CN107913712A - A kind of titanium dioxide/modification infusorial earth composite material, film and its preparation method and application - Google Patents
A kind of titanium dioxide/modification infusorial earth composite material, film and its preparation method and application Download PDFInfo
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- CN107913712A CN107913712A CN201711294790.9A CN201711294790A CN107913712A CN 107913712 A CN107913712 A CN 107913712A CN 201711294790 A CN201711294790 A CN 201711294790A CN 107913712 A CN107913712 A CN 107913712A
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- Prior art keywords
- infusorial earth
- modification infusorial
- titanium dioxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 148
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000012986 modification Methods 0.000 title claims abstract description 81
- 230000004048 modification Effects 0.000 title claims abstract description 81
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 22
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000007146 photocatalysis Methods 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- -1 alkyl quaternary ammonium salts Chemical class 0.000 claims description 4
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- HBBATKAUXPHIQN-UHFFFAOYSA-N [Cl].[Ti] Chemical compound [Cl].[Ti] HBBATKAUXPHIQN-UHFFFAOYSA-N 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 3
- 230000015556 catabolic process Effects 0.000 abstract description 18
- 238000006731 degradation reaction Methods 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 8
- 230000009881 electrostatic interaction Effects 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 20
- 239000000843 powder Substances 0.000 description 16
- 229910052719 titanium Inorganic materials 0.000 description 15
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 13
- 229960000907 methylthioninium chloride Drugs 0.000 description 13
- 238000013461 design Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000505 pernicious effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000003916 acid precipitation Methods 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- DJGLQWCKPYQFJG-UHFFFAOYSA-N hydrogen peroxide;titanium Chemical compound [Ti].OO DJGLQWCKPYQFJG-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JCDAAXRCMMPNBO-UHFFFAOYSA-N iron(3+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4].[Fe+3].[Fe+3] JCDAAXRCMMPNBO-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- 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
- 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
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention relates to a kind of titanium dioxide/modification infusorial earth composite material, film and its preparation method and application.The composite material is prepared by pH for the TiO 2 sol of 1 ~ 3 anatase titanium dioxide and modification infusorial earth mixing drying；The mass ratio of the TiO 2 sol and modification infusorial earth is 5:9 ~ 11, the modification infusorial earth is the diatomite through acid and cationic surfactant modification successively.Titanium dioxide provided by the invention/modification infusorial earth composite material is using modification infusorial earth as catalyst carrier, TiO 2 sol is photochemical catalyst source, at low temperature can be by titanium dichloride load to modification infusorial earth surface by electrostatic interaction, photocatalysis effect is good, light degradation is selectively low, reunion and recyclable recycling are not easy, preparation condition is simple and practicable, suitable a large amount of productions and application.
Description
Technical field
The present invention relates to building coating field, more particularly, to a kind of titanium dioxide/modification infusorial earth composite material,
Film and its preparation method and application.
Background technology
With environmental problem and the getting worse of energy problem, scientist is directed to how research utilizes money efficient green
Source, improves environment.
Since last century finds the light-catalyzed reaction of titanium dioxide, this light that is nontoxic, deriving from a wealth of sources of titanium dioxide is urged
Change material and obtain more extensive concern and application.Titanium dioxide non-toxic efficient, property are stablized, and luminous energy degraded can be utilized to make
It is difficult to the organic matter degraded with other physics, chemistry or biological method（Such as formaldehyde, organic dyestuff）, in building coating, environment
Administer etc. has good application prospect.But nano-titanium dioxide is lost light and is urged since nano effect is easy to reunite
Change activity.
The natural structure of natural minerals possesses excellent performance.Diatom shell structure such as diatomite uniqueness assigns its strong suction
The advantageous properties such as attached property, bigger serface, high porosity, high temperature resistant, can use as good catalyst carrier；Though it possesses
Adsorb pernicious gas（Such as formaldehyde）Ability, but cannot thoroughly degrade, when high temperature can also discharge institute's adsorbed gas, it is impossible to long-acting
The contaminant problems in environment are solved at all.
Study titanium dichloride load at present by titanium dioxide and diatomite by way of high-temperature calcination in diatom
The composite material for being not easy reunion and degradable pernicious gas is prepared on soil, but calcining can cause the transformation of titanium dioxide crystal form：
Rutile-type is changed into by the anatase titanium dioxide with preferable catalytic activity so that the catalytic activity of composite material is greatly lowered.
Therefore, exploitation one kind has preferable photocatalytic activity, is not easy the catalysis material of reunion and degradable pernicious gas
With important research significance and application value.
The content of the invention
The defects of it is an object of the invention to overcome catalysis material catalytic activity of the prior art low, there is provided one kind two
Titanium oxide/modification infusorial earth composite material.Titanium dioxide provided by the invention/modification infusorial earth composite material is with modification infusorial earth
For catalyst carrier, TiO 2 sol is photochemical catalyst source, at low temperature can be by titanium dichloride load by electrostatic interaction
To modification infusorial earth surface, photocatalysis effect is good, and light degradation is selectively low, is not easy reunion and recyclable recycling, preparation condition
It is simple and practicable, suitable a large amount of productions and application.
Another object of the present invention is to provide the preparation method of above-mentioned titanium dioxide/modification infusorial earth composite material.
Another object of the present invention is to provide a kind of titanium dioxide/modification infusorial earth photocatalysis film.
Another object of the present invention is to provide above-mentioned titanium dioxide/modification infusorial earth composite material to prepare building coating
In application.
For achieving the above object, the present invention adopts the following technical scheme that：
A kind of titanium dioxide/modification infusorial earth composite material, titanium dioxide of the composite material by pH for 1 ~ 3 anatase titanium dioxide
Colloidal sol and modification infusorial earth mixing drying are prepared；The mass ratio of the TiO 2 sol and modification infusorial earth is 5:9~
11, the modification infusorial earth is successively through acid and cationic surfactant modification infusorial earth.
The present invention by the use of the strong modification infusorial earth of high surface area, adsorption capacity as the carrier of photochemical catalyst titanium dioxide,
It can reduce and reunite caused by the skin effect that titanium dioxide nano granule footpath is brought, reduce the compound probability of electron-hole pair；Profit
With the local concentration of diatomaceous adsorptivity increase material surface organic matter, degradation rate of the complex to organic matter is improved.Together
When through acid and the modified modification infusorial earth of cationic surfactant carry positive charge, can by electrostatic interaction with bear
The TiO 2 sol of electricity is preferably adsorbed on modification infusorial earth, has higher photocatalytic activity, light degradation is selectively low.
Preferably, the mass ratio of the TiO 2 sol and modification infusorial earth is 5:10.
When TiO 2 sol dosage is less, the hole on modification infusorial earth surface is not fully utilized, performance
It is poor.When TiO 2 sol dosage is more, surface covers excessive titanium dioxide, and inactivation of easily reuniting, loses diatomite
The advantage of carried titanium dioxide；And load capacity it is more when, attraction is weaker, and the titanium dioxide of outer layer can be dispersed in solution again
In, since its recycling is difficult, cause the loss of catalyst.
Further both quality proportionings of optimization of the invention, not only can obtain the excellent composite material of photocatalysis performance, but also real
The maximum functionization for having showed TiO 2 sol and modification infusorial earth utilizes.
Preferably, the pH of the TiO 2 sol is 3.
TiO 2 sol provided in the present invention can disperse metatitanic acid precipitation to obtain peroxidating by hydrogen peroxide
Titanium solution system, and by being heated to reflux so that titanium peroxide is decomposed into nano titanic oxide sol.What this method was prepared
TiO 2 sol stability is good, and particle diameter is small, and crystal transfer will not occur.
Preferably, the TiO 2 sol is obtained by following preparation method：Metatitanic acid hydrogenperoxide steam generator is disperseed,
After being 1 ~ 3 with inorganic acid for adjusting pH, 2 ~ 4h is heated to reflux at 80 ~ 100 DEG C, obtains light yellow clear stabilized chlorine titanium colloidal sol,
The Ti and H2O2Molar ratio be 1:8~20.
H2O2Generation titanium hydrogen peroxide complexes are reacted with metatitanic acid.This structure only under strongly acidic conditions could be steady
It is fixed to exist（pH<1）, with the rise of system pH, polycondensation reaction takes place.1<pH<3, mainly generate double-core polymerization
Thing, can be represented in structure with following formula：
After sol solution is heated to reflux, due to peroxide radical ion poor chemical stability, can with the rise of system temperature and
Decompose, therefore, as shown in following equation, during being heated to reflux, the peroxide root in system can be decomposed gradually, so as to lead
Cause solution to lose stabilization of the peroxide root to titanium ion, form titanium dioxide solids（Particle diameter very little）, generate colloidal sol：
Preferably, the Ti and H2O2Molar ratio be 1:15.
Metatitanic acid used in the present invention can be prepared by conventional preparation method.
Such as metatitanic acid is prepared by titanium source of organic titanium：Organic titanium is added in organic media, magnetic agitation, is uniformly dispersed plus is gone
Ionized water, hydrolyzes organic titanium source, obtains metatitanic acid precipitation, and deionized water washing is multiple.Organic titanium can be butyl titanate, titanium
One or more in isopropyl propionate, metatitanic acid n-propyl or tetraethyl titanate.
For another example metatitanic acid is prepared by titanium source of titanate：Sulfuric acid dissolves by heating titanate, crosses and filters out after addition deionized water
Insoluble impurities is removed, recrystallizes afterwards and is filtered to remove soluble impurity crystallization, obtain titanium liquid, add alkali neutralization titanium liquid, up to partially
Metatitanic acid precipitates, and deionized water washing is multiple.Titanate can be barium titanate, calcium titanate, magnesium titanate, strontium titanates, aluminium titanates, metatitanic acid
One or more in zinc, nickel titanate, cadmium titanate or iron titanate.
For another example metatitanic acid is prepared by titanium source of inorganic titanium：Add deionized water to dissolve titanium salt, it is molten to obtain inorganic titanium precursors
Liquid；Heating hydrolyzes the precursor solution, is precipitated up to metatitanic acid, and deionized water washing is multiple.Inorganic titanium can be titanium sulfate or
One or more in titanyl sulfate.
Preferably, the inorganic acid is the one or more in hydrochloric acid, sulfuric acid or nitric acid.
The present invention can be modified diatomite by conventional sour modification and cationic surfactant method of modifying
To the diatomite being modified successively through acid and cationic surfactant.
Preferably, the modification infusorial earth is prepared via a method which to obtain：
S1：It is 1 in mass ratio by diatomite and acid solution:5 ~ 10 mixing, stir 4 ~ 5h, filtering, washing, drying at 90 ~ 100 DEG C
Obtain acidleach diatomite；
S2：The acidleach diatomite and cationic surfactant are pressed 1 ~ 2:1 mass ratio mixing, adds water to surpass into after suspension
Sound is up to the modification infusorial earth.
Preferably, the acid solution is the one or more in hydrochloric acid, sulfuric acid or nitric acid；The cationic surfactant is
One or more in alkyl quaternary ammonium salts or amine salt.
The preparation method of above-mentioned titanium dioxide/modification infusorial earth composite material, the method are as follows：By modification infusorial earth with
TiO 2 sol mixes, and forms suspension, stirring or 1 ~ 2h of ultrasound, compound up to titanium dioxide/modification infusorial earth after drying
Material.
A kind of titanium dioxide/modification infusorial earth photocatalysis film, including above-mentioned titanium dioxide/modification infusorial earth composite material
And surfactant, the mass fraction of composite material is 0.5 ~ 5% in the film.
Preferably, the surfactant is cetyl trimethylammonium bromide.
Above-mentioned titanium dioxide/application of the modification infusorial earth composite material in building coating is prepared is also in the protection of the present invention
In the range of.
Compared with prior art, the present invention has the advantages that：
Titanium dioxide provided by the invention/modification infusorial earth composite material is using modification infusorial earth as catalyst carrier, titanium dioxide
Colloidal sol is photochemical catalyst source, at low temperature can be urged titanium dichloride load to modification infusorial earth surface, light by electrostatic interaction
Change effect is good, and light degradation is selectively low, is not easy reunion and recyclable recycling, and preparation condition is simple and practicable, suitable a large amount of productions
And application.
Brief description of the drawings
Fig. 1 is the preparation flow figure of modification infusorial earth provided by the invention；
Fig. 2 is the preparation flow figure of titanium dioxide provided by the invention/modification infusorial earth composite material；
Fig. 3 is rear diatomaceous SEM shape appearance figures before modified；
Fig. 4 is the SEM shape appearance figures of photocatalyst-type material；
Fig. 5 is XRD powder diagrams；
Fig. 6 and Fig. 7 is the design sketch of photocatalyst-type material degradation methylene blue solution.
Embodiment
With reference to embodiment, the present invention is further explained.These embodiments are merely to illustrate the present invention rather than limitation
The scope of the present invention.The experimental method of actual conditions is not specified in lower example embodiment, usually according to this area normal condition or presses
The condition suggested according to manufacturer；Used raw material, reagent etc., unless otherwise specified, being can be from the business such as conventional market
The raw materials and reagents that approach obtains.The change for any unsubstantiality that those skilled in the art is done on the basis of the present invention
And replace and belong to scope of the present invention.
Embodiment 1 ~ 5
The present embodiment provides a kind of titanium dioxide/modification infusorial earth composite material, which is prepared by the following procedure method system
It is standby to obtain：
（1）It is prepared by TiO 2 sol
Take 1mL butyl titanates, under magnetic agitation effect, be scattered in the absolute ethyl alcohol of 5mL, by volume 10:1 add go from
Sub- water, obtains rapidly white emulsion；Deionized water washing is multiple；Obtained metatitanic acid precipitation is disperseed with hydrogen peroxide again,
Add the hydrogen peroxide of 2.6 ~ 6.4mL, dilute solution to 140mL, adjustment pH value is 1 ~ 3, the transparent glassy yellow of solution or slightly
It is orange, 2 ~ 4h is heated to reflux at 100 DEG C and obtains light yellow clear stabilized chlorine titanium colloidal sol.
The TiO 2 sols of different pH can be obtained according to the difference of the pH of adjustment, as TiO 2 sol that pH is 1,
TiO 2 sol that the TiO 2 sol and pH that pH is 2 are 3 etc..
The above-mentioned TiO 2 sol drying being prepared can obtain titania powder A to treat as test reference examples
With.
（2）The preparation of modification infusorial earth
Such as Fig. 1, take market purchase diatomite to be mixed with moderate amount of sulfuric acid solution, under the action of magnetic agitation, react 3h at 100 DEG C,
Filter, acid solution recycling, is washed with deionized and is precipitated to filtrate to be neutral, oven for drying obtains sour modification infusorial earth；Acid is modified
Diatomite compares diatomite with cationicsurfactants according to quality：CTAB=1:2 mixing 1 ~ 3h of ultrasound, exclude diatomite
Duct bubble, is carried out at the same time diatomite surface charge and modifies to obtain modification infusorial earth.
Commercially available diatomaceous component and character are shown in Table 1
1 TL-301# diatomite indices of table
（3）The preparation of titanium dioxide/modification infusorial earth composite material
It is formulated as described in table 2 to prepare titanium dioxide/modification infusorial earth composite material：By modification infusorial earth and TiO 2 sol
Mixing, forms suspension, stirring or 1 ~ 2h of ultrasound, and up to titanium dioxide/modification infusorial earth composite material after drying, it prepares stream
Journey is as shown in Figure 2.
The composite material that 2 embodiment 1 ~ 5 of table and reference examples 1 ~ 3 provide
Reference examples 1 ~ 2
Reference examples 1 provide a kind of titanium dioxide/modification infusorial earth composite material, and wherein titanium dioxide is dried for TiO 2 sol
Titania powder A is can obtain, the modification infusorial earth that titania powder A and embodiment are prepared is by embodiment（3）In
Method composite material is prepared.
Reference examples 2 provide a kind of titanium dioxide/modification infusorial earth composite material, and wherein titanium dioxide selects in the market purchase
The modification infusorial earth that obtained titania powder B, titania powder B and embodiment are prepared is by embodiment（3）In
Method composite material is prepared.
Performance measurement：
（1）Modification infusorial earth performance test
As shown in figure 3, it is rear diatomaceous shape appearance figure before modified.As can be seen from the figure diatomite is after modified, surface
Impurity is reduced, and effective duct substantially increases, and is conducive to increase the adsorbance of organic dyestuff and pernicious gas.
（2）The performance test of composite material
The composite material provided embodiment and reference examples carries out SEM, XRD and degradation of methylene blue solution testing.
As shown in figure 4, be SEM test (scanning electron microscope) as a result, wherein 4-a be the present embodiment 1 offer titanium dioxide/
Modification infusorial earth composite material, it can be seen that due to the electrostatic attraction and support of modification infusorial earth, titanium deoxide catalyst is changing
Property diatomite surface distribution uniform, agglomeration is less, due to the natural loose porous characteristic of modification infusorial earth, titanium dioxide
The load capacity of titanium photodissociation catalyst is more；4-b is the SEM figures that pure catalyst fines A is obtained after colloidal sol is dried, can from figure
Go out most of pure titinium dioxide easily to reunite, about 10 μm of average grain diameter；4-c is the SEM figures for the composite material that reference examples 2 provide,
The composite material provided with embodiment 1 compares contrast, its load capacity is less；4-d is the SEM for the composite material that reference examples 1 provide
Figure, it is similar with the composite material that reference examples 2 provide, since no electrostatic interaction, load capacity are extremely few.
Fig. 5 is XRD powder diffraction analysis results.Titania powder A（a）With embodiment 1（b）The composite material of offer
XRD test results are compareed with PDF cards, find the mixed crystal that titania powder A is anatase and rutile；Embodiment 1 provides
The crystal form of composite material be still mixed crystal, illustrate that diatomaceous addition can't change the crystal form of colloidal sol TiO 2 particles, because
This can retain the photo-catalysis capability of colloidal sol while playing electrostatic attraction and acting on.
By photochemical catalyst（Material containing titanium dioxide）Coating is dried on a glass, is immersed in methylene blue solution and is divided
Solution.Degradation of organic dyes, blue methylene blue can be become colorless molten by photochemical catalyst due to the redox of its own
Liquid.
Fig. 6 and Fig. 7 is the design sketch of degradation of methylene blue solution.In Fig. 6, a is titania powder A（10mg）Degraded is sub-
The design sketch of methyl blue solution, b are titania powder A（16mg）The design sketch of degradation of methylene blue solution, c are titanium dioxide
Powder B（10mg）The design sketch of degradation of methylene blue solution.As can be seen from the figure the catalytic efficiency of titania powder A is better than
The titania powder B of purchase, and can be complete by degradation of organic dyes after 4h；For titania powder A, contrast
The catalytic effect of different quality, incipient degradation is fast when quality is larger, but finally all tends towards stability, and degradation effect difference is not
It is more, illustrate that titania powder prepared by the present invention only needs to can reach good catalytic effect on a small quantity.
In Fig. 7, a is the design sketch for the composite degradation methylene blue solution that embodiment 1 provides, and b is modification infusorial earth
The design sketch of degradation of methylene blue solution, c are the design sketch for the composite degradation methylene blue solution that reference examples 2 provide.From
It can be seen from the figure that, modification infusorial earth can adsorb a certain amount of methylene blue；The composite wood that embodiment 1 and reference examples 2 provide
Expect to be not much different to the incipient degradation speed of methylene blue, the concentration of the rear methylene blues of degraded 6h or so tends towards stability, still
After the composite material processing that methylene blue is provided through embodiment 1, almost all is degraded, and photocatalysis performance is better than reference examples 2
Degradation effect.
Claims (10)
- A kind of 1. titanium dioxide/modification infusorial earth composite material, it is characterised in that the composite material by pH be 1 ~ 3 it is sharp The TiO 2 sol of titanium-type and modification infusorial earth mixing drying are prepared；The TiO 2 sol and modification infusorial earth Mass ratio is 5:9 ~ 11, the modification infusorial earth is the diatomite through acid and cationic surfactant modification successively.
- 2. titanium dioxide/modification infusorial earth composite material according to claim 1, it is characterised in that the titanium dioxide is molten The mass ratio of glue and modification infusorial earth is 5:10.
- 3. titanium dioxide/modification infusorial earth composite material according to claim 1, it is characterised in that the titanium dioxide is molten The pH of glue is 3.
- 4. titanium dioxide/modification infusorial earth composite material according to claim 1, it is characterised in that the titanium dioxide is molten Glue is obtained by following preparation method：Metatitanic acid hydrogenperoxide steam generator is disperseed, after being 1 ~ 3 with inorganic acid for adjusting pH, 80 ~ 100 DEG C are heated to reflux 2 ~ 4h, obtain light yellow clear stabilized chlorine titanium colloidal sol, the Ti and H2O2Molar ratio be 1:8~20.
- 5. titanium dioxide/modification infusorial earth composite material according to claim 4, it is characterised in that the Ti and H2O2Rub You are than being 1:15.
- 6. titanium dioxide/modification infusorial earth composite material according to claim 1, it is characterised in that the modification infusorial earth It is prepared via a method which to obtain：S1：It is 1 in mass ratio by diatomite and acid solution:5 ~ 10 mixing, stir 4 ~ 5h, filtering, washing, drying at 90 ~ 100 DEG C Obtain acidleach diatomite；S2：The acidleach diatomite and cationic surfactant are pressed 1 ~ 2:1 mass ratio mixing, adds water to surpass into after suspension Sound is up to the modification infusorial earth.
- 7. titanium dioxide/modification infusorial earth composite material according to claim 6, it is characterised in that the acid solution for hydrochloric acid, One or more in sulfuric acid or nitric acid；The cationic surfactant is alkyl quaternary ammonium salts or one kind or several in amine salt Kind.
- 8. the preparation method of any titanium dioxide/modification infusorial earth composite material of claim 1 ~ 7, it is characterised in that institute It is as follows to state method：Modification infusorial earth is mixed with TiO 2 sol, forms suspension, stirring or 1 ~ 2h of ultrasound, after drying i.e. Obtain titanium dioxide/modification infusorial earth composite material.
- 9. a kind of titanium dioxide/modification infusorial earth photocatalysis film, it is characterised in that the film includes claim 1 ~ 7 times One titanium dioxide/modification infusorial earth composite material and surfactant, the mass fraction of composite material is in the film 0.5~5%。
- 10. any titanium dioxide of claim 1 ~ 7/application of the modification infusorial earth composite material in building coating is prepared.
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