CN113441182A - Preparation method of core-shell titanium dioxide @ carboxyl chitosan nanoparticles - Google Patents
Preparation method of core-shell titanium dioxide @ carboxyl chitosan nanoparticles Download PDFInfo
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- CN113441182A CN113441182A CN202110726744.1A CN202110726744A CN113441182A CN 113441182 A CN113441182 A CN 113441182A CN 202110726744 A CN202110726744 A CN 202110726744A CN 113441182 A CN113441182 A CN 113441182A
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- titanium dioxide
- carboxyl chitosan
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- carboxyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 84
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- 238000000034 method Methods 0.000 claims abstract description 33
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- -1 CTAB cation modified titanium dioxide Chemical class 0.000 claims abstract description 31
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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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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
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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
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Abstract
The invention discloses a preparation method of core-shell titanium dioxide @ carboxyl chitosan nanoparticles, which is prepared by taking anatase type nano titanium dioxide and carboxyl chitosan prepared by ionic liquid reaction as raw materials and performing ionic gelation of CTAB cation modified titanium dioxide and phosphate and crosslinking and assembling of a high-molecular auxiliary agent. The method is simple and convenient to operate, green and environment-friendly, the prepared core-shell type nanometer particles can effectively avoid the photo-corrosion of nanometer titanium dioxide to a carrier, the amino and carboxyl of carboxyl chitosan can be respectively combined with photo-generated electrons and holes of the nanometer titanium dioxide, the photocatalysis performance of the titanium dioxide is obviously enhanced, the electrostatic repulsion force exists on the surfaces of the core-shell type nanometer particles, the defect that the nanometer particles are easy to agglomerate is overcome, and the application prospect is wide.
Description
Technical Field
The invention relates to a preparation method of core-shell titanium dioxide @ carboxyl chitosan nanoparticles, belonging to the technical field of functional nano material preparation.
Background
The chitosan is a deacetylated product of chitin, which is the second largest biomass resource in the nature, is the only natural cationic basic aminopolysaccharide in the nature, and has the advantages of wide source, reproducibility, low cost, good biocompatibility, degradability, no toxicity and the like. But the acid solution is insoluble in water and soluble in acid solution, and the acid solution has strong corrosivity and pollutes the environment. The carboxyl chitosan is a product of chitosan after being selectively oxidized by an oxidation system, and is characterized in that partial hydroxyl on C6 site is oxidized into carboxyl while the rest functional groups are unchanged, and the carboxyl chitosan has the unique advantages of good water solubility, high chemical reactivity and good biological activity.
The nano carboxyl chitosan has higher specific surface area, reaction activity and adsorbability due to the nano size effect. The ion gel method is a simple and rapid method for preparing carboxyl chitosan nanoparticles, can generate particles with the particle size of dozens to hundreds of nanometers under mild conditions, does not use organic solvents and aldehyde crosslinking agents, has simple process and good condition controllability, is easy for large-scale production, and the obtained carboxyl chitosan nanoparticles have good stability and uniform particle size. The reaction principle is as follows: under acidic conditions, carboxyl chitosan amino is protonated and positively charged, and is in ionic bond crosslinking with phosphate groups (sodium tripolyphosphate and sodium pyrophosphate) which are negatively charged. The carboxyl chitosan is long-chain macromolecules, and the long chains are broken by the combined action of multiple ionic bond crosslinking and are respectively wound into balls to form the carboxyl chitosan particles with nanometer sizes.
Titanium dioxide is a well-known N-type semiconductor photocatalytic material, and has obvious advantages compared with other semiconductor photocatalytic materialsPotential: (1) the oxidation-reduction capability is strong, and a plurality of organic pollutants can be degraded; (2) the ultraviolet light utilization rate is high; (3) the chemical property is stable; (4) the adsorption performance is good, and various organic pollutants can be adsorbed; (5) low-cost and non-toxic [ Zhang Cai Yun, microwave auxiliary method for preparing TiO2Chitosan sulfate microspheres and research thereof in dye decolorization, university of east China, 2018]. Therefore, titanium dioxide is increasingly studied and used in the field of photocatalysis. Of the three crystal forms of titanium dioxide (rutile, brookite and anatase), brookite is less in application. Anatase has higher forbidden bandwidth, more lattice defects and dislocations, smaller size and larger specific surface area compared with rutile, so that the photocatalysis effect is better [ Ningwei. preparation of titanium dioxide nanofiber material and the photocatalysis degradation performance of titanium dioxide nanofiber material to formaldehyde, university of Donghua, 2017]. However, the nano titanium dioxide has the following problems: due to high specific surface area and small size, the particles are easy to agglomerate; electrons and holes which play a main role in the photocatalysis process are easy to recombine, and the photocatalysis effect is influenced; the photocatalytic reaction is spontaneous and nonselective, and can cause serious corrosion of attached carriers while decomposing pollutants.
At present, the preparation methods of the nano titanium dioxide are various, such as an atomization hydrolysis method, a diffusion flame method, a gas phase synthesis method, a gas phase deposition method, a sol-gel method, a liquid phase deposition method, a cathode electrodeposition method, a spray thermal decomposition method, a thermal hydrolysis method, a solid mixing method, a direct roasting method [ Wang Shurong, Liu Yan Qing ] nano titanium dioxide preparation method and application research progress, synthetic material aging and application, 2020,49(5):146-]. These methods have advantages, but the sol-gel method has wide application due to simple operation, low cost, short test period and high safety. The sol-gel method for preparing anatase type nano titanium dioxide has a wide research range, and generally, anhydrous ethanol is used as a solvent, acid is used as an inhibitor, and metal alkoxide is used as a precursor to form nano titanium dioxide through hydrolytic polycondensation. And after colloid is formed, high-temperature drying is needed, and finally the anatase type nano titanium dioxide is formed. However, the metal alkoxide is hydrolyzed and condensed too fast, so that the reaction is difficult to control the crystal form of the product. In recent years, there has been a growing adoption of ions by researchersThe liquid is used as solvent to prepare anatase type nano titanium dioxide. Such as Takuya Nakashima, etc., under the condition of vigorous stirring, adding dropwise anhydrous formaldehyde solution of tetrabutyl titanate into 1-butyl-3-methylimidazolium hexafluorophosphate, adding methanol, centrifuging to obtain gel, and vacuum drying to obtain anatase type nano titanium dioxide microspheres [ Nakashima Takuya, Kimizuka nobu2microspheres in ionic liquids.Journal of the American Chemical Society,2003,125(21):6386-7]. The reaction method using the ionic liquid as the medium does not need to add excessive inhibitors to control the reaction speed, has stable product and lower reaction temperature, can recycle the ionic liquid, and can obtain the anatase type nano titanium dioxide without high-temperature calcination in the experimental process.
The chitosan serving as a porous biomass material is compounded with the nano titanium dioxide, and has great application prospects in the fields of sewage purification, formaldehyde degradation, self-cleaning and the like. Many studies have been reported on this point, but many studies require that chitosan be dissolved in an acid solution (acetic acid, hydrochloric acid, acrylic acid, etc.) containing a crosslinking agent (glutaraldehyde, polycarboxylic acid, etc.) to achieve the complex of the two. In addition, most researches on the compounding methods of the titanium dioxide and the titanium dioxide are simple and direct compounding and cannot completely coat the nano titanium dioxide, so that the composite particles have certain photocatalytic damage on the carrier, and the service life of the substrate is further influenced. Therefore, the core-shell titanium dioxide @ carboxyl chitosan composite nano-particles prepared by the method have important significance for reducing the use of acid and a cross-linking agent, avoiding the photo-corrosion effect of nano-titanium dioxide on a carrier and enhancing the photo-catalytic activity of the titanium dioxide.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a method for preparing core-shell titanium dioxide @ carboxyl chitosan nanoparticles, and aims to prepare environment-friendly core-shell nanoparticles which can effectively enhance the photocatalytic activity of titanium dioxide, reduce the photo-corrosion of the photocatalytic effect of titanium dioxide on a load, reduce nanoparticle agglomeration, improve stability and reaction activity, and can be recycled.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for preparing the core-shell titanium dioxide @ carboxyl chitosan nanoparticles uses the anatase type nano-titanium dioxide and carboxyl chitosan prepared by ionic liquid reaction as raw materials and includes such steps as modifying titanium dioxide by CTAB cation, ionic gelation of phosphate and cross-linking of high-molecular assistant. The method comprises the following steps:
step 1, adding 1-5 mL of tetrabutyl titanate into 10-20 mL of ionic liquid 1-ethyl-3-methylimidazole acetate (Emimac), uniformly mixing at room temperature, then slowly dropwise adding 2-10 mL of deionized water at a constant speed, and continuously stirring for 4-6 h at 40-60 ℃; adding 20-40 mL of absolute ethanol for dilution to reduce viscosity, performing high-speed centrifugal separation to obtain titanium dioxide, performing ultrasonic cleaning by using 50% (v/v) ethanol solution to remove residual ionic liquid on the surface of the titanium dioxide, and performing vacuum drying to obtain anatase type nano titanium dioxide;
step 2, uniformly dispersing the titanium dioxide prepared in the step 1 in 50mL of 2 vol% acetic acid solution according to the mass concentration of 0.05-0.4%, adding 1-10 mmol of Cetyl Trimethyl Ammonium Bromide (CTAB), stirring and mixing, putting into a reaction kettle, and heating in a microwave reactor at 70-90 ℃ for 20-60 min to prepare a cation modified titanium dioxide dispersion liquid;
step 3, dissolving 0.2g of carboxyl chitosan in 50mL of 2% acetic acid solution at 80 ℃, then dropwise adding Span 80 until the concentration of Span 80 in the system is 0.5-1.5 g/L, continuously stirring for 20-30 min, naturally cooling to room temperature, then dropwise adding a phosphate mixed solution until the concentration of phosphate in the system is 0.2-0.6 g/L, and continuously stirring for 30 min; the phosphate mixed solution is a mixed solution of sodium pyrophosphate and sodium tripolyphosphate;
dropwise adding 50mL of the cation modified titanium dioxide dispersion prepared in the step 2 into the system at a constant speed within 30min, continuously stirring and reacting for 1-2 h after dropwise adding, then adding 0.1-0.5 g of a high molecular additive, strongly stirring for 40-90 min, enabling phosphate to be combined with cation modified titanium dioxide particles, enabling amino cations of carboxyl chitosan and phosphate anions of phosphate to be mutually crosslinked, further performing ionic gelation and assembling of the high molecular additive to form core-shell type nanoparticles, and enabling the solution to be opalescent;
the mass ratio of the carboxyl chitosan to the phosphate is 1: 0.5-1.5; the mass ratio of the sodium pyrophosphate to the sodium tripolyphosphate is 0.5-1: 2;
and 4, standing and aging the nanoparticle dispersion liquid obtained in the step 3 for 1-3 hours, centrifuging the dispersion liquid by using a high-speed refrigerated centrifuge, removing a supernatant, adding a freeze-drying protective agent solution with the mass concentration of 0.5-1%, and freeze-drying to obtain the well-dispersed core-shell titanium dioxide @ carboxyl chitosan nanoparticles.
Preferably, in the step 1, the anatase type nano titanium dioxide has an average particle size of 16 to 25nm and a Zeta potential of 38.22 to 42.41 mV.
Preferably, in step 3, the viscosity-average molecular weight of the carboxyl chitosan is 0.85 to 1.96 ten thousand, the deacetylation degree is more than or equal to 91.3%, the carboxyl degree at the C6 position is 40.27 to 61.58%, the free amino group is 4.453 to 5.179mmol/g, and the structural formula of the carboxyl chitosan is as follows:
preferably, the particle size range of the obtained core-shell titanium dioxide @ carboxyl chitosan nano-particles is 78-137 nm, the Zeta potential is 27.18-40.76 mV, and the monodispersion coefficient is 0.208-0.501.
Preferably, in the step 2, the microwave radiation power of the microwave reactor is 600-800W.
Preferably, in the step 3, the polymer auxiliary agent is gelatin, sodium alginate or polyethylene glycol with the number average molecular weight of 400-1000.
Preferably, in step 4, the lyoprotectant is skim milk, pullulan, sucrose or glucose.
By optimizing the molar ratio of CTAB to nano titanium dioxide, the carboxyl degree of carboxyl chitosan C6, the using amount of phosphate, the reaction time and/or the types and the adding amount of polymer auxiliaries, a series of core-shell type nano particles with different particle sizes and photocatalysis effects can be obtained.
Compared with the prior art, the preparation principle and the advantages of the core-shell titanium dioxide @ carboxyl chitosan nanoparticle are as follows:
1. the invention is green and environment-friendly, does not use chemical reagents such as acid, cross-linking agent and the like, the used sodium pyrophosphate and sodium tripolyphosphate are commonly used as food additives, and CTAB is also commonly applied to cosmetics, toothpaste and hair conditioner, thereby being safe and sanitary.
2. According to the invention, ionic liquid 1-ethyl-3-methylimidazole acetate (Emimac) is used as a reaction medium to prepare anatase type nano titanium dioxide, the Emimac is easy to adsorb water, rapid hydrolysis and agglomeration of tetrabutyl titanate can be effectively avoided, and the ionic liquid can be subjected to catalytic reaction at normal temperature to generate anatase type nano titanium dioxide, high-temperature calcination is not required, and the method has the advantages of short period, high efficiency, cyclic utilization, no pollution and the like.
3. According to the invention, CTAB is used for carrying out cationic modification on titanium dioxide under the microwave irradiation condition, the microwave heating speed is high, the liquid phase synthesis reaction efficiency and uniformity can be effectively improved, and the cationized titanium dioxide material with nano-scale size and good uniformity is obtained.
4. According to the invention, CTAB cation modified titanium dioxide is adopted, carboxyl, hydroxyl and phosphate anions in carboxyl chitosan are easily combined with cationized titanium dioxide in a crosslinking manner, further, carboxyl chitosan and phosphate ions are gelled to form core-shell nano particles for encapsulating the titanium dioxide, then, hydrophilic polymer auxiliaries are utilized to be assembled with the carboxyl chitosan in a crosslinking manner, and hydrophilic polymer long chains are introduced into carboxyl chitosan molecules to improve the biocompatibility of the core-shell titanium dioxide @ carboxyl chitosan nano particles and the stability of the core-shell titanium dioxide @ carboxyl chitosan nano particles in a solution. Meanwhile, carboxyl and amino on carboxyl chitosan can be respectively combined with holes and electrons which are activated by titanium dioxide photocatalysis, so that the combination of the two is effectively prevented, and the photocatalysis effect is obviously enhanced; the prepared core-shell titanium dioxide @ carboxyl chitosan nanoparticle has the advantages of small particle size, uniform distribution, strong stability and high biological activity, and can realize non-corrosion of a matrix material and a good photocatalytic function.
5. The invention adopts carboxyl-based chitosanThe chitosan nano carrier is prepared from sugar, and carboxyl chitosan selectively oxidizes C6-site primary hydroxyl in chitosan molecules into carboxyl, does not influence the chitosan ring skeleton and the characteristics of chitosan as alkaline polysaccharide, and has the characteristics of good water solubility, biocompatibility, degradability, reactivity, bacteriostasis, environmental friendliness, safety, sanitation and the like. The carboxyl chitosan molecule contains carboxyl and amino, and is an amphoteric polyelectrolyte, and the amino in the pyranose ring can be protonated by carboxyl to have positive charge (-NH)3 +) The crosslinking effect with TPP phosphate anions is enhanced, and the nanoparticles with small particle size and strong stability are favorably formed; on the other hand, carboxyl at the C6 position of carboxyl chitosan can freely rotate on spatial conformation, has small steric hindrance and high chemical activity, is easy to contact with hydrophilic macromolecule links for binding reaction, and greatly improves the physical and chemical stability and the reaction activity of the core-shell titanium dioxide @ carboxyl chitosan nano particles through the auxiliary crosslinking action of a macromolecule auxiliary agent, so that the nano particles have smaller size, uniform particle size and wider application.
Drawings
FIG. 1 is a schematic diagram of the preparation of core-shell titanium dioxide @ carboxyl chitosan nanoparticles of the present invention.
FIG. 2 is a transmission electron microscope image of anatase type titanium dioxide nanoparticles and core-shell type nanoparticles in test item 2 of the present invention.
FIG. 3 is an X-ray diffraction pattern of anatase type titanium dioxide nanoparticles and core-shell type nanoparticles in item 3 of the present invention.
FIG. 4 is a graph showing photocatalytic degradation of methylene blue by core-shell type nano-particles and anatase type nano-titania in test item 4 of the present invention.
Detailed Description
The invention will now be further described with reference to the accompanying drawings and examples, which are given for the purpose of illustration only and are not intended to be limiting in any way.
Preparation of core-shell titanium dioxide @ carboxyl chitosan nanoparticles
Example 1
In this example, core-shell titania @ carboxyl chitosan nanoparticles were prepared as follows:
(1) dropping 1mL of tetrabutyl titanate into 10mL of ionic liquid 1-ethyl-3-methylimidazole acetate at a constant speed within 5min under strong stirring, reacting at room temperature for 0.5h, dropping 2mL of deionized water at a constant speed within 5min, reacting at 40 ℃ for 4h, adding 20mL of absolute ethyl alcohol, stirring uniformly, centrifuging at a high speed for 3 times, removing a supernatant, performing ultrasonic treatment on 50% of ethyl alcohol for three times, filtering, and performing vacuum drying at 40 ℃ to obtain the anatase type nano titanium dioxide.
(2) And (2) dispersing 0.025g of titanium dioxide prepared in the step (1) in 50mL of 2% acetic acid (v/v) solution, adding 1mmol of CTAB, strongly stirring for 30min, placing in a reaction kettle, placing in a microwave reactor, and heating at 70 ℃ for 20min to prepare the cation modified titanium dioxide dispersion. Wherein the power of the microwave reactor is 600W, and the mass concentration of the titanium dioxide is 0.05 percent.
(3) Dissolving 0.2g of carboxyl chitosan in 50mL of 2% acetic acid (v/v) solution at 80 ℃, adding 0.025g of Span 80, continuously stirring for 30min, naturally cooling to room temperature, slowly dropwise adding a phosphate mixed solution (1.4 mL of 25g/L sodium pyrophosphate solution and 2.8mL of 25g/L sodium tripolyphosphate solution), continuously stirring for 30min, dropwise adding the cation modified titanium dioxide dispersion prepared in the step (2) at a constant speed within 30min under strong stirring, reacting for 1h, adding 0.1g of macromolecular auxiliary gelatin, and stirring for 40 min. Wherein the viscosity average molecular weight of the carboxyl chitosan is 0.85 ten thousand, the deacetylation degree is 91.3 percent, the carboxyl degree at C6 is 40.27 percent, and the free ammonia is 5.153 mmol/g; the mass ratio of the carboxyl chitosan to the titanium dioxide is 8:1, and the mass ratio of the carboxyl chitosan to the phosphate is 1: 0.5.
(4) Standing and aging for 1h, centrifuging by a high-speed refrigerated centrifuge, removing supernatant, adding a freeze-drying protective agent solution with the mass concentration of 0.5%, and freeze-drying to obtain the well-dispersed titanium dioxide @ carboxyl chitosan nanoparticles with the core-shell structure. Wherein the freeze-drying protective agent is glucose; the prepared core-shell structure particle passes the test of a particle size scatterometer (DLS), the average particle diameter is 131nm, the Zeta potential is 36.25mV, and the monodisperse coefficient is 0.259.
Example 2
In this example, core-shell titania @ carboxyl chitosan nanoparticles were prepared as follows:
(1) under strong stirring, dripping 2.5mL of tetrabutyl titanate into 15mL of ionic liquid 1-ethyl-3-methylimidazole acetate at a constant speed within 10min, reacting for 1h at room temperature, dripping 5mL of deionized water at a constant speed within 10min, reacting for 5h at 45 ℃, adding 30mL of absolute ethyl alcohol, uniformly stirring, centrifuging at a high speed for 3 times, removing a supernatant, carrying out ultrasonic treatment on 50% (v/v) of ethanol for three times, filtering, and carrying out vacuum drying at 40 ℃ to obtain the anatase type nano titanium dioxide.
(2) And (2) dispersing 0.05g of titanium dioxide prepared in the step (1) in 50mL of 2% acetic acid (v/v) solution, adding 3mmol of CTAB, strongly stirring for 30min, placing the mixture into a reaction kettle, placing the reaction kettle in a microwave reactor, and heating for 30min at 80 ℃ to prepare the cation modified titanium dioxide dispersion liquid. Wherein the power of the microwave reactor is 650W, and the mass concentration of the titanium dioxide is 0.1 percent.
(3) Dissolving 0.2g of carboxyl chitosan in 50mL of 2% acetic acid (v/v) solution at 80 ℃, adding 0.05g of Span 80, continuously stirring for 30min, naturally cooling to room temperature, slowly dropwise adding phosphate mixed solution (2.8 mL of 25g/L sodium pyrophosphate solution and 5.6mL of 25g/L sodium tripolyphosphate solution), continuously stirring for 30min, dropwise adding the cation modified titanium dioxide dispersion prepared in the step (2) at a constant speed within 30min under strong stirring, reacting for 1.5h, adding 0.2g of macromolecular auxiliary agent sodium alginate, and stirring for 50 min. Wherein the viscosity average molecular weight of the carboxyl chitosan is 1.12 ten thousand, the deacetylation degree is 91.3 percent, the carboxyl degree at C6 is 48.35 percent, and the free ammonia is 4.968 mmol/g; the mass ratio of the carboxyl chitosan to the titanium dioxide is 4:1, and the mass ratio of the carboxyl chitosan to the phosphate is 1:1.
(4) Standing and aging for 1h, centrifuging by a high-speed refrigerated centrifuge, removing supernatant, adding a freeze-drying protective agent solution with the mass concentration of 0.5%, and freeze-drying to obtain the well-dispersed titanium dioxide @ carboxyl chitosan nanoparticles with the core-shell structure. Wherein the freeze-drying protective agent is skim milk; the prepared core-shell structure particles pass the test of a particle size scatterometer (DLS), the average particle size is 117nm, the Zeta potential is 29.23mV, and the monodisperse coefficient is 0.408.
Example 3
In this example, core-shell titania @ carboxyl chitosan nanoparticles were prepared as follows:
(1) under strong stirring, 5mL of tetrabutyl titanate is uniformly dripped into 20mL of ionic liquid 1-ethyl-3-methylimidazole acetate within 15min, the mixture reacts for 1.5h at room temperature, 8mL of deionized water is uniformly dripped within 20min, the mixture reacts for 6h at 50 ℃, 40mL of absolute ethyl alcohol is added, after uniform stirring, the mixture is centrifuged for 3 times at high speed, the supernatant is discarded, 50% (v/v) of ethyl alcohol is subjected to ultrasonic treatment for three times, and the anatase type nano titanium dioxide is obtained after filtration and vacuum drying at 40 ℃.
(2) And (2) dispersing 0.10g of titanium dioxide prepared in the step (1) in 50mL of 2% acetic acid (v/v) solution, adding 6mmol of CTAB, strongly stirring for 30min, placing into a reaction kettle, placing into a microwave reactor, and heating at 90 ℃ for 50min to obtain the cation modified titanium dioxide dispersion liquid. Wherein the power of the microwave reactor is 800W, and the mass concentration of the titanium dioxide is 0.2 percent.
(3) Dissolving 0.2g of carboxyl chitosan in 50mL of 2% acetic acid (v/v) solution at 80 ℃, adding 0.05g of Span 80, continuously stirring for 30min, naturally cooling to room temperature, slowly dropwise adding phosphate mixed solution (2.8 mL of 25g/L sodium pyrophosphate solution and 5.6mL of 25g/L sodium tripolyphosphate solution), continuously stirring for 30min, dropwise adding the cation modified titanium dioxide dispersion prepared in the step (2) at a constant speed within 30min under strong stirring, reacting for 1.5h, adding 0.3g of macromolecular auxiliary agent sodium alginate, and stirring for 70 min. Wherein the viscosity average molecular weight of the carboxyl chitosan is 1.67 ten thousand, the deacetylation degree is 91.3 percent, the carboxyl degree at C6 is 61.58 percent, and the free ammonia is 4.482 mmol/g; the mass ratio of the carboxyl chitosan to the titanium dioxide is 2:1, and the mass ratio of the carboxyl chitosan to the phosphate is 1:1.
(4) Standing and aging for 1h, centrifuging by a high-speed refrigerated centrifuge, removing supernatant, adding a freeze-drying protective agent solution with the mass concentration of 0.75%, and freeze-drying to obtain the well-dispersed titanium dioxide @ carboxyl chitosan nanoparticles with the core-shell structure. Wherein the freeze-drying protective agent is sucrose; the prepared core-shell structure particles pass through a particle size scatterometer (DLS) test, the average particle size is 83nm, the Zeta potential is 40.12mV, and the monodisperse coefficient is 0.356.
Example 4
In this example, core-shell titania @ carboxyl chitosan nanoparticles were prepared as follows:
(1) under strong stirring, 5mL of tetrabutyl titanate is uniformly dripped into 20mL of ionic liquid 1-ethyl-3-methylimidazole acetate within 20min, the mixture reacts for 2h at room temperature, 10mL of deionized water is uniformly dripped within 25min, the mixture reacts for 5h at 60 ℃, 30mL of absolute ethyl alcohol is added, the mixture is uniformly stirred and then centrifuged at high speed for 3 times, the supernatant is discarded, 50% (v/v) of ethyl alcohol is subjected to ultrasonic treatment for three times, and the anatase type nano titanium dioxide is obtained after filtration and vacuum drying at 40 ℃.
(2) And (2) dispersing 0.20g of titanium dioxide prepared in the step (1) in 50mL of 2% acetic acid (v/v) solution, adding 10mmol of CTAB, strongly stirring for 30min, placing into a reaction kettle, placing into a microwave reactor, and heating at 80 ℃ for 60min to obtain the cation modified titanium dioxide dispersion liquid. Wherein the power of the microwave reactor is 600W, and the mass concentration of the titanium dioxide is 0.4 percent.
(3) Dissolving 0.2g of carboxyl chitosan in 50mL of 2% acetic acid (v/v) solution at 80 ℃, adding 0.075g of Span 80, continuously stirring for 30min, naturally cooling to room temperature, slowly dropwise adding phosphate mixed solution (4.2 mL of 25g/L sodium pyrophosphate solution and 8.4mL of 25g/L sodium tripolyphosphate solution), continuously stirring for 30min, dropwise adding the cation modified titanium dioxide dispersion prepared in the step (2) at a constant speed within 30min under strong stirring, reacting for 2h, adding 0.5g of macromolecular auxiliary agent polyethylene glycol, and stirring for 90 min. Wherein the viscosity average molecular weight of the carboxyl chitosan is 1.96 ten thousand, the deacetylation degree is 91.3 percent, the carboxyl degree at C6 is 56.23 percent, and the free ammonia is 4.786 mmol/g; the mass ratio of the carboxyl chitosan to the titanium dioxide is 1:1, and the mass ratio of the carboxyl chitosan to the phosphate is 1: 1.5.
(4) Standing and aging for 1h, centrifuging by a high-speed refrigerated centrifuge, removing supernatant, adding a freeze-drying protective agent solution with the mass concentration of 1%, and freeze-drying to obtain the well-dispersed titanium dioxide @ carboxyl chitosan nanoparticles with the core-shell structure. Wherein the freeze-drying protective agent is pullulan; the prepared core-shell structure particle is tested by a particle size scatterometer (DLS), the average particle size is 108nm, the Zeta potential is 35.67mV, and the monodisperse coefficient is 0.359.
Comparative example (reference example 3, without high molecular weight auxiliary)
(1) Under strong stirring, 5mL of tetrabutyl titanate is uniformly dripped into 20mL of ionic liquid 1-ethyl-3-methylimidazole acetate within 15min, the mixture reacts for 1.5h at room temperature, 8mL of deionized water is uniformly dripped within 20min, the mixture reacts for 6h at 50 ℃, 40mL of absolute ethyl alcohol is added, after uniform stirring, the mixture is centrifuged for 3 times at high speed, the supernatant is discarded, 50% (v/v) of ethyl alcohol is subjected to ultrasonic treatment for three times, and the anatase type nano titanium dioxide is obtained after filtration and vacuum drying at 40 ℃.
(2) And (2) dispersing 0.10g of titanium dioxide prepared in the step (1) in 50mL of 2% acetic acid (v/v) solution, adding 6mmol of CTAB, strongly stirring for 30min, placing into a reaction kettle, placing into a microwave reactor, and heating at 90 ℃ for 50min to obtain the cation modified titanium dioxide dispersion liquid. Wherein the power of the microwave reactor is 800W, and the mass concentration of the titanium dioxide is 0.2 percent.
(3) Dissolving 0.2g of carboxyl chitosan in 50mL of 2% acetic acid (v/v) solution at 80 ℃, adding 0.05g of Span 80, continuously stirring for 30min, naturally cooling to room temperature, slowly dropwise adding a phosphate mixed solution (2.8 mL of 25g/L sodium pyrophosphate solution and 5.6mL of 25g/L sodium tripolyphosphate solution), continuously stirring for 30min, dropwise adding the cation modified titanium dioxide dispersion prepared in the step (2) at a constant speed within 30min under strong stirring, and reacting for 1.5 h. Wherein the viscosity average molecular weight of the carboxyl chitosan is 1.67 ten thousand, the deacetylation degree is 91.3 percent, the carboxyl degree at C6 is 61.58 percent, and the free ammonia is 4.482 mmol/g; the mass ratio of the carboxyl chitosan to the titanium dioxide is 2:1, and the mass ratio of the carboxyl chitosan to the phosphate is 1:1.
(4) Standing and aging for 1h, centrifuging by a high-speed refrigerated centrifuge, removing supernatant, adding a freeze-drying protective agent solution with the mass concentration of 0.75%, and freeze-drying to obtain the well-dispersed titanium dioxide @ carboxyl chitosan nanoparticles with the core-shell structure. Wherein the freeze-drying protective agent is sucrose; the prepared core-shell structure particles pass the test of a particle size scatterometer (DLS), the average particle size is 197nm, the Zeta potential is 38.69mV, and the monodisperse coefficient is 0.302.
Secondly, the samples obtained in the above embodiments are tested
Test item 1: average particle size test of core-shell type nanoparticles prepared by adding carboxyl chitosan and titanium dioxide in different mass ratios
Dynamic Light Scattering (DLS) instrument for particle size, Zeta potential, monodispersion coefficient, each group of samples tested three times. Dispersing the core-shell type nanometer particles with different carboxyl chitosan/titanium dioxide mass ratios in the four examples and the comparative example in 2% acetic acid (v/v) according to the mass concentration of 0.4%, and performing ultrasonic oscillation for 30min to obtain 5 parts of nanometer dispersion liquid test samples. The test results are shown in table 1.
TABLE 1 DLS test results of core-shell nanoparticles with different carboxyl chitosan/titanium dioxide mass ratios
As can be seen from the test data shown in Table 1, the core-shell nanoparticles prepared from carboxyl chitosan and titanium dioxide with different mass ratios are added into 2% acetic acid (v/v), and the prepared core-shell nanoparticles have the advantages of small particle size, uniform size, low monodispersion coefficient and good stability; compared with the core-shell type nanometer particle with the average particle size of 197nm obtained without adding the high molecular auxiliary agent, the average particle size of the core-shell type nanometer particle with the high molecular auxiliary agent is about 78-137 nm, the size of the nanometer particle is obviously reduced, the distribution is uniform, the carboxyl chitosan can be combined with the hydrophilic polymer chain for reaction, the stability and the biological activity of the core-shell type titanium dioxide @ carboxyl chitosan composite nanometer particle are obviously enhanced under the auxiliary cross-linking and assembling action of the high molecular auxiliary agent, and the core-shell type nanometer particle is smaller in size, uniform in particle size and wide in application range.
Test item 2: transmission electron microscope analysis of core-shell titanium dioxide @ carboxyl chitosan nanoparticles
And analyzing the micro-morphology of the anatase titanium dioxide nano-particles and the core-shell titanium dioxide @ carboxyl chitosan nano-particles by adopting a transmission electron microscope. Taking 2 parts of a nano dispersion liquid sample: the 1 st part and the 2 nd part are anatase type titanium dioxide nanoparticles A obtained by catalytic reaction of ionic liquid [ Emim ] Ac medium according to the method of example 3 and core-shell type titanium dioxide @ carboxyl chitosan nanoparticles B obtained by ionic gelation of phosphate and crosslinking assembly of polymer auxiliary agent, and the test results are shown in FIGS. 2(A) - (B) in sequence.
As shown in fig. 2(a), anatase titania nanoparticles are approximately spherical and have a uniform particle size, and most of the nanoparticles have a size of about 21nm, but some of the nanoparticles are likely to agglomerate because of their small particle size and large specific surface area. After titanium dioxide is modified by CTAB cations, core-shell titanium dioxide @ carboxyl chitosan nanoparticles (shown in figure 2(B)) are prepared by utilizing the ionic gelation effect of phosphate and the crosslinking assembly of a high molecular auxiliary agent, the dispersion stability of the whole system is good, a single composite particle presents a regular sphere with a core-shell structure, and the average particle size is distributed in the range of 80-100 nm, which shows that the core-shell titanium dioxide @ carboxyl chitosan composite nanomaterial prepared by the method has the advantages of small particle size, uniform distribution, strong stability and high reaction activity.
Test item 3: x-ray diffraction characterization of core-shell titanium dioxide @ carboxyl chitosan nanoparticles
And analyzing the crystal structure of the core-shell titanium dioxide @ carboxyl chitosan nanoparticles by adopting wide-angle X-ray diffraction. Taking 4 parts of samples: the 1 st part was a carboxyl chitosan a having a viscosity average molecular weight of 1.82 ten thousand, a degree of deacetylation of 91.3%, and a degree of carboxyl at the C6 position of 53.06%, the 2 nd part was a core-shell type titanium dioxide @ carboxyl chitosan nanoparticle b obtained by ionic gelation using phosphate and crosslinking assembly using a polymer assistant according to the method of example 1, the 3 rd part was a core-shell type titanium dioxide @ carboxyl chitosan nanoparticle C obtained by ionic gelation using phosphate and crosslinking assembly using a polymer assistant according to the method of example 3, the 4 th part was an anatase type titanium dioxide nanoparticle d obtained by catalytic reaction using an ionic liquid [ Emim ] Ac medium according to the method of example 3, and the results of the tests were sequentially shown in FIGS. 3(a) to (d).
As can be seen from FIG. 3, 2. theta. on the diffraction curve of the oxidized chitosan has 2 typical diffraction characteristic peaks near 10 ℃ and 20 ℃ corresponding to the (100) crystal planes of the crystalline form I and form II of the oxidized chitosan, respectively. 7 strong diffraction absorption peaks appear on a pure titanium dioxide diffraction curve, which are respectively 2 theta 25.35 degrees, 38.30 degrees, 48.10 degrees, 54.70 degrees, 62.80 degrees, 68.60 degrees and 75.50 degrees, and then representative characteristic peaks (101), (004), (200), (105), (204), (116) and (215) of an acute titanium phase are distinguished, so that the anatase type nano titanium dioxide is obtained by utilizing an ionic liquid [ Emim ] Ac medium to catalyze a reaction. Meanwhile, with the increase of the mass ratio of the oxidized chitosan, a characteristic diffraction peak of the oxidized chitosan appears near 20 degrees, and with the decrease of the mass ratio of the titanium dioxide, the intensities of the corresponding 7 anatase characteristic peaks are gradually reduced; when the mass ratio of the oxidized chitosan to the titanium dioxide reaches 8:1, diffraction peaks positioned near 62.80 degrees, 68.60 degrees and 75.50 degrees on a diffraction curve almost disappear, and obvious oxidized chitosan characteristic peaks appear at 20 degrees, which indicates that stronger crosslinking action occurs between the oxidized chitosan and the titanium dioxide, and further confirms that the titanium dioxide @ carboxyl chitosan nano-particles with the core-shell structure are formed, and the result is consistent with the analysis result of a transmission electron microscope.
Test item 4: test for photocatalytic degradation of methylene blue by core-shell type nanoparticles
And testing the photocatalytic degradation effect of the sample on methylene blue by using an ultraviolet spectrophotometer. Sampling three parts: the first part is CTAB cation modified anatase type nano titanium dioxide a prepared in the step (2), and the second part is core-shell type nano particles b prepared in the example 3, wherein the mass ratio of carboxyl chitosan to titanium dioxide is 2: 1; the third part is core-shell type nanometer particles c which are prepared by the embodiment 2 and have the mass ratio of carboxyl chitosan to titanium dioxide of 4: 1. Dispersing the three samples in 2% acetic acid (v/v) solution according to the mass concentration of 0.4%, preparing 40mg/L methylene blue solution by using 2% acetic acid (v/v), mixing the methylene blue solution and the three samples according to the volume ratio of 1:1, stirring for 30min in the dark, taking a proper amount of mixed solution, centrifuging at a high speed, and testing the absorbance of the supernatant by using a visible light-ultraviolet spectrophotometer (ultraviolet irradiation for 0 min); continuously stirring, irradiating the mixed solution under 365nm ultraviolet light for 20min, 40min, 60min, 80min and 120min, respectively sampling, centrifuging at high speed, testing the absorbance of the supernatant, and calculating the degradation rate of the photocatalytic methylene blue. Testing parameters: the solvent in the cuvette is 2% (v/v) acetic acid, the wavelength range is 500-800 nm, the scanning interval is 0.1nm, and the precision is 5. The results of the photocatalytic degradation of methylene blue are shown in FIG. 4 (a-c).
Fig. 4 shows that the degradation rate of the sample b exceeds 50% at 20min, the removal rate reaches 95% at 120min after illumination, methylene blue in the solution is almost completely removed, and the degradation rate of the core-shell type nanoparticle is slightly lower than that of pure titanium dioxide, but the degradation threshold within 2h (about 95% for the core-shell type nanoparticle and 99% for the pure titanium dioxide) is not very different. The core-shell nanoparticle prepared by the invention has excellent effect of photocatalytic degradation of methylene blue. In addition, the degradation rate of the curve b of methylene blue is abnormal in the photodegradation process, and the degradation rate of the methylene blue in the mixed solution is reduced in 40-60 min, because the carboxyl chitosan adsorbs the methylene blue during dark treatment, when the content of the methylene blue in the solution is reduced to a certain value, part of the methylene blue is desorbed from the oxidized chitosan and enters the solution again, so that the degradation rate of the methylene blue in 60min is slightly lower than that in 40min, and the reason that the photocatalytic degradation rate of the core-shell type nano-particles is lower than that of pure titanium dioxide is explained. It can be seen from curve c that carboxyl chitosan, as a porous macromolecular material, has a certain adsorption effect on dyes, has a relatively high adsorption speed, and basically reaches the absorption threshold of methylene blue within 30min of stirring in the dark, but has a limited adsorption amount (less than 20%), which further indicates that the abnormality of curve b is caused by that the carboxyl chitosan adsorbs the dyes in the solution, gradually desorbs along with the decrease of the dye concentration, and releases the dyes.
Test item 5: core-shell nanoparticle stability test
Samples of the core-shell type nanoparticles and the pure anatase type nano titanium dioxide of the comparative example, the examples 2 and 3 are respectively taken and dispersed in 2 percent acetic acid (v/v) solution according to the mass concentration of 0.4 percent, 10mL of each dispersion solution sample is taken and put into a 20mL penicillin bottle, the bottle mouth is sealed, and the penicillin bottle is placed at room temperature for 10 days. The average particle diameter of the nanoparticles and the Zeta potential were measured at predetermined times, and the change in appearance of each sample was compared, and the test results are shown in table 2.
TABLE 2 particle size and potential variation of core-shell nanoparticles after standing for 10 days
As can be seen from Table 2, the average particle size of pure nano titanium dioxide is significantly increased within 10 days, and the particles are easily aggregated and have a sedimentation phenomenon. The core-shell type nano particles without the addition of the polymer auxiliary agent are also obviously agglomerated within 10 days, and the particle size is increased; the core-shell nanoparticles of examples 2 and 3 had substantially no agglomeration, little change in particle size, and good stability. Therefore, according to the preparation method, CTAB cation modified titanium dioxide is adopted, carboxyl chitosan and phosphate ions are subjected to gelation to form core-shell nanoparticles encapsulating the titanium dioxide, and then hydrophilic polymer auxiliaries and the carboxyl chitosan are utilized for cross-linking assembly, so that hydrophilic polymer long chains are introduced into carboxyl chitosan molecules, and the stability of the core-shell nanoparticles in a solution can be effectively improved.
In conclusion, the core-shell titanium dioxide @ carboxyl chitosan composite nano-particles with small particle size, uniform size, high stability and good photocatalytic effect are prepared by taking anatase type nano-titanium dioxide and carboxyl chitosan prepared by ionic liquid reaction as raw materials and through ionic gelation of CTAB cation modified titanium dioxide and phosphate and crosslinking and assembling of a high molecular auxiliary agent. The preparation method has the advantages of simple preparation process, mild reaction conditions, no use of organic solvents and aldehyde crosslinking agents, environmental protection, safety, no toxicity and low cost, so the method has the potential of large-scale application.
The invention is not to be considered as limited to the particular embodiments shown, but is to be accorded the widest scope consistent with the principles and novel features herein disclosed.
Claims (8)
1. A preparation method of core-shell titanium dioxide @ carboxyl chitosan nanoparticles is characterized by comprising the following steps: the nano particles are prepared by taking anatase type nano titanium dioxide and carboxyl chitosan prepared by ionic liquid reaction as raw materials through ionic gelation of CTAB cation modified titanium dioxide and phosphate and crosslinking and assembling of a high molecular auxiliary agent.
2. The method of claim 1, comprising the steps of:
step 1, adding 1-5 mL of tetrabutyl titanate into 10-20 mL of ionic liquid 1-ethyl-3-methylimidazole acetate, uniformly mixing at room temperature, then dropwise adding 2-10 mL of deionized water at constant speed, and continuously stirring for 4-6 h at 40-60 ℃; adding 20-40 mL of absolute ethanol for dilution to reduce viscosity, centrifugally separating out titanium dioxide, ultrasonically cleaning with an ethanol solution with the volume concentration of 50% to remove residual ionic liquid on the surface of the titanium dioxide, and drying in vacuum to obtain anatase type nano titanium dioxide;
step 2, uniformly dispersing the titanium dioxide prepared in the step 1 in 50mL of 2 vol% acetic acid solution according to the mass concentration of 0.05-0.4%, adding 1-10 mmol of hexadecyl trimethyl ammonium bromide, stirring and mixing, putting into a reaction kettle, and heating in a microwave reactor at 70-90 ℃ for 20-60 min to prepare a cation modified titanium dioxide dispersion liquid;
step 3, dissolving 0.2g of carboxyl chitosan at 80 ℃ in 50mL of 2% acetic acid solution, then dropwise adding span 80 until the concentration of span 80 in the system is 0.5-1.5 g/L, continuously stirring for 20-30 min, naturally cooling to room temperature, then dropwise adding phosphate mixed solution until the concentration of phosphate in the system is 0.2-0.6 g/L, and continuously stirring for 30 min; the phosphate mixed solution is a mixed solution of sodium pyrophosphate and sodium tripolyphosphate;
dropwise adding the cation modified titanium dioxide dispersion liquid prepared in the step 2 into the system at a constant speed within 30min, continuously stirring and reacting for 1-2 h after dropwise adding, then adding 0.1-0.5 g of high molecular auxiliary agent, stirring for 40-90 min, enabling phosphate to be combined with cation modified titanium dioxide particles, enabling amino cation of carboxyl chitosan and phosphate anion of phosphate to be mutually crosslinked, further performing ionic gelation and assembling of the high molecular auxiliary agent to form core-shell type nano particles;
the mass ratio of the carboxyl chitosan to the phosphate is 1: 0.5-1.5; the mass ratio of the sodium pyrophosphate to the sodium tripolyphosphate is 0.5-1: 2;
and 4, standing and aging the nanoparticle dispersion liquid obtained in the step 3 for 1-3 hours, centrifuging the dispersion liquid by using a high-speed refrigerated centrifuge, removing a supernatant, adding a freeze-drying protective agent solution with the mass concentration of 0.5-1%, and freeze-drying to obtain the well-dispersed core-shell titanium dioxide @ carboxyl chitosan nanoparticles.
3. The method of claim 2, wherein: in the step 1, the anatase type nano titanium dioxide has an average particle size of 16-25 nm and a Zeta potential of 38.22-42.41 mV.
4. The method of claim 1, wherein: in the step 3, the viscosity-average molecular weight of the carboxyl chitosan is 0.85-1.96 ten thousand, the deacetylation degree is more than or equal to 91.3%, the carboxyl degree at the C6 position is 40.27-61.58%, the free amino group is 4.453-5.179 mmol/g, and the structural formula of the carboxyl chitosan is as follows:
5. the production method according to claim 1 or 2, characterized in that: the particle size range of the obtained core-shell titanium dioxide @ carboxyl chitosan nano-particle is 78-137 nm, the Zeta potential is 27.18-40.76 mV, and the monodisperse coefficient is 0.208-0.501.
6. The method of claim 2, wherein: in the step 2, the microwave radiation power of the microwave reactor is 600-800W.
7. The method of claim 2, wherein: in the step 3, the polymer auxiliary agent is gelatin, sodium alginate or polyethylene glycol with the number average molecular weight of 400-1000.
8. The manufacturing process of claim 2, wherein: in the step 4, the freeze-drying protective agent is skim milk, pullulan, sucrose or glucose.
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