CN109433174A - Silicate cladding titanium dioxide photocatalyst powder and preparation method thereof - Google Patents
Silicate cladding titanium dioxide photocatalyst powder and preparation method thereof Download PDFInfo
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- CN109433174A CN109433174A CN201811204033.2A CN201811204033A CN109433174A CN 109433174 A CN109433174 A CN 109433174A CN 201811204033 A CN201811204033 A CN 201811204033A CN 109433174 A CN109433174 A CN 109433174A
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- titanium dioxide
- photocatalyst
- dispersion liquid
- silicate
- solids
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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 99
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 87
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000000843 powder Substances 0.000 title claims abstract description 69
- 238000005253 cladding Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 82
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000007787 solid Substances 0.000 claims abstract description 67
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 32
- 239000007822 coupling agent Substances 0.000 claims abstract description 22
- -1 amino silicane Chemical compound 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- 239000002738 chelating agent Substances 0.000 claims abstract description 3
- 229960005196 titanium dioxide Drugs 0.000 claims description 95
- 235000010215 titanium dioxide Nutrition 0.000 claims description 95
- 239000007788 liquid Substances 0.000 claims description 92
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 239000012047 saturated solution Substances 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 2
- 230000004043 responsiveness Effects 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- ZMWJQGOYIBHQJG-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-ol Chemical compound CCO[Si](C)(OCC)CCCO ZMWJQGOYIBHQJG-UHFFFAOYSA-N 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000011859 microparticle Substances 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 239000005416 organic matter Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 230000009514 concussion Effects 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005421 electrostatic potential Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- 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 present invention provides a kind of silicate cladding titanium dioxide photocatalyst powders and preparation method thereof, using photocatalyst type titanium dioxide as carrier, silica solution be covering material, amino silicane coupling agent is chelating agent, silicate is coated on to the particle surface of titanium dioxide, photocatalyst of titanium dioxide diameter of particle after cladding is 0.5 ~ 1.5 μm, specific surface area >=200 m2/ g, the silicate containing mass percentage 5%~40% can be used for preparing the Photocatalyst water solution of high solids content, and using organic matter as the catalysis material of carrier.Have many advantages, such as that silicate absorption is stablized, clad ratio is high and it is controllable, oil absorption is low, photocatalytic activity is high, using this photocatalyst powder, be easy dispersion and not will cause the degradation of organic carrier.Preparation method of the invention is easy to get using raw material, simple process, and silicate cladding stablizes and clad ratio is controllable.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of silicate cladding titanium dioxide photocatalyst powder
And preparation method thereof.
Background technique
Titanium dioxide as a kind of common photocatalyst, have large specific surface area, photocatalysis and absorbability, weatherability and
The advantages that chemical corrosion resistance is good, nontoxic to the human body has certain application in photocatalysis field, by absorbing photon, dioxy
Change titanium surface and generate redox free radical, chemically reacted with external substance, such as hydrolytic hydrogen production may be implemented, removal has
The functions such as evil object.However, when preparing catalysis material using titanium dioxide, due to TiO 2 particles dispersion stabilization is poor,
It is difficult to infiltrate in organic phase, satisfactory catalytic effect can not be shown, therefore industrially carrying titanium dichloride load
It is used on body, finds suitable carrier and become and restrict one of its widely used important bottleneck.
On the one hand, for increasing specific surface area, photocatalyst type titanium dioxide powder often has porous structure, oil suction and suction
Water is higher, and dispersing powder in liquid phase carrier, which needs to add the auxiliary agents such as a large amount of surfactant, dispersing agent, to divide completely
The problems such as dissipating or reduce the consumption to lotion, causing the complication or low photocatalyst powder load capacity of preparation process, to reduce
The photocatalytic activity of catalysis material finished product.
On the other hand, when there are unit timesharing (macromolecular adhesive, or addition organic matter face such as have been used to fill out in carrier
Material), the oxidation of titanium dioxide can be by these organic matter degradations, to cause the destruction of material structure or lacking for basic performance
It loses.
Effective way regarding to the issue above first is that titanium dioxide carry out hydridization processing, to its surface wrap up, such as make
Titania-silica hydridization (the TiO of standby core-shell structure2@SiO2) nanoparticle.The approach can reduce titanium dioxide
Porosity and surface energy, while the direct contact of titanium dioxide and organic component is isolated.
Preparing above-mentioned TiO2@SiO2In the method for nanoparticle, the most common method first is that pass through surfactant will
Organosilicon is carried in titanium dioxide surface, such as CN 107008242A and has used tetraethyl orthosilicate, in titanium dioxide surface packet
TiO is obtained through calcining after covering2@SiO2.But such method is easy to appear more by-product during the preparation process, and during cladding
There may be the appearance of the problems such as gel.
Another method is to use silicate or silica as direct general in silicon-containing material, such as CN103232733A
Silica solution and not surface treated titania slurry are blended, and are used to prepare TiO after curing2@SiO2.But institute in such method
Lower using silicon-containing material activity, the surfactants such as common coupling agent are difficult to the shape between silica and titanium dioxide titanium
At stable bridge joint, to cause the problems such as clad ratio is low, clad ratio is uncontrollable.
Summary of the invention
The purpose of the present invention is to provide a kind of photocatalyst of titanium dioxide powder and preparation method thereof of silicate cladding, with
Overcome silicon materials existing in the prior art titanium dioxide surface cannot be adsorbed steadily, clad ratio is low and it is uncontrollable, degradation
The deficiencies of organic carrier, titanium dioxide difficulties in dispersion.
The photocatalyst of titanium dioxide powder of a kind of silicate cladding of the invention, which is characterized in that with photocatalyst type dioxy
Change titanium is carrier, silica solution is covering material, amino silicane coupling agent is chelating agent, and silicate is coated on to the grain of titanium dioxide
Sublist face, the photocatalyst of titanium dioxide diameter of particle after cladding are 0.5~1.5 μm, specific surface area >=200m2/ g, contains quality
The silicate of percentage composition 5%~40%.
Preferably, the photocatalyst type titanium dioxide is carbon doped anatase-type titanium dioxide, and carbon doping is 0.8%
~1.5%, partial size is 0.5~1 μm, has excellent absorption and responsiveness to visible light.
Preferably, the silica solution is the colloidal solution that nano-scale silica particles uniformly diffuse to form in water,
Wherein silica partial size is 13~29nm, and mass percentage is 30%~50%, specific surface area about 110~160m2/ g, grain
Son is in elecrtonegativity, stable in 4~10 range of pH value；Such as: the LUDOX TMA silica solution of GRACE company production.
Preferably, the amino silicane coupling agent is the silane coupling agent containing amino, such as: 3- aminopropyl front three
Oxysilane, 3-aminopropyltriethoxysilane, 3- dimethyl Ethoxysilane, 3- amino propyl methyl diethyl
One of oxysilane is a variety of, these silane coupling agents are liquid under room temperature, and the mass percentage of effective component >=
95%, it is possible to provide positively charged amino.
A kind of photocatalyst of titanium dioxide raw powder's production technology of silicate cladding of the invention, which is characterized in that including
Following steps:
(1) photocatalyst type titanium dioxide is added in dehydrated alcohol, shaken or stirred 0.5~1 hour, until photocatalyst
Type titanium dioxide is completely dispersed as dispersion liquid A；Saturated solution of sodium bicarbonate is added dropwise into dispersion liquid A while stirring, directly
8~9 are adjusted to pH, obtains dispersion liquid B；
(2) liquid amino silicane coupling agent is added dropwise into dispersion liquid B, and heats dispersion liquid B to 80~85 DEG C simultaneously；
Or liquid amino silicane coupling agent is added dropwise into dispersion liquid B, then heat dispersion liquid B to 80~85 DEG C；Or it will divide
Dispersion liquid B is heated to that liquid amino silicane coupling agent is added dropwise after 80~85 DEG C again；
(3) it in the case where being condensed back environment, is dispersed with stirring liquid B and is allowed to react 4~5 hours；Stop heating and is allowed to be cooled to
After room temperature, filtering dispersion liquid B obtains solids C, cleans and filter solids C with dehydrated alcohol and dilute sulfuric acid alternate repetition, directly
PH to filtrate is 6~7, obtains solids D；
(4) solids D is added to absolute ethanol, shaken or stirred 15~30 minutes, until being completely dispersed to obtain solid
The dispersion liquid E of object D；At normal temperature, it is slowly added to silica solution into dispersion liquid E, while stirring 30~45 minutes, makes negatively charged
Silicate adsorb and wrapped up in positively charged titanium dioxide surface, obtain silicate cladding titanium dioxide nano particle
Suspension, suspension is filtered, solids F is obtained；
(5) solids F is cleaned with deionized water, removes surface of solids unnecessary alcohol and free silicate, and be centrifuged and divide
From being obtained by filtration solids G, solids G ground after dry, gained powder is the titanium dioxide of silicate cladding of the invention
Photocatalyst powder.
Further, in photocatalyst of titanium dioxide raw powder's production technology of the invention, the photocatalyst type dioxy
Change titanium is carbon doped anatase-type titanium dioxide, and carbon doping is 0.8%~1.5%, and partial size is 0.5~1 μm, in dispersion liquid
Mass percent in A is 1.2%~5%；
Further, in photocatalyst of titanium dioxide raw powder's production technology of the invention, the dehydrated alcohol contains
Water≤1%；The dilute sulfuric acid is the aqueous sulfuric acid that mass concentration is 8%~12%.
Further, in photocatalyst of titanium dioxide raw powder's production technology of the invention, the amino silane coupling
Agent be the silane coupling agent containing amino, such as: 3- TSL 8330,3-aminopropyltriethoxysilane,
One of 3- dimethyl Ethoxysilane, 3-amino propyl methyl diethoxy silane or a variety of, effective component
Mass fraction >=95%, volumn concentration of the amino silicane coupling agent in dispersion liquid B are 0.8%~1.2%.
Further, in photocatalyst of titanium dioxide raw powder's production technology of the invention, the solids D is dispersing
Mass percent in liquid E is 1.2%~5%；The mass ratio of the silica solution and dispersion liquid E is 1:99~9.
Silicate cladding titanium dioxide photocatalyst powder of the invention has many advantages, such as that oil absorption is low, photocatalytic activity is high；
Compared to uncoated photocatalyst of titanium dioxide, powder prepared by the present invention due to surface silicates effect and have more
Excellent water phase is mutually dispersed with oil, and due to the screen effect of surface silicates, degradation of the powder in dispersion to organic matter
Effect is substantially reduced.Therefore no matter in inorganic or organic dispersion medium, can be used as the photocatalyst raw material of efficient stable and
It uses.
Silicate cladding titanium dioxide photocatalyst raw powder's production technology of the invention, raw material sources are extensive, technique letter
Just, for example, used in photocatalyst type titanium dioxide, silane coupling agent, silica solution, be industrial rank, preparation process only needs to match
Existing process equipment is covered, complex process flow is not necessarily to.Compared to the technology of existing coated with silica titanium dioxide, the present invention is logical
It crosses amino silicane coupling agent and modifies positively charged amino in titanium dioxide surface, electrostatic potential and negatively charged silica solution are made
With, silicate and TiO 2 particles are closely linked, stable absorption is formd and coats, obtained titanium-dioxide photo
Catalyst powder photocatalytic activity is higher, and the clad ratio of silicate is controllable, and therefore, this novel photocatalyst powder is as raw material
Different actual use demands can be met when use.For example, the higher powder of silicate clad ratio can improve the light of carrier material
Chemical stability, and the lower powder of silicate clad ratio can be used as efficient photocatalyst come using, it is long-term keep material compared with
Highlight catalytic active.
Detailed description of the invention
Fig. 1 is photocatalyst powder prepared by the present invention through silicate cladding traversing of probe Electronic Speculum (SEM) and Ti and Si element
Power spectrum (EDS) is distributed (Mapping) figure.
Fig. 2 is the curve that the oil absorption of photocatalyst powder prepared by the present invention changes with silicate mass fraction.
Fig. 3 is that the photocatalyst powder of different silicate mass fractions changes over time curve to nitric oxide production removal rate.
Specific embodiment
To further description of the present invention and provide embodiment below.
Raw material used in the present embodiment is commercial product, in which:
Photocatalyst type titanium dioxide: using Krono company produce 7000 type products, carbon doping be 0.8%~
1.5%, about 0.5~1 μm of partial size.
Amino silicane coupling agent: the 3- aminopropyl trimethoxysilane KH- of NanJing Shuguang Chemical Group Co., Ltd.'s production
540,3-aminopropyltriethoxysilane KH-550,3-amino propyl methyl diethoxy silane SG-Si902.
Silica solution: the LUDOX TMA silica solution of GRACE company production, wherein silica partial size is about 22nm, specific surface
Product about 130m2/ g, silica quality score is about 33%~34%, and particle is in elecrtonegativity, steady in 4~10 range of pH
It is fixed.
Embodiment 1
(the photocatalyst of titanium dioxide powder for preparing silicate mass fraction about 5%)
(1) photocatalyst type titanium dioxide is added in dehydrated alcohol, concussion stirring 1 hour, until titanium dioxide is complete
It is dispersed into dispersion liquid A, wherein its mass percent in dispersion liquid A of photocatalyst type titanium dioxide is 5%；While stirring to
Saturated solution of sodium bicarbonate is added dropwise in dispersion liquid A, until pH is adjusted to 8, obtains dispersion liquid B.
(2) liquid amino silicane coupling agent KH-540 is added dropwise into dispersion liquid B, and heats dispersion liquid B to 80 simultaneously
DEG C, the additional amount of KH-540 is the 1.2% of dispersion liquid B volume fraction；In the case where being condensed back environment, stirs at low speed and be allowed to react 4
Hour；Stop heating and being allowed to after being cooled to room temperature, filtering dispersion liquid B obtains solids C, with dehydrated alcohol and 10% dilute sulphur
Sour alternate repetition cleaning and filtering solids C take and solids D are obtained by filtration until the pH of filtrate is 6；
(3) solids D is added to absolute ethanol, is stirred 1.5 hours, until being completely dispersed to obtain the dispersion of solids D
Liquid E；At normal temperature, it is slowly added to silica solution into dispersion liquid E, while stirring 30 minutes, makes negatively charged silicate in band
The titanium dioxide surface of positive charge is adsorbed and is wrapped up, and obtains the suspension of silicate cladding titanium dioxide nano particle, right
Suspension is filtered, and obtains solids F；
Mass percent of the solids D in dispersion liquid E is 5%；The ratio of the silica solution and dispersion liquid E is
1:99；
(4) solids F is cleaned with deionized water, removes surface of solids unnecessary alcohol and free silicate, and be centrifuged and divide
From being obtained by filtration solids G, solids G ground after dry, gained powder is the titanium dioxide of silicate cladding of the invention
Photocatalyst powder.
It is analyzed through EDS, in the photocatalyst of titanium dioxide powder for determining obtained silicate cladding, silicate quality percentage contains
Amount about 5%, partial size are 0.91 μm, specific surface area 219m2/g, and surface is in sclay texture.
Embodiment 2
(the photocatalyst of titanium dioxide powder for preparing silicate mass fraction about 10%)
(1) photocatalyst type titanium dioxide is added in dehydrated alcohol, concussion stirring 0.8 hour, until titanium dioxide is complete
It is dispersed into dispersion liquid A entirely, wherein its mass percent in dispersion liquid A of photocatalyst type titanium dioxide is 5%；While stirring
Saturated solution of sodium bicarbonate is added dropwise into dispersion liquid A, until pH is adjusted to 8, obtains dispersion liquid B.
(2) amino silicane coupling agent KH-550, the additional amount of KH-550 are then added dropwise into dispersion liquid B in heating
It is the 1.0% of dispersion liquid B volume fraction；To after dispersion liquid B to 85 DEG C, in the case where being condensed back environment, high-speed stirred is allowed to react 2
Hour；Stop heating and being allowed to after being cooled to room temperature, filtering dispersion liquid B obtains solids C, with dehydrated alcohol and 10% dilute sulphur
Sour alternate repetition cleaning and filtering solids C take and solids D are obtained by filtration until the pH of filtrate is 7；
(3) solids D is added to absolute ethanol, is stirred 1.2 hours, until being completely dispersed to obtain the dispersion of solids D
Liquid E；At normal temperature, it is slowly added to silica solution, while high-speed stirred 10 minutes into dispersion liquid E, makes negatively charged silicate
It adsorbs and is wrapped up in positively charged titanium dioxide surface, obtain the suspension of silicate cladding titanium dioxide nano particle
Liquid is filtered suspension, obtains solids F；
Mass percent of the solids D in dispersion liquid E is 4%；The ratio of the silica solution and dispersion liquid E is
About 1:65；
(4) solids F is cleaned with deionized water, removes surface of solids unnecessary alcohol and free silicate, and be centrifuged and divide
From being obtained by filtration solids G, solids G ground after dry, gained powder is the titanium dioxide of silicate cladding of the invention
Photocatalyst powder.
It is analyzed through EDS, in the photocatalyst of titanium dioxide powder for determining obtained silicate cladding, silicate quality percentage contains
Amount about 10%, partial size are 0.99 μm, specific surface area 213m2/ g, surface are in sclay texture.
Embodiment 3
(the photocatalyst of titanium dioxide powder for preparing silicate mass fraction about 30%)
(1) photocatalyst type titanium dioxide is added in dehydrated alcohol, concussion stirring 1 hour, until titanium dioxide is complete
It is dispersed into dispersion liquid A, wherein its mass percent in dispersion liquid A of photocatalyst type titanium dioxide is 1.2%；While stirring
Saturated solution of sodium bicarbonate is added dropwise into dispersion liquid A until pH is adjusted to 9.
(2) after being heated to 80 DEG C, start to be condensed back, amino silane coupling is added dropwise in 1 hour into dispersion liquid A
Agent SG-Si902 is further continued for being condensed back 3 hours, obtains dispersion liquid B, and the additional amount of SG-Si902 is dispersion liquid B volume fraction
0.8%；Stop heating and simultaneously be allowed to after being cooled to room temperature, filtering dispersion liquid B obtains solids C, with dehydrated alcohol and 10%
The cleaning of dilute sulfuric acid alternate repetition and filtering solids C, until the pH about 6-7 of filtrate, takes and solids D is obtained by filtration；
(3) solids D is added to absolute ethanol, is stirred 1 hour, until being completely dispersed to obtain the dispersion liquid of solids D
E；At normal temperature, it is slowly added to silica solution into dispersion liquid E, while being slowly stirred at 10 DEG C 60 minutes, makes negatively charged
Silicate is adsorbed and is wrapped up in positively charged titanium dioxide surface, obtains silicate cladding titanium dioxide nano particle
Suspension is filtered suspension, obtains solids F；
Mass percent of the solids D in dispersion liquid E is 1.2%；The additional amount of the silica solution with point
The ratio of dispersion liquid E is about 1:27；
(4) solids F is cleaned with deionized water, removes surface of solids unnecessary alcohol and free silicate, and be centrifuged and divide
From being obtained by filtration solids G, solids G ground after dry, gained powder is the titanium dioxide of silicate cladding of the invention
Photocatalyst powder.
It is analyzed through EDS, in the photocatalyst of titanium dioxide powder for determining obtained silicate cladding, silicate quality percentage contains
Amount 30%, partial size are 1.34 μm, specific surface area 207m2/ g, surface are in sclay texture.
Embodiment 4
(the photocatalyst of titanium dioxide powder for preparing silicate mass fraction about 40%)
(1) photocatalyst type titanium dioxide is added in dehydrated alcohol, concussion stirring 1 hour, until titanium dioxide is complete
It is dispersed into dispersion liquid A, wherein its mass percent in dispersion liquid A of photocatalyst type titanium dioxide is 1.2%；While stirring
Saturated solution of sodium bicarbonate is added dropwise into dispersion liquid A, until pH is adjusted to 8, obtains dispersion liquid B.
(2) amino silicane coupling agent KH-550 is then added into dispersion liquid B, the additional amount of KH-550 is dispersion liquid B body
The 0.8% of fraction；Dispersion liquid B to 80 DEG C of heating, in the case where being condensed back environment, stirs at low speed and is allowed to react 4 hours；Stop adding
Heat is simultaneously allowed to after being cooled to room temperature, and filtering dispersion liquid B obtains solids C, with dehydrated alcohol and 10% dilute sulfuric acid alternate repetition
Cleaning and filtering solids C take and solids D are obtained by filtration until the pH of filtrate is 6-7；
(3) solids D is added to absolute ethanol, is stirred 1 hour, until being completely dispersed to obtain the dispersion liquid of solids D
E；At normal temperature, be slowly added to silica solution into dispersion liquid E, while stirring 40 minutes, make negatively charged silicate band just
The titanium dioxide surface of charge is adsorbed and is wrapped up, and obtains the suspension of silicate cladding titanium dioxide nano particle, to outstanding
Supernatant liquid is filtered, and obtains solids F；
Mass percent of the solids D in dispersion liquid E is 1.2%；The additional amount of the silica solution with point
The ratio of dispersion liquid E is about 1:9；
(4) solids F is cleaned with deionized water, removes surface of solids unnecessary alcohol and free silicate, and be centrifuged and divide
From being obtained by filtration solids G, solids G ground after dry, gained powder is the titanium dioxide of silicate cladding of the invention
Photocatalyst powder.
It is analyzed through EDS, in the photocatalyst of titanium dioxide powder for determining obtained silicate cladding, silicate quality percentage contains
Amount about 40%, partial size are 0.58 μm, specific surface area 204m2/ g, surface are in sclay texture.
Experimental example 1: the structural characterization of photocatalyst powder
The photocatalyst of titanium dioxide powder for the silicate cladding that the present invention obtains is faint yellow powder, uses scanning electron microscope
(SEM) structural characterization is carried out to the photocatalyst of titanium dioxide powder before cladding and after cladding:
Fig. 1 show the SEM figure of the cladding of embodiment 1 front and back photocatalyst of titanium dioxide powder, about 1 μm of the partial size of particle, wraps
Particle surface before covering is in porous structure, and for the particle after cladding due to the cladding of silicate, sclay texture, partial size is presented in surface
About 1 μm.
In addition, the titanium and element silicon to cladding front and back particle carry out energy spectrum analysis, spectral distribution is as shown in Figure 1, before cladding
Particle only has titanium elements, and almost without element silicon.After cladding in addition to titanium elements, there are also the element silicons of higher concentration, show silicon
Cladding of the hydrochlorate on its surface.
Experimental example 2: the oil absorption of photocatalyst powder
" pigment and extender pigment GENERAL EXPERIMENTATION " the 15th part: GB/T 5211.15-2014 according to national standards inhales
The measurement of oil mass measures the oil suction of the photocatalyst of titanium dioxide powder under the different silicate clad ratios that Examples 1 to 4 obtains
Amount.Final testing result as shown in Fig. 2, in photocatalyst of titanium dioxide powder silicate content from 0% increase to 40%, inhale
Oil mass gradually decreases.
Experimental example 3: the photocatalytic activity of photocatalyst powder
The silicate cladding titanium dioxide photocatalyst powder that Examples 1 to 4 is obtained, with Degussa (Degussa) company
The P25 nano photo-catalytic of offer is scattered in dehydrated alcohol according to the amount that the weight percent of photocatalyst is 5%, then respectively
The above-mentioned alcohol dispersion liquid of 10ml is taken to drop evenly in (10 × 20 × 0.2) cm3Fiberglass gridding cloth in, it is dry after up to negative
It is loaded with the glass fibre sample of photocatalyst powder.According to standard GB/T 23761-2009, " photocatalysis air-cleaning material property is surveyed
Method for testing " measurement various sample is to the removal rate of acetaldehyde, and photocatalyst powder is to acetaldehyde removal rate under different silicate mass fractions
Versus time curve is as shown in Figure 3.Light compared to the photocatalyst before cladding, the titanium dioxide through persilicate cladding is urged
Change activity to decrease, and activity is reduced as mass fraction increases, but still slightly above P25.
Experimental example 4: degradation of the photocatalyst powder to organic matter in carrier
The photocatalyst powder that Examples 1 to 4 is obtained is added in aqueous polyurethane emulsion (particle size analysis > 0.1 μm), light touching
The additional amount of matchmaker's powder is 40%wt, and the polyurethane that load has photocatalyst is obtained after high speed dispersion.It is coated in whiteware on piece
Sample carries out indoors artificial degradation to sample by method shown in ISO 16474-2013 after curing of coating, and light is selected
UVA-340, irradiation intensity 0.83W/m2, after experience irradiation and condensation cycle in 96 hours, by GB/T 1766-2008 " colored paint with
The ranking method of varnish coat aging " in 4.2 sections discoloration grade evaluation, value of chromatism Δ of the test sample before and after degradation
E*, test result are as shown in table 1.As it can be seen that the silicate content in photocatalyst powder is higher, the aging of polyurethane coating film is weaker.
Table 1 has loaded the degree of aging of the polyurethane film of photocatalyst powder of the invention
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Present invention specific implementation is confined to these above-mentioned explanations.For those of ordinary skill in the art to which the present invention belongs,
Without departing from the inventive concept of the premise, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the present invention
Protection scope.
Claims (10)
1. a kind of photocatalyst of titanium dioxide powder of silicate cladding, which is characterized in that with photocatalyst type titanium dioxide be to carry
Body, silica solution are covering material, amino silicane coupling agent is chelating agent, and silicate is coated on to the particle surface of titanium dioxide,
Photocatalyst of titanium dioxide diameter of particle after cladding is 0.5~1.5 μm, specific surface area >=200 m2/ g contains quality percentage
The silicate of content 5%~40%.
2. photocatalyst of titanium dioxide powder according to claim 1, which is characterized in that the photocatalyst type titanium dioxide
For carbon doped anatase-type titanium dioxide, carbon doping is 0.8%~1.5%, and partial size is 0.5~1 μm, is had to visible light excellent
Absorption and responsiveness.
3. photocatalyst of titanium dioxide powder according to claim 1, which is characterized in that the silica solution is nanoscale
The colloidal solution that silicon dioxide microparticle uniformly diffuses to form in water, wherein silica partial size is 13~29 nm, quality percentage
Content is 30%~50%, specific surface area about 110~160m2/ g, particle is in elecrtonegativity, stable in 4~10 range of pH value.
4. photocatalyst of titanium dioxide powder according to claim 1, which is characterized in that the amino silicane coupling agent is
Silane coupling agent containing amino, mass percentage >=95% of effective component, it is possible to provide positively charged amino.
5. photocatalyst of titanium dioxide powder according to claim 4, which is characterized in that the amino silicane coupling agent is
3- TSL 8330,3-aminopropyltriethoxysilane, 3- dimethyl Ethoxysilane, 3- ammonia
One of base hydroxypropyl methyl diethoxy silane is a variety of.
6. a kind of photocatalyst of titanium dioxide raw powder's production technology for preparing silicate cladding as described in claim 1, special
Sign is, includes the following steps:
(1) photocatalyst type titanium dioxide is added in dehydrated alcohol, shaken or stirred 0.5~1 hour, until photocatalyst type two
Titanium oxide is completely dispersed as dispersion liquid A；Saturated solution of sodium bicarbonate is added dropwise into dispersion liquid A while stirring, until pH
8~9 are adjusted to, dispersion liquid B is obtained；
(2) liquid amino silicane coupling agent is added dropwise into dispersion liquid B, and heats dispersion liquid B to 80~85 DEG C simultaneously；Or
Liquid amino silicane coupling agent is added dropwise into dispersion liquid B, then heats dispersion liquid B to 80~85 DEG C；Or by dispersion liquid B
It is heated to that liquid amino silicane coupling agent is added dropwise after 80~85 DEG C again；
(3) it in the case where being condensed back environment, is dispersed with stirring liquid B and is allowed to react 4~5 hours；Stop heating and is allowed to be cooled to room temperature
Afterwards, filtering dispersion liquid B obtains solids C, cleans and filter solids C with dehydrated alcohol and dilute sulfuric acid alternate repetition, until filter
The pH of liquid is 6~7, obtains solids D；
(4) solids D is added to absolute ethanol, shaken or stirred 15~30 minutes, until being completely dispersed to obtain solids D's
Dispersion liquid E；At normal temperature, it is slowly added to silica solution into dispersion liquid E, while stirring 30~45 minutes, makes negatively charged silicon
Hydrochlorate is adsorbed and is wrapped up in positively charged titanium dioxide surface, obtains the outstanding of silicate cladding titanium dioxide nano particle
Supernatant liquid is filtered suspension, obtains solids F；
(5) solids F is cleaned with deionized water, removes surface of solids unnecessary alcohol and free silicate, and be centrifugated, mistake
Filter obtains solids G, and solids G is ground after dry, and gained powder is the titanium-dioxide photo touching of silicate cladding of the invention
Matchmaker's powder.
7. preparation method according to claim 6, which is characterized in that the photocatalyst type titanium dioxide is that carbon doping is sharp
Titanium ore type titanium dioxide, carbon doping are 0.8%~1.5%, and partial size is 0.5~1 μm, the mass percent in dispersion liquid A
It is 1.2%~5%.
8. preparation method according to claim 6, which is characterized in that water content≤1% of the dehydrated alcohol；It is described
Dilute sulfuric acid be aqueous sulfuric acid that mass concentration is 8%~12%.
9. preparation method according to claim 6, which is characterized in that the amino silicane coupling agent is to contain amino
Silane coupling agent, effective component mass fraction >=95%, volumn concentration of the amino silicane coupling agent in dispersion liquid B
It is 0.8%~1.2%, the amino silicane coupling agent is 3- TSL 8330,3- aminopropyl triethoxy
One of silane, 3- dimethyl Ethoxysilane, 3-amino propyl methyl diethoxy silane are a variety of.
10. preparation method according to claim 6, which is characterized in that quality of the solids D in dispersion liquid E
Percentage composition is 1.2%~5%；The mass ratio of the silica solution and dispersion liquid E is 1:99~9.
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