the glass can reflect light seriously, the appearance and the light transmission of the glass are seriously influenced, and the strong reflected light brings inconvenience to the life of people and even threatens the safety of people; in addition, TiO2The catalytic property needs to be excited by ultraviolet light, and the ultraviolet light only accounts for a small part of sunlight. Therefore, this will greatly limit TiO2The application range and the effect of the self-cleaning glass.
With the development of the technology, researchers have synthesized a variety of TiO2Nano-structure, such as nano-tube, nano hollow microsphere (hollow sphere), etc. Wherein, TiO2Hollow sphere structures have gained much attention due to their low density, large surface area, and good photocatalytic properties. Preparation of TiO at present at home and abroad2The most common method for hollow spheresIs a template method, organic particles are taken as templates, TiO is adhered on the surfaces of the organic particles2Followed by removal of the template by calcination or dissolution to give TiO2The hollow ball. Because the substance used as the titanium source generally has higher hydrolytic activity, the substance cannot be directly added into the polystyrene emulsion for deposition reaction, polystyrene microspheres are generally obtained by a series of complicated treatments of firstly centrifugally separating the polystyrene emulsion, filtering, drying in vacuum, re-dispersing in a solvent and the like, and then the polystyrene microspheres can be subjected to sol-gel reaction with the titanium source to prepare the nano core-shell titanium dioxide, and further prepare the nano hollow titanium dioxide; and the polystyrene microsphere is easy to generate adhesion deformation in the drying process so as to influence the appearance of the nano core-shell titanium dioxide microsphere. For example, Lidaiman in the document "research on preparation of TiO2 functional materials by cationic monomer template method" discloses that styrene, butyl acrylate and cationic monomer methacryloyloxyethyl trimethyl ammonium chloride are initiated to carry out polymerization reaction by azodiisobutyl imidazole hydrochloride to prepare cationic polystyrene emulsion, then the cationic polystyrene emulsion is centrifugally separated and dried in vacuum to prepare cationic template powder, and then the cationic template powder is dispersed in absolute ethyl alcohol, and PVP is added to react with butyl titanate to prepare nano core-shell titanium dioxide; however, the preparation steps of the scheme are complicated, and the prepared nano core-shell titanium dioxide particles are not uniform in size. For another example, chinese patent 200610011885.0 discloses a method for preparing monodisperse spherical mesoporous titania colloidal particles with controllable size and morphology, which comprises dispersing commercially available PSMMA spherical templates with different particle sizes in a solvent, adding a mixed solvent solution of butyl titanate, and adding dropwise ammonia water for catalytic hydrolysis to obtain nano core-shell titania; however, according to the scheme, a template agent needs to be purchased, the particle size and the morphology of the nano core-shell titanium dioxide depend on the particle size and the morphology of PSMMA produced by a template agent manufacturing company, nano hollow titanium dioxide microspheres with the required particle size cannot be prepared according to the requirement, and the nano core-shell titanium dioxide prepared by ammonia catalytic hydrolysis is sintered at the high temperature of 600 ℃ to obtain the mesoporous titanium dioxide.
Disclosure of Invention
One of the purposes of the invention is to provide a nano hollow titanium dioxide microsphere with low refractive index and high catalytic activity and a preparation method thereof aiming at the defects in the prior art, the method directly obtains the nano core-shell titanium dioxide microsphere with controllable particle size and shell thickness by a one-step method, greatly simplifies the preparation steps, and solves the technical problem that the polystyrene microsphere is easy to generate adhesion deformation in the drying process so as to influence the appearance of the nano core-shell titanium dioxide microsphere.
The purpose of the invention is realized by the following technical scheme:
the nanometer hollow titanium dioxide microsphere with low refractive index and high catalytic activity is prepared from the following raw materials in percentage by mass:
2 to 10 percent of cation polystyrene emulsion
10 to 15 percent of titanium source
1 to 2 percent of chelating agent
73-87% of solvent;
the cationic polystyrene emulsion is prepared by polymerizing the following components in percentage by mass:
64 to 87.4 percent of water
0.5 to 5 percent of initiator
10 to 20 percent of styrene
0.1 to 1 percent of divinylbenzene
1 to 5 percent of cationic monomer
1-5% of special functional monomer;
the special functional monomer is a zwitterionic reactive emulsifier SM-JR-1 produced by St.Momo organic chemistry research institute of Shangyu.
In the above technical scheme, the cationic monomer is at least one of acryloyloxyethyl trimethoxy ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, (meth) acrylamidopropyl trimethyl ammonium chloride, diallyl dimethyl ammonium chloride, benzyl vinyl trimethyl ammonium chloride and methacryloyloxyethyl dimethyl benzyl ammonium chloride.
In the technical scheme, the initiator is at least one of potassium persulfate, ammonium persulfate, sodium persulfate, benzoyl peroxide, azobisisobutyronitrile and azobisisobutylamidine hydrochloride.
In the above technical scheme, the solvent is at least one of methanol, ethanol and isopropanol.
In the technical scheme, the titanium source is at least one of butyl titanate, isopropyl titanate, titanium tetrachloride and titanyl sulfate.
In the above technical scheme, the chelating agent is at least one of acetylacetone, ethyl acetoacetate, monoethanolamine, diethanolamine and triethanolamine.
The invention also provides a preparation method of the nano hollow titanium dioxide microsphere with low refractive index and high catalytic activity, which comprises the following steps:
step a, adding 64-87.4% of water into a reaction container according to mass percent, starting stirring and heating, adding 0.5-5% of initiator when the temperature is raised to 60-135 ℃, starting adding 10-20% of styrene, 0.1-1% of divinylbenzene, 1-5% of cationic monomer and 1-5% of special functional monomer after the temperature is stabilized, finishing the addition within a preset time, and carrying out heat preservation reaction for a period of time; after the heat preservation is finished, cooling to 30-40 ℃, adding an auxiliary agent for neutralization, adjusting the pH value to 4-10, and then filtering to obtain a cationic polystyrene emulsion;
b, uniformly mixing 2-10% of cationic polystyrene emulsion and 73-87% of solvent by mass percent, slowly and dropwise adding a mixed solution of 10-15% of titanium source and 1-2% of chelating agent into the mixed solution for reaction for 4-24 hours under the condition of stirring at room temperature, and thus obtaining the titanium dioxide coated polystyrene nano core-shell titanium dioxide microsphere emulsion; then, centrifugally separating the nano core-shell titanium dioxide microsphere emulsion, and carrying out vacuum drying on the centrifugal precipitate at the temperature of 60-80 ℃ for 2-8 h to obtain uniform titanium dioxide/polystyrene nano core-shell structure composite particles;
and c, calcining the titanium dioxide/polystyrene nano core-shell structure composite particles for 2-4 hours at the temperature of 300-650 ℃, and naturally cooling to obtain nano hollow titanium dioxide microsphere powder.
In the technical scheme, in the step a, the styrene, the divinyl benzene, the cationic monomer and the special functional monomer are added within 4-8 hours, and the reaction time is kept at 6-16 hours.
In the above technical scheme, in the step a, the auxiliary agent is at least one of ammonia water, sodium hydroxide, monoethanolamine, diethanolamine, triethanolamine and triethylamine.
In the technical scheme, in the step b, the dropping time of the mixed solution of the titanium source and the chelating agent is 2-4 h.
The invention has the beneficial effects that:
the invention relates to a nano hollow titanium dioxide microsphere with low refractive index and high catalytic activity, which is characterized in that a cationic polystyrene emulsion which can be diluted by a solvent and is not demulsified is prepared by introducing a special functional monomer-zwitter-ion reactive emulsifier SM-JR-1; then diluting the cationic polystyrene emulsion with a solvent, adding a small amount of water into the emulsion, even adding no water, adding a titanium source to perform hydrolysis reaction, coating titanium dioxide on the surface of the cationic polystyrene microsphere to prepare the nano core-shell titanium dioxide microsphere with controllable particle size and shell thickness, and further preparing the nano hollow titanium dioxide microsphere. The introduced special functional monomer-zwitter ion reactive emulsifier SM-JR-1 contains anionic and cationic groups in the molecular structure and has openable carbon-carbon double bonds, can play the role of an emulsifier in emulsion polymerization and can participate in the polymerization reaction process, and is combined with a polymerization reaction monomer through covalent bonds to form a part of polymer molecules, so that the stability of the polymer emulsion can be greatly improved, and the polymer emulsion is diluted by a large amount of solvent without emulsion breaking; on the other hand, amphoteric anion and cation groups in the molecular structure of the nano core-shell titanium dioxide microsphere have a control effect on the hydrolysis condensation speed of a titanium source, and are beneficial to depositing and coating the nano titanium dioxide on the surface of polystyrene, so that the nano core-shell titanium dioxide microsphere with controllable particle size and shell thickness can be prepared. Therefore, compared with a series of complicated processing steps of firstly performing centrifugal separation, filtering, vacuum drying on a polystyrene emulsion, then re-dispersing the polystyrene emulsion in a solvent and the like on a cation polystyrene template in the prior art, the method directly obtains the nano core-shell titanium dioxide microspheres with controllable particle sizes and shell thicknesses through a one-step method, greatly simplifies the preparation steps, and avoids the phenomenon that the polystyrene microspheres are adhered and deformed in the drying process to influence the appearance of the nano core-shell titanium dioxide microspheres; the preparation method is simple and convenient, is easy to operate, and can realize large-scale production and application.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is a TEM image of a nano hollow titanium dioxide microsphere with low refractive index and high catalytic activity according to the present invention.
Fig. 2 is a graph showing the degradation curve of methyl orange in example 1 of the hollow nano titania microspheres with low refractive index and high catalytic activity according to the present invention.
FIG. 3 is a graph showing refractive index curves at different wavelength bands of example 1 of a hollow nano-titania microsphere with low refractive index and high catalytic activity according to the present invention.
Detailed Description
The invention is further described with reference to the following examples.
Example 1:
the hollow nano titanium dioxide microsphere with low refractive index and high catalytic activity is prepared by the following steps (the following components are calculated by mass percent):
step a, adding 73.4% of water into a reaction container, starting stirring and heating, adding 2% of ammonium persulfate initiator solution when the temperature is raised to 85 ℃, starting adding 18% of styrene, 0.6% of divinylbenzene, 2% of cationic monomer acryloyloxyethyl trimethoxy ammonium chloride and 4% of zwitterionic reactive emulsifier SM-JR-1 after the temperature is stable, finishing the addition within 6 hours, and carrying out heat preservation reaction for 10 hours; after the heat preservation is finished, cooling to 30 ℃, adding auxiliary agent ammonia water for neutralization, adjusting the pH value to 8, and then filtering to obtain cationic polystyrene emulsion;
b, uniformly mixing 5% of cationic polystyrene emulsion and 81% of solvent methanol, slowly dropwise adding a mixed solution of 12% of titanium source isopropyl titanate and 2% of chelating agent ethyl acetoacetate into the mixed solution within 3 hours under the condition of stirring at room temperature, and reacting for 10 hours to obtain the nano core-shell titanium dioxide microsphere emulsion of the polystyrene coated with titanium dioxide; then centrifugally separating the nano core-shell titanium dioxide microsphere emulsion, and drying the centrifugal precipitate for 4 hours at 70 ℃ in vacuum to obtain uniform titanium dioxide/polystyrene nano core-shell structure composite particles;
and c, calcining the titanium dioxide/polystyrene nano core-shell structure composite particles for 3 hours at the temperature of 450 ℃, and naturally cooling to obtain nano hollow titanium dioxide microsphere powder.
The structure of the nano hollow titanium dioxide microsphere under TEM is shown in figure 1.
Example 2:
the hollow nano titanium dioxide microsphere with low refractive index and high catalytic activity is prepared by the following steps (the following components are calculated by mass percent):
step a, adding 64% of water into a reaction container, starting stirring and heating, adding an initiator solution of 2% of potassium persulfate and 3% of sodium persulfate when the temperature is raised to 135 ℃, starting adding 20% of styrene, 1% of divinylbenzene, cationic monomers of 4% of methacryloyloxyethyl trimethyl ammonium chloride and 1% of acrylamidopropyl trimethyl ammonium chloride and 5% of zwitterionic reactive emulsifier SM-JR-1 after the temperature is stabilized, finishing the addition within 4 hours, and carrying out heat preservation reaction for 6 hours; after the heat preservation is finished, cooling to 33 ℃, adding an auxiliary agent diethanol amine for neutralization, adjusting the pH value to 7, and then filtering to obtain a cationic polystyrene emulsion;
b, uniformly mixing 2% of cationic polystyrene emulsion and 87% of solvent ethanol, slowly dropwise adding a mixed solution of 10% of titanium source butyl titanate and 1% of chelating agent acetylacetone within 2 hours under the condition of stirring at room temperature, and reacting for 4 hours to obtain the nano core-shell titanium dioxide microsphere emulsion of the polystyrene coated by titanium dioxide; then centrifugally separating the nano core-shell titanium dioxide microsphere emulsion, and vacuum-drying 2 the centrifugal precipitate at 80 ℃ to obtain uniform titanium dioxide/polystyrene nano core-shell structure composite particles;
and c, calcining the titanium dioxide/polystyrene nano core-shell structure composite particles for 2 hours at 650 ℃, and naturally cooling to obtain nano hollow titanium dioxide microsphere powder.
Example 3:
the hollow nano titanium dioxide microsphere with low refractive index and high catalytic activity is prepared by the following steps (the following components are calculated by mass percent):
step a, adding 87.4% of water into a reaction container, starting stirring and heating, adding 0.5% of benzoyl peroxide initiator solution when the temperature is raised to 60 ℃, starting to add 10% of styrene, 0.1% of divinylbenzene, 0.5% of benzyl vinyl trimethyl ammonium chloride and 0.5% of methacryloyloxyethyl dimethyl benzyl ammonium chloride of cationic monomers and 1% of zwitterionic reactive emulsifier SM-JR-1 after the temperature is stabilized, completing the addition within 8h, and carrying out heat preservation reaction for 13 h; after the heat preservation is finished, cooling to 37 ℃, adding assistants triethanolamine and triethylamine for neutralization, adjusting the pH value to 4, and then filtering to obtain a cationic polystyrene emulsion;
b, uniformly mixing 10% of cationic polystyrene emulsion and 73% of isopropanol solvent, slowly dropwise adding a mixed solution of 6% titanium tetrachloride as a titanium source, 9% titanyl sulfate as a chelating agent, 1% ethyl acetoacetate and 1% monoethanolamine into the mixed solution within 4 hours under the condition of stirring at room temperature, and reacting for 24 hours to obtain the nano core-shell titanium dioxide microsphere emulsion of the polystyrene coated with titanium dioxide; then centrifugally separating the nano core-shell titanium dioxide microsphere emulsion, and vacuum-drying the centrifugal precipitate at 60 ℃ for 6 hours to obtain uniform titanium dioxide/polystyrene nano core-shell structure composite particles;
and c, calcining the titanium dioxide/polystyrene nano core-shell structure composite particles for 4 hours at 300 ℃, and naturally cooling to obtain nano hollow titanium dioxide microsphere powder.
Example 4:
the hollow nano titanium dioxide microsphere with low refractive index and high catalytic activity is prepared by the following steps (the following components are calculated by mass percent):
step a, adding 77.7% of water into a reaction container, starting stirring and heating, adding 2% of azobisisobutyronitrile and 1% of initiator solution of azobisisobutylamidine hydrochloride when the temperature is raised to 105 ℃, starting adding 14% of styrene, 0.3% of divinylbenzene, 3% of cationic monomer diallyl dimethyl ammonium chloride and 2% of zwitterionic reactive emulsifier SM-JR-1 after the temperature is stabilized, finishing the addition within 5 hours, and carrying out heat preservation reaction for 16 hours; after the heat preservation is finished, cooling to 40 ℃, adding an auxiliary agent sodium hydroxide for neutralization, adjusting the pH value to 10, and then filtering to obtain a cationic polystyrene emulsion;
b, uniformly mixing 8% of cationic polystyrene emulsion, 38% of ethanol and 40% of isopropanol serving as solvents, slowly dropwise adding a mixed solution of 5% of butyl titanate and 8% of isopropyl titanate serving as a titanium source, 0.8% of diethanolamine and 0.2% of triethanolamine serving as a chelating agent into the mixed solution within 3 hours under the condition of stirring at room temperature, and reacting for 18 hours to obtain the nano core-shell titanium dioxide microsphere emulsion of the polystyrene coated by titanium dioxide; then centrifugally separating the nano core-shell titanium dioxide microsphere emulsion, and drying the centrifugal precipitate for 8 hours at 65 ℃ in vacuum to obtain uniform titanium dioxide/polystyrene nano core-shell structure composite particles;
and c, calcining the titanium dioxide/polystyrene nano core-shell structure composite particles for 3 hours at 550 ℃, and naturally cooling to obtain nano hollow titanium dioxide microsphere powder.
Test and test:
1. the structure of the nano hollow titanium dioxide microsphere under TEM is shown in figure 1.
2. And (3) testing the catalytic effect:
the nano hollow titanium dioxide of example 1 has a catalytic effect on methyl orange under simulated sunlight irradiation, and as shown in fig. 2, it is understood that the nano hollow titanium dioxide has a very good catalytic decomposition effect on methyl orange.
3. And (3) testing the refractive index:
the refractive indexes of the nano hollow titanium dioxide microspheres of example 1 at different wave bands were measured by an ellipsometer, and the result is shown in fig. 3, where the average refractive index at all wave bands is 1.91. From this, the nano hollow titanium dioxide has a low refractive index.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the present invention.
Claims (9)
1. A preparation method of nano hollow titanium dioxide microspheres with low refractive index and high catalytic activity is characterized in that: the nano hollow titanium dioxide microspheres are prepared from the following raw materials in percentage by mass:
2-10% of cationic polystyrene emulsion
10 to 15 percent of titanium source
1 to 2 percent of chelating agent
73% -87% of a solvent;
the cationic polystyrene emulsion is prepared by polymerizing the following components in percentage by mass:
64 to 87.4 percent of water
0.5 to 5 percent of initiator
10 to 20 percent of styrene
0.1 to 1 percent of divinylbenzene
1 to 5 percent of cationic monomer
1-5% of special functional monomer;
the special functional monomer is a zwitterionic reactive emulsifier SM-JR-1 produced by Stmo organic chemistry research institute of Shangyu city;
the preparation method of the nano titanium dioxide hollow microsphere comprises the following steps:
step a, adding 64-87.4% of water into a reaction container according to mass percent, starting stirring and heating, adding 0.5-5% of initiator when the temperature is raised to 60-135 ℃, starting adding 10-20% of styrene, 0.1-1% of divinylbenzene, 1-5% of cationic monomer and 1-5% of special functional monomer after the temperature is stabilized, finishing the addition within a preset time, and carrying out heat preservation reaction for a period of time; after the heat preservation is finished, cooling to 30-40 ℃, adding an auxiliary agent for neutralization, adjusting the pH value to 4-10, and then filtering to obtain a cationic polystyrene emulsion;
b, uniformly mixing 2-10% of cationic polystyrene emulsion and 73-87% of solvent by mass percent, slowly and dropwise adding a mixed solution of 10-15% of titanium source and 1-2% of chelating agent into the mixed solution for reaction for 4-24 hours under the condition of stirring at room temperature, and thus obtaining the titanium dioxide coated polystyrene nano core-shell titanium dioxide microsphere emulsion; then, centrifugally separating the nano core-shell titanium dioxide microsphere emulsion, and carrying out vacuum drying on the centrifugal precipitate at the temperature of 60-80 ℃ for 2-8 h to obtain uniform titanium dioxide/polystyrene nano core-shell structure composite particles;
and c, calcining the titanium dioxide/polystyrene nano core-shell structure composite particles for 2-4 hours at the temperature of 300-650 ℃, and naturally cooling to obtain nano hollow titanium dioxide microsphere powder.
2. The method for preparing nano hollow titanium dioxide microspheres with low refractive index and high catalytic activity according to claim 1, wherein the method comprises the following steps: the cationic monomer is at least one of acryloyloxyethyl trimethoxy ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, (methyl) acrylamidopropyl trimethyl ammonium chloride, diallyl dimethyl ammonium chloride, benzyl vinyl trimethyl ammonium chloride and methacryloyloxyethyl dimethyl benzyl ammonium chloride.
3. The method for preparing nano hollow titanium dioxide microspheres with low refractive index and high catalytic activity according to claim 1, wherein the method comprises the following steps: the initiator is at least one of potassium persulfate, ammonium persulfate, sodium persulfate, benzoyl peroxide, azobisisobutyronitrile and azobisisobutylamidine hydrochloride.
4. The method for preparing nano hollow titanium dioxide microspheres with low refractive index and high catalytic activity according to claim 1, wherein the method comprises the following steps: the solvent is at least one of methanol, ethanol and isopropanol.
5. The method for preparing nano hollow titanium dioxide microspheres with low refractive index and high catalytic activity according to claim 1, wherein the method comprises the following steps: the titanium source is at least one of butyl titanate, isopropyl titanate, titanium tetrachloride and titanyl sulfate.
6. The method for preparing nano hollow titanium dioxide microspheres with low refractive index and high catalytic activity according to claim 1, wherein the method comprises the following steps: the chelating agent is at least one of acetylacetone, ethyl acetoacetate, monoethanolamine, diethanolamine and triethanolamine.
7. The method for preparing nano hollow titanium dioxide microspheres with low refractive index and high catalytic activity according to claim 1, wherein the method comprises the following steps: in the step a, the styrene, the divinyl benzene, the cationic monomer and the special functional monomer are added within 4-8 hours, and the reaction time is kept for 6-16 hours.
8. The method for preparing nano hollow titanium dioxide microspheres with low refractive index and high catalytic activity according to claim 1, wherein the method comprises the following steps: in the step a, the auxiliary agent is at least one of ammonia water, sodium hydroxide, monoethanolamine, diethanolamine, triethanolamine and triethylamine.
9. The method for preparing nano hollow titanium dioxide microspheres with low refractive index and high catalytic activity according to claim 1, wherein the method comprises the following steps: in the step b, the dropping time of the mixed solution of the titanium source and the chelating agent is 2-4 h.
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| CN106816539B (en) * | 2016-12-08 | 2018-10-12 | 瑞声科技（南京）有限公司 | Light emitting diode with quantum dots device and its manufacturing method |
| CN106770264A (en) * | 2017-03-01 | 2017-05-31 | 福建医科大学 | A kind of method that nanoscale molybdenum oxide analogue enztme based on paper micro-fluidic chip detects glucose |
| CN108822249A (en) * | 2018-07-17 | 2018-11-16 | 常州工程职业技术学院 | A kind of Organic-inorganic composite lotion for field of metal surface treatment |
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