CN107497433A - A kind of composite photocatalyst diatom plate and preparation method thereof - Google Patents
A kind of composite photocatalyst diatom plate and preparation method thereof Download PDFInfo
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- CN107497433A CN107497433A CN201710731741.0A CN201710731741A CN107497433A CN 107497433 A CN107497433 A CN 107497433A CN 201710731741 A CN201710731741 A CN 201710731741A CN 107497433 A CN107497433 A CN 107497433A
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- tio
- diatom plate
- mixed liquor
- preparation
- composite photocatalyst
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 108010025899 gelatin film Proteins 0.000 claims abstract description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 46
- 239000010936 titanium Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 27
- 229910052719 titanium Inorganic materials 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001879 gelation Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- 241000195493 Cryptophyta Species 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000012163 sequencing technique Methods 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 239000003344 environmental pollutant Substances 0.000 abstract description 11
- 231100000719 pollutant Toxicity 0.000 abstract description 11
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 52
- 235000019441 ethanol Nutrition 0.000 description 29
- 239000002105 nanoparticle Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000007146 photocatalysis Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 238000013019 agitation Methods 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000002572 peristaltic effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000033228 biological regulation Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910003978 SiClx Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000009514 concussion Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical class O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000002604 ultrasonography Methods 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Abstract
The invention provides a kind of composite photocatalyst diatom plate and preparation method thereof, the method comprises the steps of firstly, preparing Fe TiO2Gel, then by diatom plate in Fe TiO2Impregnated and lifted in gel, obtain being coated with Fe TiO2The diatom plate of gel film, the Fe TiO for making to be coated on diatom plate surface finally by drying and calcination2Gel is dehydrated crystallization, obtains composite photocatalyst diatom plate.Preparation method provided by the invention is simple to operate, and production cost is low, it is easy to accomplish industrialization；And absorption capturing ability of the obtained composite photocatalyst diatom plate to pollutant is strong, photocatalytic activity is good, and the photochemical catalyst of diatom plate surface is difficult for drop-off.
Description
Technical field
The present invention relates to light-catalysed technical field, more particularly to a kind of composite photocatalyst diatom plate and preparation method thereof.
Background technology
Photocatalysis technology can utilize luminous energy degraded and mineralized water and the various pollutants in air, be a kind of preferable environment
Pollutant abatement technology.With nano-TiO2For the conductor photocatalysis material of representative, the light induced electron-sky generated under illumination condition
Cave is to that with Strong oxdiative reproducibility, can occur redox reaction with the material of its adsorption, can drop organic pollution
Solve as CO2, the inorganic molecules such as water, heavy metal ion can be reduced to the low price ion of nonhazardous, can also degrade automobile
Tail gas, disinfection etc., good application prospect is shown in numerous areas.
But nano level photocatalytic particle is easily agglomerated into second particle in actual applications, make its photocatalytic activity
Reduce.In order to solve this problem, it has been proposed that nano-photo catalytic particle immobilization technology, prior art generally with glass plate,
Ceramics, metal, ceramic tile etc. are base material, and nanoscale catalysis material is supported on base material by film or sputtering technology, are prepared
Into composite board.But nano-photocatalyst particle easily comes off in these current composite boards, causes photo-catalysis capability to become
Difference.
The content of the invention
In view of this, present invention aims at provide a kind of composite photocatalyst diatom plate and preparation method thereof.The present invention carries
The adhesion of nano-photocatalyst material and base material in the composite photocatalyst diatom plate of confession is strong, and difficult for drop-off, photo-catalysis capability is strong.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of preparation method of composite photocatalyst diatom plate, comprise the following steps：
(1) alcohol, delayer and soluble titanium source are mixed, obtains the first mixed liquor；
(2) alcohol, water and soluble source of iron are mixed, the pH value of mixed liquor is adjusted to 1~3 with acid, obtains the second mixing
Liquid；
(3) second mixed liquor is added and sol gel reaction is carried out in first mixed liquor, obtain Fe-
TiO2Gel；
(4) by diatom plate in the Fe-TiO2Impregnated and lifted in gel, obtain being coated with Fe-TiO2Gel film
Diatom plate；
(5) it is coated with Fe-TiO by described2The diatom plate of gel film is dried and calcined successively, obtains complex light and urges
SiClx algae plate；
The limitation of the step (1) and step (2) without time sequencing.
Preferably, the alcohol in the step (1) is one or more of in ethanol, ethylene glycol, glycerine and isopropanol
Mixture；
The delayer is one or more of mixtures in acetic acid, citric acid, glycine and acetylacetone,2,4-pentanedione；
The titanium source is butyl titanate and/or titanium tetraisopropylate.
Preferably, the volume ratio of alcohol, delayer and titanium source is 20 in the step (1):3~10:5~15.
Preferably, the alcohol in the step (2) is one or more of in ethanol, ethylene glycol, glycerine and isopropanol
Mixture；The volume ratio of the alcohol and water is 1:1~3；
The source of iron is ferric nitrate and/or iron chloride.
Preferably, in the step (3) amount of the first mixed liquor and the second mixed liquor with iron and the gauge of the material of titanium；
In second mixed liquor amount of the material of ferro element be the first mixed liquor in titanium elements material amount 0.5~
10%.
Preferably, the sol gel reaction includes solation reaction and the gelation reaction carried out successively；
The time of the solation reaction is 0.5~3h；
The time of the gelation reaction is 6~24h.
Preferably, the dipping and the number of lifting are 5~20 times；
The time of the single impregnation is 2~10min；
The speed of the lifting is 5~20cm/min.
Preferably, the temperature of the drying is 100~110 DEG C；The time of the drying is 0.5~3h；
The temperature of the calcining is 350~850 DEG C；The time of the calcining is 1~5h.
The invention provides composite photocatalyst diatom plate prepared by preparation method described in such scheme, including diatom plate and bag
Overlay on the Fe-TiO of the diatom plate surface2Film.
Preferably, the Fe-TiO2The thickness of film is 300~1500nm.
The invention provides a kind of preparation method of composite photocatalyst diatom plate, Fe-TiO is prepared first2Gel, then by silicon
Algae plate is in Fe-TiO2Gel is impregnated and lifted, and obtains being coated with Fe-TiO2The diatom plate of gel film, finally by drying
Make the Fe-TiO that is coated on diatom plate surface with calcining2Gel is dehydrated crystallization, obtains composite photocatalyst diatom plate.The present invention uses
Sol-gel, dip-coating method prepare composite photocatalyst diatom plate, make Fe-TiO2Nano particle passes through Si-O-Ti keys and diatom
Plate is combined, and the two adhesion is strong, Fe-TiO2Nano particle is difficult for drop-off, and the loose structure of diatom plate will not be destroyed, and
And the preparation method of the present invention is simple to operate, production cost is low, it is easy to accomplish industrialization.
Present invention also offers composite photocatalyst diatom plate prepared by above-mentioned preparation method, including diatom plate and it is coated on silicon
The Fe-TiO of algae plate surface2Film.The present invention is using diatom plate as base material, using diatom plate is porous and the performance of large specific surface area
Make photochemical catalyst Fe-TiO2Film is strong to be attached on diatom plate matrix, and diatom plate is to being supported on the photocatalysis on surface
The reunion of agent particle have it is obvious suppress and inhibition, photochemical catalyst can be evenly dispersed in diatom plate surface, and can be with
The recombination rate in light induced electron and hole is reduced, forms the photocatalyst film that can play high light catalytic activity；Photochemical catalyst is thin
The main component that photocatalysis is played in film is Fe-TiO2Nano-particle, the present invention use Fe3+Titanium dioxide is doped
It is modified, by TiO2Photoresponse scope expand to visible region, improve the visible light photocatalysis active of photochemical catalyst.The present invention
Absorption capturing ability of the composite photocatalyst diatom plate of offer to pollutant is strong, and photocatalytic activity is good.Embodiment result shows, light
After 12h, the degradation rate of composite photocatalyst diatom plate PARA FORMALDEHYDE PRILLS(91,95) provided by the invention can reach 94.32%.
Brief description of the drawings
Fig. 1 is the SEM figures of common diatom plate and the gained composite photocatalyst diatom plate of the embodiment of the present invention 1；
Fig. 2 is the XPS collection of illustrative plates of the gained composite photocatalyst diatom plate of the embodiment of the present invention 1.
Embodiment
The invention provides a kind of preparation method of composite photocatalyst diatom plate, comprise the following steps：
(1) alcohol, delayer and soluble titanium source are mixed, obtains the first mixed liquor；
(2) alcohol, water and soluble source of iron are mixed, the pH value of mixed liquor is adjusted to 1~3 with acid, obtains the second mixing
Liquid；
(3) second mixed liquor is added and sol gel reaction is carried out in first mixed liquor, obtain Fe-
TiO2Gel；
(4) by diatom plate in the Fe-TiO2Impregnated and lifted in gel, obtain being coated with Fe-TiO2Gel film
Diatom plate；
(5) it is coated with Fe-TiO by described2The diatom plate of gel film is dried and calcined successively, obtains complex light and urges
SiClx algae plate；
The limitation of the step (1) and step (2) without time sequencing.
The present invention mixes alcohol, delayer and soluble titanium source, obtains the first mixed liquor.In the present invention, the alcohol is excellent
Elect one or more of mixtures in ethanol, ethylene glycol, glycerine and isopropanol, more preferably ethanol as；The delayer
One or more of mixtures preferably in acetic acid, citric acid, glycine and acetylacetone,2,4-pentanedione, more preferably acetic acid；The titanium
Source is preferably butyl titanate and/or titanium tetraisopropylate.In the present invention, the volume of the alcohol, delayer and soluble titanium source
Than being preferably 20:3~10:5~15, more preferably 20:4~8:8~12.In the present invention, delayer can play two coordinations
The effect of body, and macromolecule polyalcohol of the titanium source reaction generation containing two ligand groups, the macromolecule polyalcohol is in follow-up water
The space net structure of three-dimensional can be formed in solution preocess, so as to play a part of delaying titanium source to hydrolyze, avoids titanium source follow-up
The step of in hydrolyze it is too fast.
The present invention preferably first mixes alcohol and delayer, obtains the alcoholic solution of delayer, then titanium source is added drop-wise into described prolong
In the alcoholic solution of slow agent, the first mixed liquor is obtained.In the present invention, the rate of addition of the titanium source is preferably 2~4mL/min,
More preferably 3mL/min；The present invention preferably carries out alcohol and the mixing of delayer and the dropwise addition of titanium source under agitation；This hair
It is bright there is no particular/special requirement to the rotating speed of stirring and time, can be well mixed by system.
The present invention mixes alcohol, water and soluble source of iron, and the pH value of mixed liquor is adjusted into 1~3 with acid, and it is mixed to obtain second
Close liquid.In the present invention, the alcohol is preferably one or more of mixtures in ethanol, ethylene glycol, glycerine and isopropanol,
More preferably ethanol；The source of iron is preferably soluble ferric iron salt, more preferably ferric nitrate and/or iron chloride；The present invention is to described
Water does not have particular/special requirement, specific such as deionized water using water well known to those skilled in the art.
In the present invention, the volume ratio of alcohol and water is preferably 1 in second mixed liquor:1~3, more preferably 1:1.5~
2.5.In the present invention, the source of iron adds preferably in the form of the source of iron aqueous solution；The concentration of the source of iron aqueous solution is preferably
0.05~0.2mol/L, more preferably 0.1mol/L；When the source of iron is added with source of iron solution, the amount of the material of the source of iron with
The gauge of source of iron solute；Water in the source of iron aqueous solution is not included within the dosage of the water.
The present invention preferably first mixes alcohol and water, obtains the mixed liquor of alcohol and water, then by the source of iron aqueous solution be added drop-wise to alcohol and
In the mixed liquor of water, mixed liquor is obtained.In the present invention, the rate of addition of the titanium source aqueous solution is preferably 2~4mL/min,
More preferably 3mL/min；The present invention preferably carries out the mixing of alcohol and water and the dropwise addition of the source of iron aqueous solution under agitation；This
Invention does not have particular/special requirement to the rotating speed of stirring and time, can be well mixed by system.
After obtaining mixed liquor, the present invention is adjusted the pH value of mixed liquor to 1~3 using acid, obtains the second mixed liquor.At this
In invention, the acid is preferably one or more of mixtures in hydrochloric acid, nitric acid and sulfuric acid, more preferably hydrochloric acid；The salt
Acid is preferably the concentrated hydrochloric acid that mass fraction is 36~38%；The nitric acid is preferably the concentrated nitric acid that mass fraction is 65%；It is described
The mass fraction of sulfuric acid is preferably 60~90%, and more preferably 70~80%.The present invention adjusts the pH of mixed liquor to 1~3, more
Preferably 2；The present invention controls the hydrolysis rate of titanium source in subsequent step by controlling the pH value of the second mixed liquor, avoids titanium source
Hydrolysis rate is too fast.
After obtaining the first mixed liquor and the second mixed liquor, second mixed liquor is added first mixed liquor by the present invention
Middle progress sol gel reaction, obtains Fe-TiO2Gel.In the present invention, the sol gel reaction is included successively
The solation reaction of progress and gelation reaction；The time of the solation reaction is preferably 0.5~3h, more preferably 1~2h；
The time of the gelation reaction is preferably 6~24h, more preferably 10~20h；The solation reaction and gelation reaction are excellent
It is selected in and carries out at room temperature, without carries out extra heating or cooling.Second mixed liquor is preferably added drop-wise to the first mixing by the present invention
In liquid, the rate of addition of second mixed liquor is preferably 1~3mL/min, more preferably 2mL/min；The solation of the present invention
Reaction time since the second mixed liquor be added dropwise after calculate.In the present invention, first mixed liquor and the second mixed liquor
Amount preferably with iron and the gauge of the material of titanium, specifically, in the source of iron material of ferro element amount be titanium source in titanium elements
The 0.5~10% of the amount of material, more preferably 2~5%.The present invention preferably carries out solation reaction under agitation；This hair
The rotating speed of bright stirring and time do not have particular/special requirement, can be well mixed by system.
In the present invention, big point containing two ligand groups of titanium source and delayer reaction generation in the first mixed liquor be present
Sub- polymer, after the second mixed liquor is added in the second mixed liquor, the macromolecule polyalcohol meets water and hydrolysis condensation reaction occurs, and produces
Titanium dioxide hydrates, and Fe present in the second mixed liquor3+Into TiO2Lattice, part substitute Ti4+Lattice position, from
And modification is doped to titanium dioxide, obtain Fe-TiO2Hydrate, Fe-TiO2Hydrate is dispersed in the liquid phase, is formed
Colloidal sol.The present invention uses Fe3+Modification is doped to titanium dioxide, widens TiO2Photoresponse scope, improve photochemical catalyst
Visible light photocatalysis active.
In the present invention, the gelation reaction is specially and is aged the colloidal sol that solation reacts to obtain at room temperature, shape
Into Fe-TiO2Gel.In the present invention, the Fe-TiO in ageing process in colloidal sol2Hydrate is further assembled, and forms Fe-TiO2
Gel.
Obtain Fe-TiO2After gel, the present invention is by diatom plate in the Fe-TiO2Impregnated and lifted successively in gel,
Obtain being coated with Fe-TiO2The diatom plate of gel film.In the present invention, the diatom plate is given birth to by primary raw material of diatomite
A kind of light porous calcium silicate board of production, compared with common calcium silicate board with microporous, have that density is small, hole is flourishing, moderate strength etc.
Feature, and with good absorption, humidity conditioning function, insulation, eliminate the unusual smell, the function such as the pollutant such as formaldehyde adsorption；The present invention
There is no particular/special requirement to the source of the diatom plate, using the diatom plate in source known to those skilled in the art, specifically
Such as commercially available diatom plate.
In the present invention, the dipping and the number of lifting are preferably 5~20 times, more preferably 8~15 times；The single
The time of dipping is preferably 2~10min, more preferably 3~8min；The speed of the lifting is preferably 5~20cm/min, more excellent
Elect 10~15cm/min as.In a particular embodiment of the present invention, preferably by diatom plate vertical immersion in Fe-TiO2In gel,
After impregnating 2~10min, diatom plate is lifted vertically upward, the lifting completely of diatom plate is come out, treats the gel of diatom plate surface certainly
After so drying, the process of dipping-lifting is repeated, finally gives and is coated with Fe-TiO2The diatom plate of gel film；In the present invention
In, the time of the natural drying is preferably 3~10min, more preferably 5min；The present invention is to the equipment that lifting uses without spy
It is different to require, using lifting equipment well known to those skilled in the art, in a particular embodiment of the present invention, preferably using small
Type at the uniform velocity elevator is lifted.The present invention is secondary by controlling dip time, pull rate and the dipping-lifting of dipping-lifting
Numerical control Fe-TiO2The thickness of gel film.
In the present invention, during lifting, the Fe-TiO on dip direction2Gel film can form certain thickness ladder
Degree, about 1nm/ μm, to ensure the smooth of diatom plate surface, the present invention, which preferably often lifts, once turns clockwise diatom plate
90 °, then carry out dipping-lifting next time.
Obtain being coated with Fe-TiO2After the diatom plate of gel film, the present invention is coated with Fe-TiO by described2Gel film
Diatom plate be dried and calcine successively, obtain composite photocatalyst diatom plate.In the present invention, the drying is preferably to dry
Dry, the temperature of the drying is preferably 100~110 DEG C, more preferably 105 DEG C；The time of the drying is preferably 0.5~3h,
More preferably 1~2h.The present invention does not have particular/special requirement to drying equipment, uses drying equipment well known to those skilled in the art
, it is specific such as baking oven.The present invention removes the moisture adsorbed in gel film by drying.
In the present invention, the temperature of the calcining is preferably 350~850 DEG C, more preferably 400~800 DEG C, is most preferably
500~600 DEG C；The time of the calcining is preferably 1~5h, more preferably 2~4h, most preferably 3h.The present invention is preferably dry
After the completion of dry, drying temperature is directly warming up to calcining heat and calcined；The speed of the heating is preferably 3~10 DEG C/
Min, more preferably 5~8 DEG C/min.The present invention makes the Fe-TiO in gel film by calcining2Hydrate is dehydrated crystallization, is formed
Fe-TiO2Film.
The present invention utilizes the means such as Best-Effort request, drying and calcination by Fe-TiO2The uniform overlay film of photochemical catalyst is to diatom plate
Surface, avoid Fe-TiO2Agglomeration, and remain the loose structure of diatom plate surface.
The invention provides composite photocatalyst diatom plate prepared by preparation method described in such scheme, including diatom plate and bag
Overlay on the Fe-TiO of the diatom plate surface2Film.In the present invention, the Fe-TiO2Film is by Fe-TiO2Nano particle group
Into the Fe-TiO2The particle diameter of nano particle is preferably 10~20nm, more preferably 11~15nm；The Fe-TiO2Film
Thickness is preferably 300~1500nm, more preferably 500~1200nm, most preferably 800~1000nm.
Composite photocatalyst diatom plate provided by the invention urges the efficient absorption capture function and light of pollutant diatom plate
The photocatalytic degradation function of agent is combined into one, and the absorption capturing ability to pollutant is strong, and photocatalytic activity is good, and Fe-TiO2
Nano particle is combined by Si-O-Ti keys and diatom plate, and the two adhesion is strong, Fe-TiO2Nano particle is difficult for drop-off, in dirt
Dye thing process field has broad application prospects.
Composite photocatalyst diatom plate provided by the invention and preparation method thereof is carried out specifically with reference to embodiment
It is bright, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) at room temperature, 100mL absolute ethyl alcohol is mixed with 10mL acetic acid, after magnetic agitation 15min, passes through wriggling
5mL butyl titanate (TBOT) is added dropwise in pump, obtains the first mixed solution；
(2) at room temperature, 60mL deionized waters are mixed with 30mL absolute ethyl alcohols, after magnetic agitation 15min, with step (1)
The middle mole for adding butyl titanate (TBOT) is foundation, according to the ratio that n (Fe)/n (Ti) is 0.5%, passes through peristaltic pump
7.5mL ferric chloride solutions (0.01mol/L) are added, is afterwards 2 with concentrated hydrochloric acid regulation solution ph, obtains the second mixed liquor；
(3) the second mixed liquor is slowly added in the first mixed liquor by peristaltic pump, stirring is anti-at room temperature after being added dropwise to complete
1h is answered to form Fe-TiO2Colloidal sol, gelation reaction is then carried out at ambient temperature, Fe-TiO is formed after reacting 18h2Gel；
(4) by diatom plate (10cm × 10cm × 50mm, purchased from the new Mahayana Environmental Protection Technology Co., Ltd in Jiangsu) vertical immersion
To Fe-TiO2In gel, 2min is impregnated, slowly lifting diatom plate, pull rate 5cm/min, repeated impregnations carry vertically upward
Draw 5 times (often dipping-lifting once turns clockwise diatom plate 90 °), obtain being covered with Fe-TiO2The diatom plate of gel film,
Film thickness is 300nm.
(5) and then it is covered with Fe-TiO2The diatom plate of gel film, which is placed in 105 DEG C of baking oven, dries 1h, then with 5 DEG C/
Min heating rate is warming up to 450 DEG C, and 2h is calcined under the conditions of 450 DEG C, obtains with photo-catalysis function Fe-TiO2Coating
Compound diatom plate, as composite photocatalyst diatom plate (Fe-TiO2/ diatom plate).
The composite photocatalyst diatom plate that common diatom plate and the present embodiment obtain is observed using ESEM, gained
SEM figures are as shown in Figure 1；(a) is that the SEM of common diatom plate schemes in Fig. 1, and scale is 100 μm；(b) the SEM figures of common diatom plate,
Scale is 10 μm；(c) scheme for the SEM of composite photocatalyst diatom plate, scale is 2 μm；(d) it is the SEM of composite photocatalyst diatom plate
Figure, scale are 1 μm.According to Fig. 1 as can be seen that composite photocatalyst diatom plate surface has particulate material, as photochemical catalyst is received
Rice Fe-TiO2Particle, and Fe-TiO2It is evengranular to be dispersed in compound diatom plate surface, without agglomeration.
To pure Fe-TiO2XPS atlas analysis, gained XPS figures are carried out with the present embodiment gained composite photocatalyst diatom plate
Spectrum is as shown in Figure 2；According to Fig. 2 as can be seen that Ti members are known as two class combination energy in composite photocatalyst diatom plate：Ti2p3/2With reference to energy
In 459.1eV or so main peak and Ti2p1/2With reference to can be at 464.8eV or so attached peak, thus may determine that complex light is urged
Ti elements are mainly with the oxidation state (Ti of positive tetravalence in SiClx algae plate4+) form presence.With pure Fe-TiO2Middle Ti2p3/2With reference to energy
(459.1eV) is compared, Ti2p in composite photocatalyst diatom plate3/2It increased with reference to energy (459.3eV), this is due to TiO2With
The silicone hydroxyl of diatom plate surface interacts and causes the electron density around Ti atoms to change, because compared with Ti, Si
Atom has bigger electronegativity, it is possible to determines Fe-TiO2It is to pass through Si-O-Ti between nano particle and matrix diatom plate
What key was combined closely, therefore there is stronger adhesion, Fe-TiO2Nano particle is difficult for drop-off.
Embodiment 2
(1) at room temperature, 100mL absolute ethyl alcohol is mixed with 15mL acetic acid, after magnetic agitation 15min, passes through wriggling
7mL butyl titanate (TBOT) is added dropwise in pump, obtains the first mixed solution；
(2) at room temperature, 70mL deionized waters are mixed with 35mL absolute ethyl alcohols, after magnetic agitation 15min, with step (1)
The middle mole for adding butyl titanate (TBOT) is foundation, according to the ratio that n (Fe)/n (Ti) is 1.5%, passes through peristaltic pump
31.5mL ferric chloride solutions (0.01mol/L) are added, is afterwards 2 with concentrated hydrochloric acid regulation solution ph, obtains the second mixed liquor；
(3) the second mixed liquor is slowly added in the first mixed liquor by peristaltic pump, stirring is anti-at room temperature after being added dropwise to complete
1h is answered to form Fe-TiO2Colloidal sol, gelation reaction is then carried out at ambient temperature, Fe-TiO is formed after reacting 18h2Gel；
(4) by diatom plate (10cm × 10cm × 50mm, purchased from the new Mahayana Environmental Protection Technology Co., Ltd in Jiangsu) vertical immersion
To Fe-TiO2In gel, 4min is impregnated, slowly lifting diatom plate, pull rate 8cm/min, repeated impregnations carry vertically upward
Draw 7 times (often dipping-lifting once turns clockwise diatom plate 90 °), obtain being covered with Fe-TiO2The diatom plate of gel film,
Film thickness is 550nm.
(5) and then it is covered with Fe-TiO2The diatom plate of gel film, which is placed in 105 DEG C of baking oven, dries 1h, then with 5 DEG C/
Min heating rate is warming up to 550 DEG C, and 2h is calcined under the conditions of 550 DEG C, obtains with photo-catalysis function Fe-TiO2Coating
Compound diatom plate, as composite photocatalyst diatom plate.
Gained composite photocatalyst diatom plate is observed using ESEM, acquired results and embodiment 1 are similar.
XPS atlas analysis is carried out to gained composite photocatalyst diatom plate, acquired results and embodiment 1 are similar.
Embodiment 3
(1) at room temperature, 100mL absolute ethyl alcohol is mixed with 12mL glycine, after magnetic agitation 15min, by compacted
5mL titanium tetraisopropylate is added dropwise in dynamic pump, obtains the first mixed solution；
(2) at room temperature, 65mL deionized waters are mixed with 32mL absolute ethyl alcohols, after magnetic agitation 15min, with step (1)
The middle mole for adding titanium tetraisopropylate is foundation, according to the ratio that n (iron chloride)/n (titanium tetraisopropylate) is 1%, by compacted
Dynamic pump adds 17.5mL ferric chloride solutions (0.01mol/L), is afterwards 2 with concentrated hydrochloric acid regulation solution ph, obtains the second mixing
Liquid；
(3) the second mixed liquor is slowly added in the first mixed liquor by peristaltic pump, stirring is anti-at room temperature after being added dropwise to complete
1h is answered to form Fe-TiO2Colloidal sol, gelation reaction is then carried out at ambient temperature, Fe-TiO is formed after reacting 18h2Gel；
(4) by diatom plate (10cm × 10cm × 50mm, purchased from the new Mahayana Environmental Protection Technology Co., Ltd in Jiangsu) vertical immersion
To Fe-TiO2In gel, 3min is impregnated, slowly lifting diatom plate, pull rate 6cm/min, repeated impregnations carry vertically upward
Draw 6 times (often dipping-lifting once turns clockwise diatom plate 90 °), obtain being covered with Fe-TiO2The diatom plate of gel film,
Film thickness is 480nm.
(5) and then it is covered with Fe-TiO2The diatom plate of gel film, which is placed in 105 DEG C of baking oven, dries 1h, then with 5 DEG C/
Min heating rate is warming up to 650 DEG C, and 1.5h is calcined under the conditions of 650 DEG C, obtains with photo-catalysis function Fe-TiO2Coating
Compound diatom plate, as composite photocatalyst diatom plate.
Gained composite photocatalyst diatom plate is observed using ESEM, acquired results and embodiment 1 are similar.
XPS atlas analysis is carried out to gained composite photocatalyst diatom plate, acquired results and embodiment 1 are similar.
Embodiment 4
(1) at room temperature, 100mL ethylene glycol is mixed with 18mL citric acid, after magnetic agitation 15min, passes through wriggling
8mL titanium tetraisopropylate is added dropwise in pump, obtains the first mixed solution；
(2) at room temperature, 80mL deionized waters are mixed with 40mL ethylene glycol, after magnetic agitation 15min, with step (1)
The mole for adding titanium tetraisopropylate is foundation, and according to the ratio that n (Fe)/n (Ti) is 1%, 84mL nitre is added by peristaltic pump
Sour ferrous solution (0.01mol/L), it is afterwards 2 with concentrated hydrochloric acid regulation solution ph, obtains the second mixed liquor；
(3) the second mixed liquor is slowly added in the first mixed liquor by peristaltic pump, stirring is anti-at room temperature after being added dropwise to complete
0.5h is answered to form Fe-TiO2Colloidal sol, gelation reaction is then carried out at ambient temperature, Fe-TiO is formed after reacting 10h2Gel；
(4) by diatom plate (10cm × 10cm × 50mm, purchased from the new Mahayana Environmental Protection Technology Co., Ltd in Jiangsu) vertical immersion
To Fe-TiO2In gel, 4min is impregnated, slowly lifting diatom plate, pull rate 10cm/min, repeated impregnations carry vertically upward
Draw 9 times (often dipping-lifting once turns clockwise diatom plate 90 °), obtain being covered with Fe-TiO2The diatom plate of gel film,
Film thickness is 800nm.
(5) and then it is covered with Fe-TiO2The diatom plate of gel film, which is placed in 105 DEG C of baking oven, dries 1h, then with 5 DEG C/
Min heating rate is warming up to 450 DEG C, and 3h is calcined under the conditions of 450 DEG C, obtains with photo-catalysis function Fe-TiO2Coating
Compound diatom plate, as composite photocatalyst diatom plate.
Gained composite photocatalyst diatom plate is observed using ESEM, acquired results and embodiment 1 are similar.
XPS atlas analysis is carried out to gained composite photocatalyst diatom plate, acquired results and embodiment 1 are similar.
Embodiment 5
Formaldehyde is common indoor pollutant,《The sanitary standard of formaldehyde in GB/T 16127-1995 indoor airs》Regulation
Indoor formaldehyde maximum permissible concentration be 0.08mg/m3.The composite photocatalyst diatom plate obtained to embodiment 1~4 carries out light and urged
Change degradation of formaldehyde performance test, step is as follows：
In the present embodiment, using the PFD-5060 type photochemical reaction instrument (250L) of Hunan Hua Si Instrument Ltd. production
Carry out simulating living room environment, and made composite photocatalyst diatom plate photocatalytic degradation gaseous formaldehyde performance is tested, for simulation
Indoor natural light and lighting source are occupied, visible light source used in this test experiments is 5, and the T5 straight tubes that every power is 14W are glimmering
Light lamp tube.
Composite photocatalyst diatom plate is put into experimental cabin, regulation lifting platform make it that the distance of sample surfaces and lamp is 20cm,
Closed test, the formalin for being then 0.016mg/ μ L with the μ L concentration of micro syringe accurate measuring 30, by instrument certainly
The sampling device of band, while by auxiliary heating and air-breather formaldehyde is entered in gaseous form and be uniformly dispersed in experiment
In cabin.Then turn on fluorescent tube, fan (20W), carry out light-catalyzed reaction, after illumination 12h, 10L is sampled with constant current air sampler
(flow velocity 1L/min, gas production time 10min).Finally according to national standard《GB/T 16129-1995 residential areas Formaldehyde in Atmosphere is defended
Raw test stone method-AAS》Concentration of formaldehyde is tested, the degradation rate calculation formula of formaldehyde is shown in formula I：
The Formulas I of η=(A0-A12)/A0 × 100%；
In Formulas I：η is degradation rate, and A0 is the concentration of formaldehyde value of blank (n.s) experimental cabin at the end of testing, and A12 is survey
The concentration of formaldehyde value in sampling test cabin is placed with the end of examination.
It is as shown in table 1 to test acquired results；
The Degradation Formaldehyde rate of the gained composite photocatalyst diatom plate of 1 embodiment of table 1~4
| Performance indications | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Degradation Formaldehyde rate (%) | 87.64 | 94.32 | 90.53 | 83.97 |
According to table 1 as can be seen that the degradation rate of present invention gained composite photocatalyst diatom plate PARA FORMALDEHYDE PRILLS(91,95) is high, after illumination 12h,
Degradation rate can be reached 94.32% by formaldehyde, illustrate that there is the composite photocatalyst diatom plate that the present invention obtains excellent light to urge
Change performance, it is good that the absorption to pollutant catches performance.
Embodiment 6
Circulation experiment, detection diatom plate surface Fe-TiO are carried out to composite photocatalyst diatom plate prepared by embodiment 1~42
The expulsion rate of nano particle, step are as follows：
The compound diatom plate carried out in embodiment 5 after a formaldehyde degradation by photocatalytic oxidation process is tested is placed in baking oven (105
DEG C) drying 20min so that the undegradable formaldehyde gas that absorption remains in compound diatom plate surface volatilizees away, Ran Houzhun
The quality of now compound diatom plate is really weighed, is designated as m1, water bath sonicator oscillator is then fixed in (with mechanical rocking equipment
And Vltrasonic device) in, ultrasound is again placed in baking oven (105 DEG C) with after machinery concussion 30min, claims its matter after drying 60min
Amount is designated as m2, the step 5 time of water bath sonicator concussion and drying is repeated, the quality of final compound diatom plate is weighed, is designated as m5, definition
Expulsion rate η '=(m5-m1)/m1, to characterize Fe-TiO2The complexity that comes off of nano particle, acquired results are shown in Table 2；
The expulsion rate of the gained composite photocatalyst diatom plate of 2 embodiment of table 1~4
| Performance indications | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Expulsion rate η ' (%) | 1.786 | 1.9603 | 1.6429 | 2.0859 |
According to table 2 as can be seen that the Fe-TiO of photocatalysis diatom plate surface of the present invention2The expulsion rate η ' of nano particle
Value is between 1%~3%, it was demonstrated that Fe-TiO2The adhesion of nano particle and diatom plate is strong, difficult for drop-off.
As seen from the above embodiment, photocatalysis diatom plate provided by the invention catches diatom plate to the efficient absorption of pollutant
The photocatalytic degradation function of catching function and photochemical catalyst is combined into one, and the absorption capturing ability to pollutant is strong, photocatalytic activity
It is good, and Fe-TiO2Nano particle is combined by Si-O-Ti keys and diatom plate, and the two adhesion is strong, Fe-TiO2Nano particle is not
It is easy to fall off；And the preparation method of composite photocatalyst diatom plate provided by the invention is simple to operate, production cost is low, it is easy to accomplish work
Industry.
As seen from the above embodiment, it is only the preferred embodiment of the present invention that the present invention is described above, it is noted that for
For those skilled in the art, under the premise without departing from the principles of the invention, can also make it is some improvement and
Retouching, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of composite photocatalyst diatom plate, comprises the following steps：
(1) alcohol, delayer and soluble titanium source are mixed, obtains the first mixed liquor；
(2) alcohol, water and soluble source of iron are mixed, the pH value of mixed liquor is adjusted to 1~3 with acid, obtains the second mixed liquor；
(3) second mixed liquor is added and sol gel reaction is carried out in first mixed liquor, obtain Fe-TiO2It is solidifying
Glue；
(4) by diatom plate in the Fe-TiO2Impregnated and lifted in gel, obtain being coated with Fe-TiO2The silicon of gel film
Algae plate；
(5) it is coated with Fe-TiO by described2The diatom plate of gel film is dried and calcined successively, obtains composite photocatalyst silicon
Algae plate；
The limitation of the step (1) and step (2) without time sequencing.
2. preparation method according to claim 1, it is characterised in that alcohol in the step (1) is ethanol, ethylene glycol,
One or more of mixtures in glycerine and isopropanol；
The delayer is one or more of mixtures in acetic acid, citric acid, glycine and acetylacetone,2,4-pentanedione；
The titanium source is butyl titanate and/or titanium tetraisopropylate.
3. preparation method according to claim 1 or 2, it is characterised in that alcohol, delayer and titanium source in the step (1)
Volume ratio be 20:3~10:5~15.
4. preparation method according to claim 1, it is characterised in that alcohol in the step (2) is ethanol, ethylene glycol,
One or more of mixtures in glycerine and isopropanol；The volume ratio of the alcohol and water is 1:1~3；
The source of iron is soluble ferric iron salt.
5. the preparation method according to claim 1 or 4, it is characterised in that the first mixed liquor and second in the step (3)
The amount of mixed liquor is with iron and the gauge of the material of titanium；
The amount of the material of ferro element is 0.5~10% of the amount of titanium elements material in the first mixed liquor in second mixed liquor.
6. preparation method according to claim 1, it is characterised in that the sol gel reaction includes carrying out successively
Solation reaction and gelation reaction；
The time of the solation reaction is 0.5~3h；
The time of the gelation reaction is 6~24h.
7. preparation method according to claim 1, it is characterised in that the number for impregnating and lifting is 5~20 times；
The time of the single impregnation is 2~10min；
The speed of the lifting is 5~20cm/min.
8. preparation method according to claim 1, it is characterised in that the temperature of the drying is 100~110 DEG C；It is described
The dry time is 0.5~3h；
The temperature of the calcining is 350~850 DEG C；The time of the calcining is 1~5h.
9. composite photocatalyst diatom plate prepared by preparation method described in claim 1~8 any one, including diatom plate and cladding
In the Fe-TiO of the diatom plate surface2Film.
10. composite photocatalyst diatom plate according to claim 9, it is characterised in that the Fe-TiO2The thickness of film is
300~1500nm.
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| CN109781676A (en) * | 2017-11-10 | 2019-05-21 | 陕西秦云农产品检验检测有限公司 | A kind of aflatoxin biodegrade testing tool and the method for breeding using it |
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