CN116940417A - Method for preparing core-shell hollow structure nano particles by micro-nano bubbles - Google Patents
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- 239000002101 nanobubble Substances 0.000 title claims abstract description 58
- 239000011258 core-shell material Substances 0.000 title claims abstract description 51
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 40
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 31
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 30
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000011973 solid acid Substances 0.000 claims abstract description 23
- 238000010008 shearing Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 239000003595 mist Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- -1 i.e. Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
- C01B33/151—After-treatment of sols by progressively adding a sol to a different sol, i.e. "build-up" of particles using a "heel"
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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Abstract
A method for preparing core-shell hollow nano particles by micro-nano bubbles is disclosed. It comprises the following steps: (1) Mixing titanium tetrachloride with a water mist to obtain a titanium dioxide solid/hydrochloric acid droplet mixture; (2) Shearing, stirring and mixing the titanium dioxide solid/hydrochloric acid liquid drop mixture and the ethyl orthosilicate liquid through a micro-nano bubble generator so as to obtain micro-nano bubbles; (3) Separating, drying and calcining the precipitate to obtain the core-shell hollow structure nano particles. The obtained core-shell hollow structure widens the active surface of catalytic reaction, improves the activity, has simple method and is easy for mass industrialized production.
Description
The present disclosure relates to the field of high molecular materials, and in particular, to a method for preparing core-shell hollow structure nanoparticles by using micro-nano bubbles.
Titanium dioxide is a common semiconductor photocatalytic material. Under the irradiation of light, it can convert light energy into chemical energy, and can decompose toxic and harmful organic matters in a short time. In addition, it has the characteristics of high stability, light corrosion resistance, no toxicity and the like, and does not produce secondary pollution in the treatment process, so that the method is attracting attention in the fields of antibiosis, deodorization, oil stain decomposition, mildew and algae prevention, air purification and the like. However, since the catalytic reaction is essentially a surface contact reaction, which occurs only on the surface of the material, the limited surface area for the catalyst is used for the catalytic reaction, and the task of particle loading and immobilization is also assumed, which tends to greatly affect the catalytic effect.
The core-shell structure is a nano-scale ordered assembly structure formed by coating one nano material with another nano material through chemical bonds or other acting forces. The catalyst has the important functions of maintaining the functional stability of the catalyst, adjusting the physical and chemical properties of the material to achieve complementary advantages, preventing the agglomeration of nano particles and controlling the interface reaction of the particles, and has wide application prospects in photocatalysis, batteries, gas storage and separation. However, how to solve the problem of the shell covering the surface of the core and interfering with the catalytic activity of the core for the nano-catalytic material that relies on the surface area to drive the reaction is always an unreliable obstacle on the way of application of the nano-catalyst.
Further improvements are needed in how to obtain nanomaterials with high catalytic activity.
Disclosure of Invention
The present disclosure aims to solve, at least to some extent, one of the technical problems in the related art. The method utilizes the characteristic that titanium tetrachloride, which is a precursor of titanium dioxide, is unstable when meeting water, can smoke in air to generate a titanium dioxide solid/hydrochloric acid liquid drop mixture, and utilizes a micro-nano bubble generator to mix smoke generated after titanium tetrachloride and water mist with pure solution of tetraethoxysilane to form bubbles, and the bubbles are subjected to gyratory shearing and stirring to form micro-nano bubbles. Meanwhile, hydrochloric acid byproducts generated after titanium tetrachloride meets water can promote the hydrolysis of tetraethoxysilane on the gas-liquid surface of micro-nano bubbles to form a stable silicon dioxide shell, and finally the photocatalysis core-shell hollow structure nano particles with hollow structures between cores and shells are obtained.
Specifically, the present disclosure provides the following technical solutions:
a first aspect of the present disclosure provides a method of preparing core-shell hollow structure nanoparticles by micro-nano bubbles, comprising:
(1) Mixing titanium tetrachloride with a water mist to obtain a titanium dioxide solid/hydrochloric acid droplet mixture;
(2) Shearing, stirring and mixing the titanium dioxide solid/hydrochloric acid liquid drop mixture and the ethyl orthosilicate liquid through a micro-nano bubble generator so as to obtain micro-nano bubbles;
(3) Separating, drying and calcining the precipitate to obtain the core-shell hollow structure nano particles.
According to an embodiment of the present disclosure, the method described above may further include the following technical features:
further, step (1) further comprises: 8 to 15 parts by weight of titanium tetrachloride is added into a closed container with 10 to 15L of internal air circulation, and air with the humidity of 5 to 30 percent is introduced, and the closed circulation is carried out for 1 to 4 hours.
Further, in the step (2), the ethyl orthosilicate liquid is added in an amount of 80 to 120 parts by weight, preferably 90 to 110 parts by weight, based on 8 to 15 parts by weight of titanium tetrachloride.
Further, in the step (2), the diameter of the micro-nano bubbles is 200-1000 nanometers.
Further, the shearing time in the step (2) is 3 to 9 hours.
Further, in the step (3), the calcination temperature is 400-500 ℃ and the calcination time is 1-3 hours.
Further, in the step (3), the drying temperature is 70-90 ℃ and the drying time is 10-15 hours.
Further, the separation is performed by centrifugation in step (3).
A second aspect of the present disclosure provides a method of preparing core-shell hollow structure nanoparticles by micro-nano bubbles, comprising:
(1) Adding 8-15 parts by weight of titanium tetrachloride into a closed container, introducing air with the humidity of 5-30%, and performing closed circulation for 1-4 hours to obtain a titanium dioxide solid/hydrochloric acid liquid drop mixture;
(2) Shearing, crushing and mixing the titanium dioxide solid/hydrochloric acid liquid drop mixture and 80-120 parts by weight of tetraethoxysilane liquid through a micro-nano bubble generator for 3-9 hours so as to obtain micro-nano bubbles, wherein the particle size of the micro-nano bubbles is 200-1000 nanometers;
(3) And (3) centrifugally separating, drying the precipitate at 70-90 ℃ and calcining at 400-500 ℃ to obtain the core-shell hollow structure nano particles.
Further, the method comprises:
(1) Adding 10 parts by weight of titanium tetrachloride into a closed container, introducing air with the humidity of 5-30%, and performing closed circulation for 1-4 hours to obtain a titanium dioxide solid/hydrochloric acid liquid drop mixture;
(2) Shearing, crushing and mixing the titanium dioxide solid/hydrochloric acid liquid drop mixture and 100 parts by weight of tetraethoxysilane liquid through a micro-nano bubble generator for 3-9 hours so as to obtain micro-nano bubbles, wherein the particle size of the micro-nano bubbles is 200-1000 nanometers;
(3) And (3) centrifugally separating, drying the precipitate at 80 ℃, and calcining at 400-500 ℃ to obtain the core-shell hollow structure nano particles.
A third aspect of the present disclosure provides a core-shell hollow structure nanoparticle prepared according to the method of any one of the embodiments of the first aspect or any one of the embodiments of the second aspect.
The beneficial effects obtained by the method are as follows: the method provided by the disclosure obtains the nano particle with the photocatalysis core-shell hollow structure. The provided core-shell hollow structure widens the active surface of catalytic reaction, improves the activity and can save raw materials. The preparation process of the product is relatively simple, the conditions are easy to control, and the product is easy for mass industrialized production.
Fig. 1 is an electron microscope image of a core-shell hollow structure nanoparticle provided according to example 1 of the present disclosure.
Fig. 2 is an XRD pattern of core-shell hollow structure nanoparticles provided according to example 1 of the present disclosure.
Fig. 3 is a graph of catalytic activity results of core-shell hollow structure nanoparticles provided in example 1 according to the present disclosure.
Fig. 4 is a graph of antibacterial effect results of core-shell hollow structure nanoparticles provided in example 1 according to the present disclosure.
Fig. 5, 6, and 7 are electron microscope images of a sample provided in comparative example 1 according to the present disclosure.
Embodiments of the present disclosure will be described in detail below with reference to the drawings, it being noted that the illustrated embodiments are exemplary and intended to illustrate the present disclosure and not to be construed as limiting the present disclosure. Herein, unless otherwise specified, the mentioned contents and the like are mass percentages.
Titanium tetrachloride, also known as or titanium (IV) chloride, is TiCl 4 Is an inorganic compound of (a). Titanium tetrachloride is an important intermediate for the production of titanium dioxide. At room temperature, titanium tetrachloride is colorless liquid, and when exposed to air, titanium tetrachloride can react with water in the air rapidly to TiCl 4 +2H 2 O→TiO 2 +4HCl. Micro-nano bubbles exist in a special gas state at the interface of gas and liquid, and can exist in the liquid stably for a long time. The micro-nano bubble generators commonly found in the market all belong to high shear generationThe micro-nano bubbles are generally obtained by adopting dynamic or static high-speed shearing equipment and by a mode of crushing gas-liquid mixed large bubbles. The method utilizes the characteristic that titanium tetrachloride, which is a precursor of titanium dioxide, is unstable when meeting water, can smoke in air to generate a titanium dioxide solid/hydrochloric acid liquid drop mixture, and utilizes a commercially available micro-nano bubble generator to mix smoke generated by mixing titanium tetrachloride with water mist with pure solution of tetraethoxysilane to form bubbles, and carries out gyratory shearing and stirring on the bubbles to form micro-nano bubbles. Meanwhile, hydrochloric acid byproducts generated after titanium tetrachloride meets water can promote hydrolysis of tetraethoxysilane on the gas-liquid surface of micro-nano bubbles to form a stable silicon dioxide shell, and finally the photocatalysis core-shell hollow structure nano particles with hollow structures between cores and shells are obtained.
The present disclosure provides a method for preparing core-shell hollow structure nanoparticles by micro-nano bubbles, comprising: (1) Mixing titanium tetrachloride with a water mist to obtain a titanium dioxide solid/hydrochloric acid droplet mixture;
(2) Shearing, stirring and mixing the titanium dioxide solid/hydrochloric acid liquid drop mixture and the ethyl orthosilicate liquid through a micro-nano bubble generator so as to obtain micro-nano bubbles;
(3) Separating, drying and calcining the precipitate to obtain the core-shell hollow structure nano particles.
According to a specific embodiment, step (1) further comprises: 8 to 15 parts by weight of titanium tetrachloride is added into a closed container with 10 to 15L of internal air circulation, and air with the humidity of 5 to 30 percent is introduced, and the closed circulation is carried out for 1 to 4 hours. Titanium tetrachloride reacts with water vapor to form titanium dioxide nanoparticles, which appear as white smoke, i.e., titanium dioxide particles. TiCl 4 The water-soluble glass is extremely active and easy to hydrolyze, and can form smog with water vapor in the air, so that the water-soluble glass has extremely strong reaction with water; tiCl is reacted 4 +H 2 O---->TiCl 3 (OH) +hcl; and hydrolyzing step by step to finally form TiO 2 。
According to a specific embodiment, in the step (2), the ethyl orthosilicate liquid is added in an amount of 80 to 120 parts by weight based on 8 to 15 parts by weight of titanium tetrachloride. When mixing, shearing and crushing the titanium dioxide solid/hydrochloric acid droplet mixture and the ethyl orthosilicate, if the amount of the ethyl orthosilicate is too small, nano particles with a core-shell hollow structure are not easy to form; if the amount of the tetraethoxysilane is too large, the catalytic activity of the formed core-shell hollow structure nano particles is affected to a certain extent. According to a specific embodiment, the amount of the tetraethyl orthosilicate liquid added in step (2) is 90 to 110 parts by weight, for example 90 parts by weight, 95 parts by weight, 100 parts by weight, 105 parts by weight, 110 parts by weight, etc., based on 8 to 15 parts by weight of titanium tetrachloride.
According to a specific embodiment, the diameter of the micro-nano bubbles in the step (2) is 200-1000 nanometers. For example, the micro-nano bubbles may have a diameter of 300 to 900 nm, for example, 300 nm, 400 nm, 500nm, 600 nm, 700 nm, 800nm, 900 nm, or the like.
According to a specific embodiment, the shearing time in step (2) is 3 to 9 hours.
According to a specific embodiment, the calcination temperature in step (3) is 400-500 ℃ and the calcination time is 1-3 hours.
According to a specific embodiment, the drying temperature in the step (3) is 70-90 ℃ and the drying time is 10-15 hours.
The present disclosure provides a method for preparing core-shell hollow structure nanoparticles by micro-nano bubbles, comprising:
(1) Adding 8-15 parts by weight of titanium tetrachloride into a closed container, introducing air with the humidity of 5-30%, and performing closed circulation for 1-4 hours to obtain a titanium dioxide solid/hydrochloric acid liquid drop mixture;
(2) Shearing, crushing and mixing the titanium dioxide solid/hydrochloric acid liquid drop mixture and 80-120 parts by weight of tetraethoxysilane liquid through a micro-nano bubble generator for 3-9 hours so as to obtain micro-nano bubbles, wherein the particle size of the micro-nano bubbles is 200-1000 nanometers;
(3) And (3) centrifugally separating, drying the precipitate at 70-90 ℃ and calcining at 400-500 ℃ to obtain the core-shell hollow structure nano particles.
The present disclosure also provides a method of preparing core-shell hollow structure nanoparticles by micro-nano bubbles, comprising:
(1) Adding 10 parts by weight of titanium tetrachloride into a closed container, introducing air with the humidity of 5-30%, and performing closed circulation for 1-4 hours to obtain a titanium dioxide solid/hydrochloric acid liquid drop mixture;
(2) Shearing, crushing and mixing the titanium dioxide solid/hydrochloric acid liquid drop mixture and 100 parts by weight of tetraethoxysilane liquid through a micro-nano bubble generator for 3-9 hours so as to obtain micro-nano bubbles, wherein the particle size of the micro-nano bubbles is 200-1000 nanometers;
(3) And (3) centrifugally separating, drying the precipitate at 80 ℃, and calcining at 400-500 ℃ to obtain the core-shell hollow structure nano particles.
The disclosure is further illustrated below in connection with the following examples. The examples are for illustration only and are not intended to limit the present disclosure. The aspects of the present disclosure will be explained below with reference to examples. Those skilled in the art will appreciate that the following examples are illustrative of the present disclosure and should not be construed as limiting the scope of the present disclosure. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The micro-nano bubble generator used therein is commercially available.
Example 1
Embodiment 1 provides a method for preparing a core-shell hollow structure nanoparticle, comprising:
1. 10 parts by weight of titanium tetrachloride was spread on the bottom of a 10L sealed container with internal air circulation, and air having a humidity of 10% was introduced and circulated in a sealed state for 2 hours.
2. And (3) pumping the flue gas generated in the process into a pure solution of 100 parts by weight of tetraethoxysilane through a commercially available micro-nano bubble generator, and obtaining micro-nano bubbles by shearing and crushing the mode of mixing large bubbles with gas and liquid. The diameter of the micro-nano bubbles is controlled to be about 500nm, and the shearing time is 6 hours.
3. After the reaction, the solution obtained in the step 2 is centrifugally separated, and the precipitate is dried for 12 hours at 80 ℃. Finally, calcining at 400 ℃ for 3 hours to obtain the core-shell hollow structure nanoparticle.
Example 2
Embodiment 2 provides a method for preparing a core-shell hollow structure nanoparticle, comprising:
1. 15 parts by weight of titanium tetrachloride was spread on the bottom of a 10L sealed container with internal air circulation, and air having a humidity of 20% was introduced, and the sealed container was circulated for 4 hours.
2. And (3) pumping the flue gas generated in the process into a pure solution of 100 parts by weight of tetraethoxysilane through a commercially available micro-nano bubble generator, and obtaining micro-nano bubbles by shearing and crushing the mode of mixing large bubbles with gas and liquid. The diameter of the micro-nano bubbles is controlled to be about 800nm, and the shearing time is 8 hours.
3. After the reaction, the solution obtained in the step 2 is centrifugally separated, and the precipitate is dried for 12 hours at 80 ℃. Finally, calcining for 2 hours at 500 ℃ to obtain the core-shell hollow structure nanoparticle.
Characterization was performed by taking the core-shell hollow-structure nanoparticle prepared in example 1 as an example. Wherein the electron microscope image is shown in fig. 1. Other characterization results were as follows:
1. XRD data
XRD data showed that the lattice structure of the core-shell hollow titania particles was not changed, and all exhibited anatase phases of titania, as shown in fig. 2.
2. Catalytic activity data
The photocatalysis fading experiment of rhodamine B solution also shows that the core-shell hollow structure nano particle with the addition amount of 1-4 percent of the solution can be used for adding 5x10 in three hours -5 The mol/L rhodamine B (Rh B) solution is subjected to photocatalytic fading, and shows that the dye has good performanceAs shown in fig. 3 a and b. RbB in a represents rhodamine B solution without adding any photocatalytic material, 1 represents rhodamine B solution with the addition amount of the core-shell hollow structure nano particles being 1% of the total solution, 2 represents rhodamine B solution with the addition amount of the core-shell hollow structure nano particles being 2% of the total solution, 3 represents rhodamine B solution with the addition amount of the core-shell hollow structure nano particles being 3% of the total solution, and 4 represents rhodamine B solution with the addition amount of the core-shell hollow structure nano particles being 4% of the total solution. The absorption peak value in the step b is 0h of catalysis time, 0.5h of catalysis time, 1h of catalysis time, 1.5h of catalysis time, 2h of catalysis time, 2.5h of catalysis time and 3h of catalysis time in sequence from high to low, and the used sample solution is sample 4 solution of the graph a.
3. Antibacterial effect
The core-shell hollow structure nano particles are added into a bacterial culture solution (the comparison is a sample added with silicon dioxide, S0-S4 are the addition amounts of the core-shell hollow structure nano particles which are respectively 0 thousandth, 1 thousandth, 2 thousandth, 3 thousandth and 4 thousandth), and the sample added with the core-shell hollow titanium dioxide particles has good antibacterial effect after 24 hours. The results are shown in FIG. 4.
Comparative example 1
Comparative example 1 in the process of preparing core-shell hollow structure nanoparticles, the difference from example 1 is that: when a certain humidity is introduced into the sample, parameters such as flow rate and the like are not adjusted reasonably, the flow rate is too high, so that a sample with a shell layer cannot be formed, and the electron microscope result is shown in fig. 5. And sometimes a sample with unstable silica layer is formed, and the electron microscopic result is shown in fig. 6. Some samples with stable silica layers but uneven titania core distribution were formed, and the electron microscope results are shown in fig. 7.
The foregoing is merely a preferred embodiment of the present disclosure, and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present disclosure, which are intended to be comprehended within the scope of the present disclosure.
Claims (10)
- A method for preparing core-shell hollow structure nanoparticles by micro-nano bubbles, which is characterized by comprising the following steps:(1) Mixing titanium tetrachloride with a water mist to obtain a titanium dioxide solid/hydrochloric acid droplet mixture;(2) Shearing, stirring and mixing the titanium dioxide solid/hydrochloric acid liquid drop mixture and the ethyl orthosilicate liquid through a micro-nano bubble generator so as to obtain micro-nano bubbles;(3) Separating, drying and calcining the precipitate to obtain the core-shell hollow structure nano particles.
- The method of claim 1, wherein step (1) further comprises:8 to 15 parts by weight of titanium tetrachloride is added into a closed container with 10 to 15L of internal air circulation, and air with the humidity of 5 to 30 percent is introduced, and the closed circulation is carried out for 1 to 4 hours.
- The method according to claim 1, wherein the ethyl orthosilicate liquid is added in an amount of 80 to 120 parts by weight, preferably 90 to 110 parts by weight, based on the amount of titanium tetrachloride in step (2) of 8 to 15 parts by weight.
- The method of claim 1, wherein the micro-nano bubbles in step (2) have a diameter of 200 to 1000 nanometers.
- The method of claim 1, wherein the shear time in step (2) is 3 to 9 hours.
- The method according to claim 1, wherein the calcination temperature in step (3) is 400 to 500 degrees celsius and the calcination time is 1 to 3 hours.
- The method according to claim 1, wherein the drying temperature in step (3) is 70 to 90 degrees celsius and the drying time is 10 to 15 hours;optionally, the separation is performed by centrifugation in step (3).
- A method for preparing core-shell hollow structure nanoparticles by micro-nano bubbles, which is characterized by comprising the following steps:(1) Adding 8-15 parts by weight of titanium tetrachloride into a closed container, introducing air with the humidity of 5-30%, and performing closed circulation for 1-4 hours to obtain a titanium dioxide solid/hydrochloric acid liquid drop mixture;(2) Shearing, crushing and mixing the titanium dioxide solid/hydrochloric acid liquid drop mixture and 80-120 parts by weight of tetraethoxysilane liquid through a micro-nano bubble generator for 3-9 hours so as to obtain micro-nano bubbles, wherein the particle size of the micro-nano bubbles is 200-1000 nanometers;(3) And (3) centrifugally separating, drying the precipitate at 70-90 ℃ and calcining at 400-500 ℃ to obtain the core-shell hollow structure nano particles.
- A method for preparing core-shell hollow structure nanoparticles by micro-nano bubbles, which is characterized by comprising the following steps:(1) Adding 10 parts by weight of titanium tetrachloride into a closed container, introducing air with the humidity of 5-30%, and performing closed circulation for 1-4 hours to obtain a titanium dioxide solid/hydrochloric acid liquid drop mixture;(2) Shearing, crushing and mixing the titanium dioxide solid/hydrochloric acid liquid drop mixture and 100 parts by weight of tetraethoxysilane liquid through a micro-nano bubble generator for 3-9 hours so as to obtain micro-nano bubbles, wherein the particle size of the micro-nano bubbles is 200-1000 nanometers;(3) And (3) centrifugally separating, drying the precipitate at 80 ℃, and calcining at 400-500 ℃ to obtain the core-shell hollow structure nano particles.
- A core-shell hollow structure nanoparticle prepared according to the method of any one of claims 1 to 9.
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