CN109433174B - Silicate-coated titanium dioxide photocatalyst powder and preparation method thereof - Google Patents
Silicate-coated titanium dioxide photocatalyst powder and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 97
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 79
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000000843 powder Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 73
- 239000002245 particle Substances 0.000 claims abstract description 28
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 22
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
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- 238000001914 filtration Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
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- 238000000227 grinding Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- GLISOBUNKGBQCL-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(C)CCCN GLISOBUNKGBQCL-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 25
- 239000011248 coating agent Substances 0.000 abstract description 24
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
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- 230000015556 catabolic process Effects 0.000 abstract description 3
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- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 239000012047 saturated solution Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
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- TVUBDAUPRIFHFN-UHFFFAOYSA-N dioxosilane;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].O=[Si]=O TVUBDAUPRIFHFN-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- B01J21/08—Silica
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/50—
-
- B01J35/615—
Abstract
The invention provides a silicate-coated titanium dioxide photocatalyst powder and a preparation method thereof, which takes photocatalyst-type titanium dioxide as a carrier, silica sol as a coating material and aminosilane coupling agent as a chelating agent to coat silicate on the surface of titanium dioxide particles, wherein the particle diameter of the coated titanium dioxide photocatalyst powder is 0.5-1.5 mu m, and the specific surface area is more than or equal to 200m2The silicate with the mass percentage content of 5-40 percent is used for preparing photocatalyst aqueous solution with high solid content and photocatalytic material with organic matter as a carrier. The photocatalyst powder has the advantages of stable silicate adsorption, high and controllable coating rate, low oil absorption, high photocatalytic activity and the like, and is easy to disperse and can not cause the degradation of organic carriers. The preparation method of the invention has the advantages of easily obtained raw materials, simple and convenient process, stable silicate coating and controllable coating rate.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to silicate-coated titanium dioxide photocatalyst powder and a preparation method thereof.
Background
Titanium dioxide is used as a common photocatalyst, has the advantages of large specific surface area, high photocatalytic and absorption capacity, high weather resistance, high chemical corrosion resistance, no toxicity to human bodies and the like, has a certain application in the field of photocatalysis, and can realize the functions of preparing hydrogen by hydrolysis, removing harmful substances and the like by absorbing photons and generating redox free radicals on the surface of the titanium dioxide to perform chemical reaction with external substances. However, when the titanium dioxide is used for preparing the photocatalytic material, because the titanium dioxide particles have poor dispersion stability, are difficult to infiltrate in an organic phase, and cannot show a satisfactory catalytic effect, the titanium dioxide is industrially loaded on a carrier for use, and the search for a suitable carrier becomes one of important bottlenecks which restrict the wide use of the carrier.
On one hand, in order to increase the specific surface area, the photocatalyst-type titanium dioxide powder often has a porous structure and high oil absorption and water absorption, and the powder is dispersed in a liquid-phase carrier, so that a large amount of auxiliary agents such as a surfactant and a dispersing agent are required to be added to completely disperse or reduce the consumption of emulsion, and the problems of complicated preparation process or low photocatalyst powder loading capacity and the like are caused, thereby reducing the photocatalytic activity of a finished photocatalyst material.
On the other hand, when organic components exist in the carrier (such as a polymer adhesive is used or organic pigment and filler are added), the oxidation of titanium dioxide can degrade the organic components, so that the structure of the material is damaged or the basic performance is lost.
One of the effective approaches to the above problems is to perform hybridization treatment on titanium dioxide and coat the surface thereof, such as preparation of titanium dioxide-silicon dioxide hybrid (TiO) with core-shell structure2@SiO2) Nanoparticles. This approach can reduce the porosity and surface energy of the titanium dioxide while isolating direct contact of the titanium dioxide and the organic component.
In the preparation of the above TiO2@SiO2Among the methods of nanoparticles, one of the most common methods is to load organosilicon on the surface of titanium dioxide by using a surfactant, for example, tetraethyl silicate is used in CN 107008242A, and TiO is obtained by calcining after the surface of titanium dioxide is coated2@SiO2. However, the method is easy to generate more byproducts in the preparation process, and the problems of gel and the like may occur in the coating process.
Another method is to use silicate or silicon dioxide as raw material containing silicon, such as CN103232733A, directly blend silica sol and titanium dioxide slurry without surface treatment, and use the mixture after curing for preparing TiO2@SiO2. However, the activity of the silicon-containing raw material used in the method is low, and the common surfactants such as the coupling agent are difficult to form stable bridging between the silicon dioxide and the titanium dioxide, so that the problems of low coating rate, uncontrollable coating rate and the like are caused.
Disclosure of Invention
The invention aims to provide a titanium dioxide photocatalyst powder coated by silicate and a preparation method thereof, which overcome the defects that silicon materials in the prior art can not be stably adsorbed on the surface of titanium dioxide, the coating rate is low and uncontrollable, an organic carrier is degraded, the titanium dioxide is difficult to disperse, and the like.
A silicate coated according to the inventionThe titanium dioxide photocatalyst powder is characterized in that photocatalyst type titanium dioxide is used as a carrier, silica sol is used as a coating material, and aminosilane coupling agent is used as a chelating agent, silicate is coated on the particle surface of the titanium dioxide, the particle diameter of the coated titanium dioxide photocatalyst powder is 0.5-1.5 mu m, and the specific surface area is more than or equal to 200m2The silicate with the mass percentage of 5 percent to 40 percent is contained in the water.
Preferably, the photocatalyst titanium dioxide is carbon-doped anatase titanium dioxide, the carbon doping amount is 0.8% -1.5%, the particle size is 0.5-1 μm, and the photocatalyst titanium dioxide has excellent absorption and responsiveness to visible light.
Preferably, the silica sol is a colloidal solution formed by uniformly diffusing nano-scale silica particles in water, wherein the particle size of the silica is 13-29 nm, the mass percentage content of the silica is 30-50%, and the specific surface area of the silica is about 110-160 m2The particles are electronegative and are stable within the pH value range of 4-10; for example: LUDOX TMA silica sol manufactured by GRACE.
Preferably, the aminosilane coupling agent is an amino group-containing silane coupling agent, such as: one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylethoxysilane and 3-aminopropylmethyldiethoxysilane, wherein the silane coupling agent is liquid at normal temperature, the mass percentage of the active ingredients is not less than 95%, and the positively charged amino can be provided.
The invention discloses a preparation method of titanium dioxide photocatalyst powder coated with silicate, which is characterized by comprising the following steps:
(1) adding photocatalyst type titanium dioxide into absolute ethyl alcohol, and shaking or stirring for 0.5-1 hour until the photocatalyst type titanium dioxide is completely dispersed into a dispersion liquid A; dropwise adding a saturated sodium bicarbonate solution into the dispersion liquid A while stirring until the pH is adjusted to 8-9 to obtain a dispersion liquid B;
(2) dropwise adding a liquid aminosilane coupling agent into the dispersion liquid B, and simultaneously heating the dispersion liquid B to 80-85 ℃; or dropwise adding a liquid aminosilane coupling agent into the dispersion liquid B, and then heating the dispersion liquid B to 80-85 ℃; or heating the dispersion liquid B to 80-85 ℃, and then dropwise adding a liquid aminosilane coupling agent;
(3) stirring the dispersion B to react for 4 to 5 hours in a condensing reflux environment; stopping heating, cooling to room temperature, filtering the dispersion liquid B to obtain a solid C, alternately and repeatedly cleaning and filtering the solid C by using absolute ethyl alcohol and dilute sulfuric acid until the pH value of the filtrate is 6-7, and obtaining a solid D;
(4) adding the solid D into absolute ethyl alcohol, and oscillating or stirring for 15-30 minutes until the solid D is completely dispersed to obtain a dispersion liquid E of the solid D; slowly adding silica sol into the dispersion liquid E at normal temperature, stirring for 30-45 minutes at the same time, adsorbing and wrapping the silicate with negative charges on the surface of the titanium dioxide with positive charges to obtain a suspension of the titanium dioxide nano particles coated with the silicate, and filtering the suspension to obtain a solid F;
(5) and washing the solid F with deionized water, removing redundant ethanol and free silicate on the surface of the solid, centrifugally separating, filtering to obtain a solid G, drying, and grinding the solid G to obtain the powder, namely the titanium dioxide photocatalyst powder coated with the silicate.
Further, in the preparation method of the titanium dioxide photocatalyst powder, the photocatalyst titanium dioxide is carbon-doped anatase titanium dioxide, the carbon doping amount is 0.8-1.5%, the particle size is 0.5-1 μm, and the mass percentage of the photocatalyst titanium dioxide in the dispersion liquid A is 1.2-5%;
further, in the preparation method of the titanium dioxide photocatalyst powder, the water content of the absolute ethyl alcohol is less than or equal to 1 percent; the dilute sulfuric acid is a sulfuric acid aqueous solution with the mass concentration of 8-12%.
Further, in the preparation method of the titanium dioxide photocatalyst powder of the present invention, the amino silane coupling agent is a silane coupling agent containing amino groups, such as: one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylethoxysilane and 3-aminopropylmethyldiethoxysilane, wherein the mass fraction of the effective components is more than or equal to 95 percent, and the volume percentage content of the aminosilane coupling agent in the dispersion liquid B is 0.8 to 1.2 percent.
Further, in the preparation method of the titanium dioxide photocatalyst powder, the mass percentage of the solid D in the dispersion liquid E is 1.2-5%; the mass ratio of the silica sol to the dispersion liquid E is 1: 99 to 9.
The silicate-coated titanium dioxide photocatalyst powder has the advantages of low oil absorption, high photocatalytic activity and the like; compared with the uncoated titanium dioxide photocatalyst, the powder prepared by the invention has more excellent water phase and oil phase dispersibility due to the action of the surface silicate, and the degradation effect of the powder on organic matters in the dispersion is obviously reduced due to the shielding effect of the surface silicate. Therefore, the photocatalyst can be used as a highly efficient and stable photocatalyst material in both inorganic and organic dispersion media.
The preparation method of the silicate-coated titanium dioxide photocatalyst powder has wide raw material sources and simple and convenient process, for example, the used photocatalyst-type titanium dioxide, silane coupling agent and silica sol are all in industrial grade, and the preparation process only needs to be matched with the existing process equipment and does not need complex process flow. Compared with the prior art of coating titanium dioxide with silicon dioxide, the invention modifies amino with positive charge on the surface of titanium dioxide through aminosilane coupling agent, and the electrostatic potential and silica sol with negative charge act to tightly combine silicate and titanium dioxide particles together to form stable adsorption coating. For example, the powder with a higher silicate coating rate can improve the photochemical stability of the carrier material, and the powder with a lower silicate coating rate can be used as a high-efficiency photocatalyst to maintain the higher photocatalytic activity of the material for a long time.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) before and after the photocatalyst powder prepared by the present invention is coated with silicate, and an energy spectrum (EDS) distribution (Mapping) chart of Ti and Si elements.
FIG. 2 is a graph showing that the oil absorption of the photocatalyst powder prepared by the present invention varies with the mass fraction of silicate.
FIG. 3 is a graph showing the removal rate of NO from photocatalyst powders with different silicate mass fractions as a function of time.
Detailed Description
The invention is further described and examples are given below.
The raw materials used in this example are all commercially available products, wherein:
photocatalyst-type titanium dioxide: the 7000 type product produced by Krono company is adopted, the carbon doping amount is 0.8% -1.5%, and the grain size is about 0.5-1 μm.
Amino silane coupling agent: 3-aminopropyltrimethoxysilane KH-540, 3-aminopropyltriethoxysilane KH-550 and 3-aminopropylmethyldiethoxysilane SG-Si902, which are available from Nanjing eosin chemical group, Ltd.
Silica sol: LUDOX TMA silica sol produced by GRACE, in which the silica has a particle size of about 22nm and a specific surface area of about 130m2The silicon dioxide is 33-34% in mass fraction, the particles are electronegative and stable within the pH range of 4-10.
Example 1
(preparation of titanium dioxide photocatalyst powder having silicate of about 5% by mass)
(1) Adding photocatalyst type titanium dioxide into absolute ethyl alcohol, and stirring for 1 hour by shaking until the titanium dioxide is completely dispersed into a dispersion liquid A, wherein the mass percent of the photocatalyst type titanium dioxide in the dispersion liquid A is 5%; to the dispersion a, a saturated solution of sodium hydrogencarbonate was added dropwise with stirring until the pH was adjusted to 8 to obtain a dispersion B.
(2) Dropwise adding a liquid aminosilane coupling agent KH-540 into the dispersion liquid B, and simultaneously heating the dispersion liquid B to 80 ℃, wherein the addition amount of KH-540 is 1.2% of the volume fraction of the dispersion liquid B; stirring at low speed under the condition of condensing reflux to react for 4 hours; stopping heating, cooling to room temperature, filtering the dispersion liquid B to obtain a solid C, alternately and repeatedly cleaning and filtering the solid C by using absolute ethyl alcohol and 10% dilute sulfuric acid until the pH value of the filtrate is 6, and filtering to obtain a solid D;
(3) adding the solid D into absolute ethyl alcohol, and stirring for 1.5 hours until the solid D is completely dispersed to obtain a dispersion liquid E of the solid D; slowly adding silica sol into the dispersion liquid E at normal temperature, stirring for 30 minutes at the same time, adsorbing and wrapping the silicate with negative charges on the surface of the titanium dioxide with positive charges to obtain a suspension of titanium dioxide nano particles coated with the silicate, and filtering the suspension to obtain a solid F;
the mass percent of the solid D in the dispersion liquid E is 5 percent; the ratio of the silica sol to the dispersion E is 1: 99;
(4) and washing the solid F with deionized water, removing redundant ethanol and free silicate on the surface of the solid, centrifugally separating, filtering to obtain a solid G, drying, and grinding the solid G to obtain the powder, namely the titanium dioxide photocatalyst powder coated with the silicate.
EDS analysis proves that the silicate-coated titanium dioxide photocatalyst powder contains about 5% of silicate by mass, has the particle size of 0.91 mu m and the specific surface area of 219m2/g, and the surface of the product is in a scaly structure.
Example 2
(preparation of titanium dioxide photocatalyst powder having silicate of about 10% by mass)
(1) Adding photocatalyst type titanium dioxide into absolute ethyl alcohol, and stirring for 0.8 hour in a shaking way until the titanium dioxide is completely dispersed into a dispersion liquid A, wherein the mass percent of the photocatalyst type titanium dioxide in the dispersion liquid A is 5%; to the dispersion a, a saturated solution of sodium hydrogencarbonate was added dropwise with stirring until the pH was adjusted to 8 to obtain a dispersion B.
(2) Then, dropwise adding an aminosilane coupling agent KH-550 into the dispersion liquid B while heating, wherein the addition amount of KH-550 is 1.0 percent of the volume fraction of the dispersion liquid B; after the temperature of the dispersion liquid B is between 85 ℃, the dispersion liquid B is stirred at high speed to react for 2 hours in a condensation reflux environment; stopping heating, cooling to room temperature, filtering the dispersion liquid B to obtain a solid C, alternately and repeatedly cleaning and filtering the solid C by using absolute ethyl alcohol and 10% dilute sulfuric acid until the pH value of the filtrate is 7, and filtering to obtain a solid D;
(3) adding the solid D into absolute ethyl alcohol, and stirring for 1.2 hours until the solid D is completely dispersed to obtain a dispersion liquid E of the solid D; slowly adding silica sol into the dispersion liquid E at normal temperature, stirring at high speed for 10 minutes at the same time, adsorbing and wrapping the silicate with negative charges on the surface of the titanium dioxide with positive charges to obtain a suspension of the titanium dioxide nano particles coated with the silicate, and filtering the suspension to obtain a solid F;
the mass percent of the solid D in the dispersion liquid E is 4 percent; the ratio of silica sol to dispersion E is about 1: 65;
(4) and washing the solid F with deionized water, removing redundant ethanol and free silicate on the surface of the solid, centrifugally separating, filtering to obtain a solid G, drying, and grinding the solid G to obtain the powder, namely the titanium dioxide photocatalyst powder coated with the silicate.
EDS analysis proves that the silicate-coated titanium dioxide photocatalyst powder contains about 10 percent of silicate by mass, has the particle size of 0.99 mu m and the specific surface area of 213m2And/g, the surface of the product is in a scaly structure.
Example 3
(preparation of titanium dioxide photocatalyst powder having silicate of about 30% by mass)
(1) Adding photocatalyst type titanium dioxide into absolute ethyl alcohol, and stirring for 1 hour by shaking until the titanium dioxide is completely dispersed into a dispersion liquid A, wherein the mass percent of the photocatalyst type titanium dioxide in the dispersion liquid A is 1.2%; to the dispersion a, a saturated solution of sodium hydrogencarbonate was added dropwise with stirring until the pH was adjusted to 9.
(2) Heating to 80 ℃, then starting condensation reflux, dropwise adding an aminosilane coupling agent SG-Si902 into the dispersion liquid A within 1 hour, and continuing condensation reflux for 3 hours to obtain dispersion liquid B, wherein the addition amount of SG-Si902 is 0.8% of the volume fraction of the dispersion liquid B; stopping heating, cooling to room temperature, filtering the dispersion liquid B to obtain a solid C, alternately and repeatedly cleaning and filtering the solid C by using absolute ethyl alcohol and 10% dilute sulfuric acid until the pH value of the filtrate is about 6-7, and filtering to obtain a solid D;
(3) adding the solid D into absolute ethyl alcohol, and stirring for 1 hour until the solid D is completely dispersed to obtain a dispersion liquid E of the solid D; slowly adding silica sol into the dispersion liquid E at normal temperature, and slowly stirring at 10 ℃ for 60 minutes to enable the silicate with negative charges to be adsorbed on the surface of the titanium dioxide with positive charges and wrap the titanium dioxide with positive charges to obtain suspension of titanium dioxide nano particles coated with the silicate, and filtering the suspension to obtain a solid F;
the mass percent of the solid D in the dispersion liquid E is 1.2 percent; the ratio of the added amount of the silica sol to the dispersion E is about 1: 27;
(4) and washing the solid F with deionized water, removing redundant ethanol and free silicate on the surface of the solid, centrifugally separating, filtering to obtain a solid G, drying, and grinding the solid G to obtain the powder, namely the titanium dioxide photocatalyst powder coated with the silicate.
EDS analysis determines that the obtained titanium dioxide photocatalyst powder coated with the silicate contains 30 percent of silicate by mass, the particle size is 1.34 mu m, and the specific surface area is 207m2And/g, the surface of the product is in a scaly structure.
Example 4
(preparation of titanium dioxide photocatalyst powder having silicate content of about 40%)
(1) Adding photocatalyst type titanium dioxide into absolute ethyl alcohol, and stirring for 1 hour by shaking until the titanium dioxide is completely dispersed into a dispersion liquid A, wherein the mass percent of the photocatalyst type titanium dioxide in the dispersion liquid A is 1.2%; to the dispersion a, a saturated solution of sodium hydrogencarbonate was added dropwise with stirring until the pH was adjusted to 8 to obtain a dispersion B.
(2) Then adding an aminosilane coupling agent KH-550 into the dispersion liquid B, wherein the addition amount of KH-550 is 0.8 percent of the volume fraction of the dispersion liquid B; heating the dispersion liquid B to 80 ℃, and stirring at a low speed to react for 4 hours in a condensation reflux environment; stopping heating, cooling to room temperature, filtering the dispersion liquid B to obtain a solid C, alternately and repeatedly cleaning and filtering the solid C by using absolute ethyl alcohol and 10% dilute sulfuric acid until the pH value of the filtrate is 6-7, and filtering to obtain a solid D;
(3) adding the solid D into absolute ethyl alcohol, and stirring for 1 hour until the solid D is completely dispersed to obtain a dispersion liquid E of the solid D; slowly adding silica sol into the dispersion liquid E at normal temperature, stirring for 40 minutes at the same time, adsorbing and wrapping the silicate with negative charges on the surface of the titanium dioxide with positive charges to obtain a suspension of titanium dioxide nano particles coated with the silicate, and filtering the suspension to obtain a solid F;
the mass percent of the solid D in the dispersion liquid E is 1.2 percent; the ratio of the added amount of silica sol to the dispersion E was about 1: 9;
(4) and washing the solid F with deionized water, removing redundant ethanol and free silicate on the surface of the solid, centrifugally separating, filtering to obtain a solid G, drying, and grinding the solid G to obtain the powder, namely the titanium dioxide photocatalyst powder coated with the silicate.
EDS analysis proves that the silicate-coated titanium dioxide photocatalyst powder contains about 40 percent of silicate by mass, has the particle size of 0.58 mu m and the specific surface area of 204m2And/g, the surface of the product is in a scaly structure.
Experimental example 1: structural characterization of photocatalyst powder
The silicate-coated titanium dioxide photocatalyst powder obtained by the invention is light yellow powder, and Scanning Electron Microscopy (SEM) is used for carrying out structural characterization on the titanium dioxide photocatalyst powder before and after coating:
FIG. 1 is a SEM photograph showing the titania photocatalyst powder before and after coating in example 1, in which the particle diameter of the particles is about 1 μm, the surface of the particles before coating is a porous structure, and the surface of the particles after coating is a scaly structure and the particle diameter is about 1 μm, due to the coating of the silicate.
Further, when the titanium and silicon elements of the particles before and after coating were subjected to energy spectrum analysis, the energy spectrum distribution was as shown in fig. 1, and the particles before coating had only the titanium element and almost no silicon element. Besides titanium, silicon with higher concentration is added after coating, which indicates that the silicate is coated on the surface of the silicate.
Experimental example 2: oil absorption of photocatalyst powder
According to the national standard GB/T5211.15-2014, part 15 of the "general test methods for pigments and extender pigments": measurement of oil absorption the oil absorption of the titanium dioxide photocatalyst powders obtained in examples 1 to 4 at different silicate coating ratios was measured. The final test result is shown in fig. 2, and as the silicate content in the titanium dioxide photocatalyst powder is increased from 0% to 40%, the oil absorption is gradually reduced.
Experimental example 3: photocatalytic activity of photocatalyst powder
The silicate-coated titanium dioxide photocatalyst powders obtained in examples 1 to 4 and P25 nano photocatalyst provided by Degussa were dispersed in absolute ethanol in an amount of 5% by weight of the photocatalyst, and 10ml of the ethanol dispersion was uniformly added dropwise to (10X 20X 0.2) cm3And drying the glass fiber mesh cloth to obtain the glass fiber sample loaded with the photocatalyst powder. The removal rate of acetaldehyde by different samples is determined according to the standard GB/T23761-2009 Performance test method for photocatalytic air purification materials, and the change curve of the removal rate of acetaldehyde by photocatalyst powder with different mass fractions along with time is shown in FIG. 3. The photocatalytic activity of the silicate-coated titanium dioxide is reduced compared to the photocatalyst before coating, and the activity decreases with increasing mass fraction, but still slightly higher than P25.
Experimental example 4: degradation of organic matter in carrier by photocatalyst powder
The photocatalyst powders obtained in examples 1 to 4 were added to an aqueous polyurethane emulsion (particle size of colloidal particles)>0.1 μm), the addition amount of the photocatalyst powder is 40 wt%, and the polyurethane loaded with the photocatalyst is obtained after high-speed dispersion. Coating a sample on a white ceramic chip, and after the coating is cured, carrying out an indoor artificial aging test on the sample according to a method shown in ISO 16474-2013, wherein UVA-340 is selected as lamp light, and the irradiation intensity is 0.83W/m2After 96 hours of irradiation and condensation cycles, the color difference Δ E before and after the aging test was measured according to the color change rating of section 4.2 in GB/T1766-. As can be seen, the higher the silicate content in the photocatalyst powder, the more the polyurethane coating film is agedWeak.
TABLE 1 degree of aging of the photocatalyst powder-loaded polyurethane film of the present invention
The foregoing is a more detailed description of the present invention in connection with specific preferred embodiments thereof, and it is not intended that the invention be limited to the specific details set forth herein. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (7)
1. A preparation method of titanium dioxide photocatalyst powder coated by silicate is characterized by comprising the following steps: (1) adding photocatalyst type titanium dioxide into absolute ethyl alcohol, and shaking or stirring for 0.5-1 hour until the photocatalyst type titanium dioxide is completely dispersed into a dispersion liquid A; dropwise adding a saturated sodium bicarbonate solution into the dispersion liquid A while stirring until the pH is adjusted to 8-9 to obtain a dispersion liquid B; (2) dropwise adding a liquid aminosilane coupling agent into the dispersion liquid B, and simultaneously heating the dispersion liquid B to 80-85 ℃; or dropwise adding a liquid aminosilane coupling agent into the dispersion liquid B, and then heating the dispersion liquid B to 80-85 ℃; or heating the dispersion liquid B to 80-85 ℃, and then dropwise adding a liquid aminosilane coupling agent; (3) stirring the dispersion B to react for 4 to 5 hours in a condensing reflux environment; stopping heating, cooling to room temperature, filtering the dispersion liquid B to obtain a solid C, alternately and repeatedly cleaning and filtering the solid C by using absolute ethyl alcohol and dilute sulfuric acid until the pH value of the filtrate is 6-7, and obtaining a solid D; (4) adding the solid D into absolute ethyl alcohol, and oscillating or stirring for 15-30 minutes until the solid D is completely dispersed to obtain a dispersion liquid E of the solid D; slowly adding silica sol into the dispersion liquid E at normal temperature, stirring for 30-45 minutes at the same time, adsorbing and wrapping the silicate with negative charges on the surface of the titanium dioxide with positive charges to obtain a suspension of the titanium dioxide nano particles coated with the silicate, and filtering the suspension to obtain a solid F; (5) and cleaning the solid F with deionized water, removing redundant ethanol and free silicate on the surface of the solid, centrifugally separating, filtering to obtain a solid G, drying, and grinding the solid G to obtain the powder, namely the titanium dioxide photocatalyst powder coated with silicate.
2. The method according to claim 1, wherein the photocatalytic titanium dioxide is carbon-doped anatase titanium dioxide, the amount of carbon doping is 0.8 to 1.5%, the particle size is 0.5 to 1 μm, and the mass percentage of the photocatalytic titanium dioxide in the dispersion A is 1.2 to 5%.
3. The method according to claim 1, wherein the absolute ethanol has a water content of 1% or less; the dilute sulfuric acid is a sulfuric acid aqueous solution with the mass concentration of 8-12%.
4. The preparation method according to claim 1, characterized in that the aminosilane coupling agent is a silane coupling agent containing amino, the mass fraction of the active ingredient is not less than 95%, and the volume percentage content of the aminosilane coupling agent in the dispersion liquid B is 0.8-1.2%.
5. The method according to claim 4 or 1, wherein the aminosilane coupling agent is one or more selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylethoxysilane, and 3-aminopropylmethyldiethoxysilane.
6. The preparation method according to claim 1, wherein the silica sol is a colloidal solution formed by uniformly diffusing nano-scale silica particles in water, wherein the silica has a particle size of 13-29 nm, a mass percentage of 30-50%, and a specific surface area of 110-160 m2The particles are electronegative and stable within the pH value range of 4-10.
7. The process according to claim 1, wherein the solid D is contained in the dispersion E in an amount of 1.2 to 5% by mass; the mass ratio of the silica sol to the dispersion liquid E is 1: 99 to 9.
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